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WO2008022996A1 - Lightening agents and/or colorants containing polyol esters - Google Patents

Lightening agents and/or colorants containing polyol esters Download PDF

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Publication number
WO2008022996A1
WO2008022996A1 PCT/EP2007/058643 EP2007058643W WO2008022996A1 WO 2008022996 A1 WO2008022996 A1 WO 2008022996A1 EP 2007058643 W EP2007058643 W EP 2007058643W WO 2008022996 A1 WO2008022996 A1 WO 2008022996A1
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WIPO (PCT)
Prior art keywords
amino
acid
group
formula
hydroxyethyl
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PCT/EP2007/058643
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German (de)
French (fr)
Inventor
Hartmut Manneck
Horst Höffkes
Denise Fuhr
Christiane Witte
Georg KNÜBEL
Kristin Pauli
Anja Reichert
Original Assignee
Henkel Ag & Co. Kgaa
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Publication of WO2008022996A1 publication Critical patent/WO2008022996A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8135—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers, e.g. vinyl esters (polyvinylacetate)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/08—Preparations for bleaching the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair

Definitions

  • the present invention relates to means for dyeing and / or whitening keratinic fibers, i. Agent for use on keratin fibers, in particular human hair, and their use.
  • Coupler and developer components are also referred to as oxidation dye precursors.
  • hair dyeing and / or lightening agents are mixed in solid or pasty form with dilute aqueous hydrogen peroxide solution. This mixture is then applied to the hair and rinsed again after a certain exposure time.
  • the duration of exposure to the hair to achieve a complete coloration or whitening is between about 30 and 40 minutes. It is obvious that there is a need among users of these hair dyes or bleaching agents to reduce this exposure time.
  • coloration and bleaching processes on keratinic fibers usually proceed at alkaline pH values, in particular between 9.0 and 10.5. These pH values are necessary to ensure an opening of the outer cuticle (cuticle) and to allow a penetration of the active species (dye precursors and / or hydrogen peroxide) into the hair.
  • the alkalizing agent used is usually ammonia, which however has the disadvantage of intense odor and possible irritation for the users.
  • aminomethylpropanol or monoethanolamine are used as alternative alkalizing agents to ammonia.
  • they are usually used in admixture with ammonia. But even here, the performance of the ammonia is impaired, especially with regard to the parameters gray covering, whitening performance and color result.
  • the object of the present invention was to provide lightening or bleaching agents which are increased in their whitening or bleaching performance and yet have an increased skin compatibility. Bleaching agents should also have a neutral color result and to reduce yellowing when bleaching and to reduce yellowing on keratinic fibers.
  • polyol esters can be incorporated with particular advantage into hair dyeing and whitening agents and lead to an increase in the performance of these agents.
  • the use of the polyol ester leads to the desired advantages, wherein in particular the combination with azoles brings these advantages to light.
  • German Offenlegungsschrift DE 23 44 990 A1 discloses mixtures for activating inorganic peroxygen bleaches containing at least one acetic acid ester of a monosaccharide or a disaccharide or a sugar alcohol or of erythritol in combination with at least one acetic acid ester of a polyhydric alcohol, in particular glycerol triacetate.
  • Compositions for treating keratinous fibers are not disclosed in this document.
  • WO00 / 77297 discloses the use of glycerol esters of mono-, di- or tri-formic acid, acetic acid or propionic acid as bleach activators in paper bleaching. Again, compositions for treating keratinic fibers are not disclosed.
  • German Utility Model DE 20 2006 002 355 U1 discloses cosmetic or dermatological preparations containing glycerol triacetate.
  • the agents disclosed in this document are preferably free of dyes and do not serve the color change keratinischer fibers.
  • the present invention relates to agents for dyeing and / or lightening keratin fibers, in particular human hair, containing-based on their weight-a) 0.5 to 15% by weight, preferably 1 to 12.5% by weight. -%, particularly preferably 2.5 to 10 wt .-% and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H 2 O 2 ), b) 0.001 to 15 wt .-% of at least one polyol ester of the formula (I) wherein
  • R 1 and R 2 independently of one another are -H or a straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 24 -alkyl or -alkenyl radical, preferably -H, -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
  • R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3 n is from 1 to 12, preferably from 2, 3, 4, 5, 6.
  • Keratin fibers mean furs, wool, feathers and in particular human hair. Although the compositions according to the invention are primarily suitable for dyeing and / or whitening keratin fibers, in principle, there is nothing to prevent their use in other fields as well.
  • compositions of the invention contain as the first essential ingredient 0.5 to 15 wt .-%, preferably 1 to 12.5 wt .-%, particularly preferably 2.5 to 10 wt .-% and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H 2 O 2 ).
  • the hydrogen peroxide may also be used in the form of its attachment compounds to solid supports, preferably hydrogen peroxide itself is used.
  • the hydrogen peroxide is used as a solution or in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H 2 O 2 (n is a positive integer greater than 0), urea peroxide and melamine peroxide, used.
  • Very particularly preferred according to the invention are aqueous hydrogen peroxide solutions.
  • the concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6-12% solutions in water are used.
  • compositions according to the invention may additionally comprise further oxidizing agents, which are also referred to as "boosters.”
  • the usual peroxo compounds known to the person skilled in the art are, for example, ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, ammonium persulfate, potassium persulfate, sodium persulfate, percarbonates
  • Magnesium percarbonate, peroxides such as barium peroxide and perborates, urea peroxide and melamine peroxide are among these peroxo compounds which can also be used in combination and / or lightening keratinic fibers which additionally comprise from 0.01 to 2% by weight of at least one solid peroxy compound selected from Am mono-, alkali metal and alkaline earth metal persulfates, peroxomonosulfates and peroxydisulfates, preferred agents containing peroxydisulfates, which are preferably selected from sodium peroxydisul
  • persulfates in particular the mixture of potassium peroxosulfate, potassium hydrogen sulfate and potassium sulfate, referred to as Caro's salt.
  • compositions according to the invention contain as the second essential ingredient 0.001 to 15% by weight of at least one polyol ester of the formula (I)
  • the radicals R 1 and R 2 independently of one another represent -H or one of a straight-chain or branched, saturated or mono- or polyunsaturated C 1-. 24 alkyl or alkenyl radical, preferably -H, -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
  • n stands for values from 1 to 12, preferably for 2, 3, 4, 5, 6.
  • the most important hexithexaesters are esters of galactitol, mannitol and sorbitol.
  • R 3 and R 4 in formula (I) are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
  • n in formula (I) stands for the number 2, and the radicals R 1 and R 2 stand for -H), ie esters of glycerol are used.
  • preferred agents for dyeing and / or lightening keratinic fibers are characterized in that they contain 0.1 to 15% by weight, preferably 1 to 12.5% by weight, more preferably 2.5 to 10% by weight and in particular 5 to 7.5% by weight of at least one polyol ester of the formula (Ia)
  • R 1 and R 2 independently represent -H or a straight or branched, saturated or mono- or polyunsaturated Ci- 24 alkyl or alkenyl group, preferably -H, -CH 3; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
  • R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
  • compounds of the formula (I) according to the invention can be used in which n is the number 3 and the radicals R 1 and R 2 are -H, ie esters of 1, 2,3 , 4-butanetetrols used.
  • inventively preferred means for dyeing and / or whitening keratinic fibers characterized in that they contain 0.1 to 15% by weight, preferably 1 to 12.5% by weight, more preferably 2.5 to 10% by weight and in particular 5 to 7 5% by weight of at least one polyol ester of the formula (Ib)
  • R 1 and R 2 independently of one another are -H or a straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 24 -alkyl or -alkenyl radical, preferably -H, -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
  • R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
  • the agents according to the invention serve as agents for dyeing and / or lightening keratinic fibers.
  • Pure brighteners which are also referred to as Blondierstoff, additionally preferably contain oxidizing agents (see below).
  • the agents according to the invention are provided as colorants which do not serve (only) to lighten, but also or exclusively to a color change of the keratinic fibers treated with them.
  • Agents which simultaneously dye and brighten are also referred to as lightening dyes.
  • Preferred agents for dyeing and / or lightening keratinic fibers according to the invention are characterized in that they additionally contain, based on their weight, from 0.001 to 5% by weight of one or more oxidation dye precursors and / or direct dyes.
  • the agents according to the invention are preferably colorants, ie agents for changing the color of keratinic fibers.
  • Oxidation colorants according to the invention contain at least one coupler and at least one developer component. Coupler and developer components are also referred to as oxidation dye precursors.
  • the oxidation colorants according to the invention may also contain substantive dyes as nuances. According to preferred means for dyeing and / or lightening keratinischer fibers are therefore characterized in that they contain at least one oxidation dye precursor of the developer type and / or coupler type.
  • the developer components are usually primary aromatic amines with a further, located in the para or ortho position free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone and 2,4,5,6-tetraaminopyrimidine and its derivatives used.
  • m-phenylenediamine derivatives naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used.
  • Coupler substances are in particular CC-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-Amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1, 3-bis (2 , 4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylamino pyridine and 3,5-diamino-2,6-dimethoxypyridine.
  • the present invention is not subject to any restrictions.
  • the colorants according to the invention can be used as further dye precursors
  • Precursors of natural analog dyes such as indole and indoline derivatives, and mixtures of representatives of these groups.
  • the colorant further contains at least one developer component.
  • developer components are usually primary aromatic Amines with a further, located in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine, heterocyclic hydrazones, 4-amino pyrazolderivate and 2,4,5,6-tetraaminopyrimidine and its derivatives used.
  • p-phenylenediamine derivatives of the formula (E1) it may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)
  • G 1 is a hydrogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -
  • G 2 is a hydrogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -
  • G 3 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -monohydroxyalkyl radical, a C 2 - to C 4 -
  • Polyhydroxyalkyl radical a C 1 - to C 4 -hydroxyalkoxy radical, a C 1 - to C 4 -
  • G 4 represents a hydrogen atom, a halogen atom or a C 1 - to C 4 -alkyl radical or when G 3 and G 4 are ortho to each other, they may together form a bridging ⁇ , ⁇ -alkylenedioxy group, such as, for example, an ethylenedioxy group.
  • C 1 - to C 4 -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals.
  • C 1 -C 4 -alkoxy radicals which are preferred according to the invention are, for example, one Methoxy or ethoxy group.
  • a C 1 -C 4 -hydroxyalkyl group there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or an A-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred.
  • a particularly preferred C 2 to C 4 polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group.
  • halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred.
  • the other terms used are derived according to the invention from the definitions given here.
  • nitrogen-containing groups of the formula (E1) are in particular the amino groups, C 1 to C 4 monoalkylamino groups, C 1 to C 4 dialkylamino groups, C 1 to C 4 trialkylammonium groups, C 1 to C 4 monohydroxyalkylamino groups, Imidazolinium and ammonium.
  • Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- ( ⁇ -hydroxyethyl) amino-2- methylaniline, 4-N,
  • Methoxyethyl -p-phenylenediamine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.
  • Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.
  • developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
  • binuclear developer components which can be used in the colorants according to the invention, mention may be made in particular of the compounds which correspond to the following formula (E2) and their physiologically tolerated salts: in which:
  • Z 1 and Z 2 independently of one another represent a hydroxyl or NH 2 -ReSt which is optionally substituted by a C 1 -C 4 -alkyl radical, by a C 1 -C 4 -hydroxyalkyl radical and / or by a bridging Y or which optionally represents part of a bridging ring system
  • the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, of one or more nitrogen-containing groups and / or one or more heteroatoms such
  • Oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or C 1 - to C 8 -Al koxyreste, or a direct bond,
  • G 5 and G 6 independently represent a hydrogen or halogen atom, a C 1 - to
  • G 7 , G 8 , G 9 , G 10 , G 11 and G 12 independently represent a hydrogen atom, a direct bond to the bridge Y or a C 1 - to C 4 -alkyl radical, with the provisos that the compounds of the formula (E2) contain only one bridging Y per molecule and the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom.
  • Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - (.beta.
  • Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiologically acceptable salts.
  • p-aminophenol derivatives of the formula (E3) it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)
  • G 13 represents a hydrogen atom, a halogen atom, a C 1 - to C 4 alkyl, C 1 - to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (C 1 - to C 4) - Alkoxy- (C- ⁇ - to C 4 ) -alkyl radical, a C 1 - to C 4 -Aminoalkylrest, a hydroxy (C- ⁇ - to C 4 ) -alkylamino, a C 1 - to C 4 -Hydroxyalkoxyrest, a C 1 - to C 4 -hydroxyalkyl- (C 1 -C 4 ) -aminoalkyl or a (di-C 1 - to C 4 -alkylamino) - (C 1 -C 4 ) -alkyl, and
  • G 14 represents a hydrogen or halogen atom, a C 1 - to C 4 alkyl, C 1 - to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (C 1 - to C 4) - Alkoxy (C 1 -C 4 ) -alkyl radical, a C 1 -C 4 -aminoalkyl radical or a C 1 -C 4 -cyanoalkyl radical,
  • G 15 is hydrogen, C 1 - to C 4 -alkyl, C 1 - to C 4 -monohydroxyalkyl, C 2 - to C 4 -polyhydroxyalkyl, phenyl or benzyl, and G 16 is hydrogen or a halogen atom.
  • Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- ( ⁇ -hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- ( ⁇ -hydroxyethyl-aminomethyl) phenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, A-amino-2- (diethyl-aminomethyl) -phenol and their
  • Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) -phenol and 4-amino 2- (diethylaminomethyl) phenol.
  • the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
  • the developer component may be selected from heterocyclic developer components, such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.
  • Preferred pyridine derivatives are in particular the compounds 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxypyridine, 2- ( ⁇ -methoxyethyl ) amino-3-amino-6-methoxypyridine and 3,4-diamino-pyridine.
  • Preferred pyrimidine derivatives are in particular 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6- triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.
  • Preferred pyrazole derivatives are in particular 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- ( ⁇ -hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'- chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4- Amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1 tert-butyl-3-naphthylpyrazole, 4,5-diamino-1- ( ⁇ -hydroxyethy
  • Preferred pyrazole-pyrimidine derivatives are in particular the derivatives of pyrazolo [1, 5-a] -pyrimidine of the following formula (E4) and its tautomeric forms, provided that a tautomeric equilibrium exists:
  • G 17 , G 18 , G 19 and G 20 independently of one another represent a hydrogen atom, a C 1 - to C 4 -alkyl radical, an aryl radical, a C 1 - to C 4 -hydroxyalkyl radical, a C 2 - to C 4 - polyhydroxyalkyl a (d- to C 4) alkoxy (d- to C 4) alkyl, a d- to C 4 - aminoalkyl radical, which may be optionally protected by an acetyl ureide or a sulfonyl residue, a ( d- to C 4 ) -alkylamino (C 1 to C 4 ) -alkyl radical, a di - [(C 1 to C 4 ) -alkyl] - (C 1 to C 4 ) -aminoalkyl radical, where the dialkyl radicals optionally have a form carbocycle or a heterocycle with 5 or 6 chain links, a d- to C
  • the pyrazolo [1, 5-a] -pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization from an aminopyrazole or from hydrazine.
  • Oxidation colorants particularly preferred according to the invention are characterized in that the developer component is selected from 3-methyl-1,4-diaminobenzene, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 2- (2,5-diaminophenoxy) ethanol , N, N-bis (2'-hydroxyethyl) -1, 4-diaminobenzene, 3-methyl-4-aminophenol and 2-methylamino-4-aminophenol, p-phenylenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine , N, N-bis ( ⁇ -hydroxyethyl) -p-phenylenediamine, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino propan-2-ol, bis (2-hydroxy-5-aminophenyl) methane, N, N
  • Preferred agents according to the invention comprise as oxidation dye precursor at least one developer component, preferred developer components being selected from p-phenylenediamine, p-toluenediamine, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (2-hydroxyethyl) amino-p-phenylenediamine, 1, 3-bis - [(2-hydroxyethyl-4 'aminophenyl) amino] -propan-2-ol, 1, 10-bis (2', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane, 4-aminophenol, 4-amino-3-methylphenol, bis (5-amino-2-hydroxyphenyl) methane, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5 , 6-triaminopyrimidine, 4,5-diamino-1- (2-hydroxyethyl) pyrazole.
  • preferred developer components
  • the colorants of the invention may further contain at least one coupler component.
  • coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used.
  • Suitable coupler substances are in particular 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-nnethylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3 -methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, A-chloro-resorcinol, 2-chloro 6-methyl-3-anninophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.
  • Coupler components preferred according to the invention are m-aminophenol and its derivatives such as, for example, 5-amino-2-naphthylphenol, N-cyclopentyl-3-aminophenol, S-amino-1-chloro- ⁇ -methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6 -Dimethyl-3-anninophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-naphthylphenol, 5-amino-4-nethoxy-2-naphthylphenol, 5- (2'-hydroxyethyl ) amino-2-naphthylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylannino) benzene, 3-ethylamino-4-naphthylphenol and 2,4-dichloro 3-aminophenol
  • Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
  • Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4 dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
  • Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1 , 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
  • Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine, quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as 4,6-diaminopyrinnidine, 4-amino-2,6-dihydroxypyrinnidine, 2,4-diamino-6-hydroxypyrinnidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrinnidine, 2-amino-4-hydroxy-6-methylpyrinnidine and 4,6-dihydroxy-2-methylpyrinnidine, or
  • Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.
  • coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-naphthylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-anninophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
  • indoles and indolines which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring.
  • these groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group.
  • the colorants contain at least one indole and / or indoline derivative.
  • Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (RN-Ia),
  • R 1 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxy-alkyl group
  • R 2 is hydrogen or a -COOH group, where the -COOH group is also present as a salt may be a physiologically compatible cation
  • R 3 is hydrogen or a C 1 -C 4 -alkyl group
  • R 4 is hydrogen, a C 1 -C 4 -alkyl group or a group -CO-R 6 , in which R 6 is a C 1 -C 4 -alkyl group, and R 5 is one of the groups mentioned under R 4 , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.
  • Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.
  • N-methyl-5,6-dihydroxyindoline N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.
  • Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (RN-I b),
  • R 1 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxyalkyl group
  • R 2 is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
  • R 3 is hydrogen or a C 1 -C 4 -alkyl group
  • R 4 is hydrogen, a C 1 -C 4 -alkyl group or a group -CO-R 6 , in which R 6 is a C 1 -C 4 -alkyl group, and
  • R 5 is one of the groups mentioned under R 4 , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.
  • Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
  • N-methyl-5,6-dihydroxyindole N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 - Dihydroxyindole.
  • the indoline and indole derivatives can be used in the colorants used in the process according to the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for.
  • the hydrochlorides the sulfates and Hydrobromide used.
  • the indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.
  • the indoline or indole derivative in hair dyes in combination with at least one amino acid or an oligopeptide.
  • the amino acid is advantageously an ⁇ -amino acid;
  • Very particularly preferred ⁇ -amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.
  • oxidation colorants are characterized in that the coupler component is selected from m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives, preferred agents being resorcinol, 3-amino-2-methylamino-6-methoxypyridine, 3-amino-6-methylphenol, 3-amino-2-hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 5-methyl-resorcinol, 2.5 Dimethyl resorcinol and 4-chlororesorcinol 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4- Chlororesorcinol,
  • Preferred agents for dyeing and / or lightening keratinic fibers according to the invention are characterized in that they contain at least one coupler component as the oxidation dye precursor, preferred coupler components being selected from resorcinol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 4- Chlororesorcinol, resorcinol monomethyl ether, 5-aminophenol, 5-amino-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 3-amino-4-chloro-2-methylphenol, 3-amino-2-chloro-6 -methylphenol, 3-amino-2,4-dichlorophenol, 2,4-diaminophenoxyethanol, 2-amino-4- (2 '-hydroxyethyl) amino-anisolsulfat, 1, 3-bis- (2,4-diaminophenoxy) propane, 2-amino-3-hydroxypyridine, 2-methylamino-3-annino-6-
  • coupler and developer components are used in a particular ratio to each other.
  • oxidation colorants of the present invention containing the coupler component (s) in an amount of 0.01 to 20 wt%, preferably 0.5 to 5 wt%, and the developer component (n) in an amount of 0, are preferable. 01 to 20 wt .-%, preferably from 0.5 to 5 wt .-%, each based on the total oxidation colorant included.
  • the colorants may contain one or more substantive dyes for shade.
  • Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, triphenylmethane dyes, acid dyes, basic dyes, preferably from the group of the international trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 1, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, Acid Red 92, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Disperse Red 17, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds and 1, 4-diamino-2-nitrobenzene, 2-amino-4-
  • Disodium salt 4- [2'-hydroxy-1'-naphthyl) azo] -benzenesulfonic acid sodium salt; 3 ', 6'-dihydroxy-
  • Inaphthol sodium salt 2 ', 4', 5 ', 7'-tetrabromo-4151617-tetrachloro-3'16'-dihydroxy-spiro [isobenzofuran-1 (3H), 9' [9H] xanthene] -3-one-dinatrium salt; 4- (2-hydroxy-1-naphthylazo) -3-methylbenzenesulfonic acid sodium salt; Basic Orange 31, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic, Brown 16, Basic Brown 17, Natural Brown 7, Basic Green 1, Basic Red 2, Basic Red 12 Basic Red 22, Basic Red 51, Basic Red 76, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 10, Basic Violet 14, Basic Yellow 57, Basic Yellow 87, Basic Red 46.
  • Agents preferred according to the invention for dyeing and / or brightening keratinic fibers are characterized in that they contain at least one substantive dye selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group known by the international names or trade names Dye HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, Acid Black 52, Basic Yellow 87, Basic Orange 31 and Basic Red 51 known compounds as well as 1 , 4-diamino-2-nitro
  • agents according to the invention may contain a cationic substantive dye. Particularly preferred are
  • aromatic systems substituted with a quaternary nitrogen group such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
  • Preferred cationic substantive dyes of group (c) are in particular the following compounds:
  • the compounds of the formulas (DZ1), (DZ3) and (DZ5) which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).
  • the cationic direct dyes which are sold under the trademark Arianor ®, according to the invention are also very particularly preferred cationic direct dyes.
  • the agents according to the invention according to this embodiment preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the total colorant.
  • preparations of the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.
  • oxidation dye precursors or the direct dyes it is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, further components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.
  • Staining of keratinic fibers can also be accomplished by dyes formed in an oxidatively catalyzed reaction of C, H-acidic compounds with reactive carbonyl compounds.
  • the agent according to the invention therefore contains a combination of
  • B compounds selected from (a) CH-acidic compounds, (b) compounds having a primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (c) amino acids, (d) from 2 to 9 amino acids constructed oligopeptides.
  • Compounds according to the invention having a reactive carbonyl group (also referred to below as reactive carbonyl compounds or component A) have at least one carbonyl group as reactive group which reacts with the compounds of component B to form a chemical bond linking both components. Furthermore, those compounds according to the invention are also included as component A in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to component B is always present.
  • These derivatives are preferably condensation compounds of reactive carbonyl compounds with a) amines and derivatives thereof to form imines or oximes as condensation compound b) of alcohols to form acetals or ketals as condensation compound c) of water to form hydrates as addition compound.
  • Component A is preferably selected from the group formed from acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2.5-
  • Benzaldehyde, cinnamic aldehyde and naphthaldehyde and their derivatives, in particular having one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl compound in the agents according to the invention.
  • the compounds according to formula (Ca-1) are preferred,
  • R 1, R 2 and R 3 are independently a hydrogen atom, a halogen atom, a C- ⁇ -C6 alkyl group, a hydroxy group, a dC 6 alkoxy group, a C- ⁇ -C 6 -Dialkylanninoè, a di (C 2 -C 6 -hydroxyalkyl) -annino group, a di (C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl) -annino group, a C 1 -C 6 -hydroxyalkyloxy group, a sulfonyl group, a carboxy group, a sulfonic acid group, a sulfonamido group, a sulfonamide group, a carbamoyl group, a C 2 -C 6 acyl group or a nitro group,
  • Z ' is a direct bond or a vinylene group
  • R 4 * and R 5 * represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.
  • the derivatives of the benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component C are particularly preferably selected from certain aldehydes.
  • Agents preferred according to the invention are characterized in that they are formulated as hair colorants, based on their weight from 0.01 to 20 wt .-%, preferably 0.05 to 15 wt .-%, particularly preferably 0.1 to 12.5 wt .-% and in particular 0.2 to 10 wt .-% of one or more reactive carbonyl compound (s).
  • CH-acidic compounds are generally considered to carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents activation of the corresponding carbon-hydrogen bond is effected.
  • CH-acidic compounds also include enamines which are formed by alkaline treatment of quaternized N-heterocycles with a CH-acidic alkyl group in conjugation with the quaternary nitrogen.
  • the CH-acidic compounds of component B are preferably selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium-p-toluenesulfonate Fonate, 2,3-dimethylnaphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methylnaphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine 3-acetic
  • Suitable compounds having primary or secondary amino group as component B are, for example, primary aromatic amines such as N, N-dimethyl, N, N-diethyl, N- (2-hydroxyethyl) -N-ethyl, N, N-bis ( 2-hydroxyethyl) -, N- (2-methoxyethyl), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4 - morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenoi, 2-hydroxymethyl-4-aminophenoi, o-, p-phenylenediamine, o-toluenediamine, 2,5-diaminotoluene, -phenot , - phenethole, 4-amino-3-methylphenoi, 2- (2,5-dia
  • R 7 represents a hydroxy or an amino group represented by CI_ 4 alkyl, Ci. 4 -Hydroxyalkyl-, d- 4 - alkoxy- or Ci. 4- alkoxy-Ci. 4- alkyl groups may be substituted,
  • R 8, R 9, R 10, R 11 and R 12 independently represent a hydrogen atom, a hydroxy or an amino group by C 4 alkyl, C- ⁇ -C 4 hydroxyalkyl, C 1 -C 4 -Aikoxy, C 1 -C 4 -aminoalkyl or C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl groups may be substituted, and
  • P is a direct bond, a saturated or unsaturated, optionally substituted by hydroxy groups carbon chain having 1 to 4 carbon atoms, a carbonyl, sulfoxy, sulfonyl or imino group, an oxygen or sulfur atom, or a group
  • Q signifies a direct bond, a CH 2 or CHOH group
  • Q 'and Q are each independently an oxygen atom, an NR 13 group, wherein R 13 is a hydrogen atom alkyl group, a C 4 alkyl or a hydroxy-CI_ 4, wherein both groups together with the remainder of the molecule is a 5 , 6- or 7-membered ring, means the group O- (CH 2 ) P -NH or NH- (CH 2 ) P -O, wherein p and p 'are 2 or 3, and O is a number from 1 to 4,
  • the abovementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid.
  • Suitable nitrogen-containing heterocyclic compounds are e.g. 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5-amino, 2-methylamino-3-amino-6-methoxy, 2,3-diamino-6-methoxy, 2,6-dimethoxy-3,5-diamino, 2,4,5-triamino, 2, 6-Dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino, 4,5,6-triamino, 4-hydroxy-2,5,6-triamino, 2-hydroxy-4 , 5,6-triamino, 2, 4,5,6-tetraamino, 2-methylamino-4,5,6-triamino, 2,4-, 4,5-diamino, 2-amino-4- methoxy-6-methyl-pyrimidine, 3,5-d
  • indole or indoline derivatives 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
  • Preferred amino acids are all naturally occurring and synthetic (alpha-amino acids, eg the amino acids obtainable by hydrolysis from vegetable or animal proteins, eg collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (Dihydroxyphenylalanine), ornithine, lysine and tryptophan. But it can also be used other amino acids, such as. B. 6-aminocaproic acid.
  • the oligopeptides may be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolysates, provided that they have sufficient water solubility for use in the inventive colorants.
  • the oligopeptides contained in polypeptide or protein hydrolysates e.g. Glutathione or the oligopeptides contained in the hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein.
  • Suitable aromatic hydroxy compounds are e.g. 2-, A-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, catechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, - phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, acetophenone, 2-, A-chlororesorcinol, 1-naphthol , 1, 5, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.
  • CH-active compounds there can be exemplified 1, 2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium-p-toluoisulfonate, 1,2,3,3-tetramethyl 3H indolium methanesulfonate, Fischer's base (1,3,3-trimethyl-2-methylenindoline), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid , 1-ethyl-2-quinaldinium iodide, 1-methyl-2-quinaldinium iodide barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxylacetate
  • the CH-acidic compounds are preferably selected from the formulas (II) and / or (III) and / or (IV)
  • R 8 and R 9 are independently a linear or cyclic dC 6 alkyl group, a C 2 -C 6 alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl C- ⁇ -C6 alkyl group, a C- ⁇ -C 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C- ⁇ -C alkyl 6 -alkoxy-C- ⁇ -C 6, a group R'R "N- (CH 2) m in which R 1 and R "independently of one another represent a hydrogen atom, a C 1 -C 4 -alkyl group, a C 1 -C 4 -hydroxyalkyl group or an aryl-C 1 -C 6 -alkyl group, where R 1 and R 11 together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
  • R 10 and R 12 independently represent a hydrogen atom, or a Ci-C 6 - alkyl group, wherein at least one of the radicals R 10 and R 12 is a Ci-C 6 alkyl group, R 11 stands for a hydrogen atom, a dC 6 - alkyl group, a dC 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl, a dC 6 alkoxy group, a dC 6 -hydroxyalkoxy group, a group R m R lv N- (CH 2) q - wherein R 1 "and R ⁇ v independently represent a hydrogen atom, a dC 6 alkyl group, a dC 6 hydroxyalkyl group, or an aryl-dC 6 - alkyl group, and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R 11 together with one of R 10 or R 12 may form a 5- or 6-membered aromatic ring optionally substituted with a
  • R 13 and R 14 either form together with the nitrogen atom form a saturated or unsaturated 5- or 6-membered ring, or independently represent a (Ci-C 6) - alkyl group, a (C 2 -C 6) alkenyl group, an aryl group , an aryl- (C 1 -C 6 ) -alkyl group, a (C 2 -C 6 ) -hydroxyalkyl group, a (C 2 -C 6 ) -polyhydroxyalkyl group or a group R 1 R 11 N- (CH 2) m - wherein R 1 and R 11 are independently a hydrogen atom, a (Ci-C 6) - alkyl group, a (C- ⁇ -C 6) alkenyl group or an aryl C- ⁇ -C 6 alkyl group, wherein R 1 and R 11 together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, and
  • R 15 represents a hydrogen atom, a (dC 6) alkyl group, a (C 2 -C 6) alkenyl group, an aryl group, an aryl (dC 6) alkyl group, a (C 2 -C 6) hydroxyalkyl group, a (C 2 -C 6 ) - Polyhydroxyalkyl distr or a group R m R lv N- (CH 2 ) n -, wherein R m and R IV independently represent a hydrogen atom, a (dC 6 ) alkyl group, a (dC 6 ) Alkenyl group or an aryl-dC 6 alkyl group, wherein R m and R ⁇ v together with the nitrogen atom can form a 5-, 6- or 7-membered ring and n is a number 2, 3, 4, 5 or 6
  • Y represents an oxygen atom, a sulfur atom or a group NR V ", wherein R v" stands for a
  • Hydrogen atom an aryl group, a heteroaryl group, a C 1 -C 6 -alkyl group or a C 1 -C 6 -arylalkyl group,
  • X ' is a physiologically acceptable anion
  • Het is an optionally substituted heteroaromatic
  • X 1 represents a direct bond or a carbonyl group.
  • At least one group R 10 or R 12 according to formula II necessarily stands for a C 1 -C 6 -alkyl group.
  • This alkyl group preferably carries at least two hydrogen atoms on its alpha carbon atom.
  • Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, neo-pentyl, n-hexyl group.
  • R 10 and R 12 are each independently hydrogen or a methyl group, wherein at least one group R 10 or R 12 is a methyl group.
  • Y is an oxygen or sulfur atom, more preferably an oxygen atom.
  • the radical R 8 is preferably selected from a (C 1 -C 6 ) -alkyl group (particularly preferably a methyl group), a C 2 -C 6 -alkenyl group (in particular an allyl group), a hydroxy (C 2 -C 6 ) -alkyl group, in particular a 2-hydroxyethyl group, or an optionally substituted benzyl group.
  • R 11 is preferably a hydrogen atom.
  • the radicals R 9 , R 10 and R 12 are a methyl group
  • the radical R 11 is a hydrogen atom
  • Y is an oxygen or sulfur atom
  • the radical R 8 is selected from a (C- ⁇ -C 6 ) Alkyl group (particularly preferably a methyl group), a C 2 -C 6 alkenyl group (in particular an allyl group), a hydroxy (C 2 to C 6 ) alkyl group, in particular a 2-hydroxyethyl group, or an optionally substituted benzyl group.
  • the compounds according to formula II are selected from one or more
  • X ' in formula (II) and in the lists above preferably for halide, benzenesulfonate, p-toluenesulfonate, dC 4 alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogen sulfate, tetrafluoroborate, hexafluorophosphate or Tetrachlorozinkat.
  • the anions chloride, bromide, iodide, hydrogen sulfate or p-toluenesulfonate are used as X ' .
  • the radical Het according to formula (III) preferably represents the molecule fragment of the formula (V),
  • R 16 and R 17 independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic dC 6 alkyl group, a C 2 -C 6 - alkenyl group, an optionally substituted aryl group, a cyanomethyl group, a cyanomethylcarbonyl, an optionally substituted heteroaryl group, an aryl-dC 6 - alkyl group, a C- ⁇ -C 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C 1 -C 6 - alkoxy group, a dC 6 alkoxycarbonyl group, a C ⁇ -C 6 -alkoxy-C 2 -C 6 alkyl group, a C 1 - C 6 sulfoalkyl, a C- ⁇ -C 6 carboxyalkyl group, a group R vm R lx N- (CH 2) m -
  • X 2 and X 3 independently represent a nitrogen atom or a group CR 15 , wherein
  • R 15 represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic dC 6 alkyl group, a C 2 -C 6 alkenyl group, an optionally substituted aryl group, a cyanomethyl group, a cyanomethylcarbonyl group, an optionally substituted heteroaryl group, an aryl Ci-C 6 alkyl group, a C 1 -C 6 - hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a dC 6 alkoxy group, a C 1 -C 6 - alkoxycarbonyl group, a C- ⁇ -C 6 Alkoxy C 2 -C 6 alkyl group, a dC 6 -Sulfoalkyl distr, a dC 6 -Carboxyalkyl distr and a group R x R xl N- (CH 2 ) n -, wherein R x
  • X 4 is an oxygen atom, a sulfur atom, a vinyl group or an NH group, which latter two groups are independently optionally substituted with a linear or cyclic dC 6 alkyl group, a C 2 -C 6 alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-dC 6 -alkyl group, a C 2 -C 6 -hydroxyalkyl group, a C 2 -C 6 -polyhydroxyalkyl group, a C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl group, a dC 6- sulfoalkyl group, a dC 6 -Carboxyalkyl distr, a group R x "R xm N- (CH 2 ) p -, wherein R x " and R x ⁇ "independently represent a hydrogen atom, a linear or cyclic dC 6 alkyl group
  • the radical Het according to formula (III) is particularly preferably derived from the heteroaromatics furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, pyridine, pyridazine, pyrimidine, pyrazine, 1, 2,3-triazine, 1, 2 , 4-triazine, 1, 3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, indole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, acridine, benzoquinoline, benzoisoquinoline, benzothiazole , Phenazine, benzocinnoline, benzoquinazoline, benzoquinox
  • the compounds according to formula (III) are selected from the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 2- (5-methyl-2-trifluoromethyl- 3-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5- Fluoro-2-thenoyl) -acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) -acetonitrile , 2- (2,5-Dimethylpyrrole-3-oyl) -acetonitrile, 2-
  • Agents preferred according to the invention are characterized in that they are formulated as hair colorants, based on their weight from 0.01 to 20 wt .-%, preferably 0.05 to 15 wt .-%, particularly preferably 0.1 to 12.5 wt .-% and in particular 0.2 to 10 wt .-% of one or more CH-acidic compound (s) included.
  • Agents preferred according to the invention for dyeing and / or brightening keratinic fibers are therefore characterized in that they contain from 1 to 20% by weight of at least one optionally substituted, in particular benzannellated, azole, preferably at least one optionally substituted and / or benzannellated pyrrole and / or pyrazole and / or imidazole and / or 1, 2,3-triazole and / or 1, 2,4-triazole and / or 1, 2,3,4-tetrazole.
  • the azoles may carry or be substituted by a hydrogen atom on the N atoms marked with a bond.
  • Aryl, alkyl or alkenyl radicals have proven useful as substituents on the respective N atom.
  • the azoles may be substituted or benzannellated at the carbon atom (s).
  • Preferred benzene-substituted azoles which can be used according to the invention have the following structures, where the araomatic rings may optionally be further substituted.
  • preferred according to the invention is the use of pyrazoles.
  • preferred agents according to the invention are characterized in that they contain at least one imidazole compound of the formula (VI) and / or their physiologically tolerated salts
  • R 1 represents a hydrogen atom, an optionally substituted aryl group or a (dC 6 ) -alkyl group,
  • R z represents a hydrogen atom, a carboxaldehyde group, a (C 1 -C 6 ) -alkyl group or a nitro group,
  • R 3 represents a hydrogen atom, a carboxy (dC 6 ) alkyl group, an amino (C 1 -C 6 ) alkyl group, a carboxyl group, a Carboxaldehyde group, a (dC 6 ) alkyl group, a nitro group, a 2-amino-3-hydroxypropyl group or a group -CH 2 -CH (NH 2 ) -COOH,
  • R 4 represents a hydrogen atom, a carboxaldehyde group or a
  • the imidazole compound (s) of formula (VI) is / are used within narrower ranges.
  • agents according to the invention for dyeing and / or lightening keratinic fibers are preferred which contain at least one imidazole compound of the formula (VI) and / or physiologically tolerable salts thereof in amounts of from 2 to 15% by weight, preferably from 2.5 to 12.5 Wt .-%, particularly preferably from 3 to 10 wt .-% and in particular from 4 to 8 wt .-%.
  • the imidazole compounds of formula (VI) are selected from at least one member of a group formed from histamine, D-histidine, L-histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, imidazole , imidazole-4-acetic acid, imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazole-2-carboxaldehyde, imidazole-4-carboxaldehyde, imidazole-5-carboxaldehyde, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole 5-carboxaldehyde, N-methylimidazole-2-carboxaldehyde, 4-methylimidazole, 2-methylimidazole, N-methylimidazole, N- (4-aminophenyl) -imidazole, and the physiologically acceptable salt
  • preferred agents according to the invention are characterized in that they contain at least one imidazole compound of the formula (VI) and / or their physiologically tolerable salts in amounts of from 2 to 15% by weight, preferably from 2.5 to 12.5% by weight, particularly preferably from 3 to 10% by weight and in particular from 4 to 8% by weight, preferred imidazole compounds according to formula (VI) and / or their physiologically tolerated salts being selected from histamine, D-histidine, Histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, imidazole, imidazole-4-acetic acid, imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazole-2-carboxaldehyde, imidazole-4 carboxaldehyde, imidazole-5-carboxaldehyde, 2-nitroimidazole, A-nitroimidazole, 4-
  • Preferred agents according to the invention for dyeing and / or lightening keratinic fibers are characterized in that they additionally contain 0.1 to 25% by weight, preferably 0.5 to 20% by weight, especially preferably 1 to 15 wt.% And in particular 1, 5 to 10 wt.% Of at least one substance from the groups of ii. Carbonates and / or iii. Monoalkyl carbonates (carbonic acid monoesters) and / or iv. Carbonic acid monoamides and / or v. Silyl carbonates and / or vi. Silylcarbamate included.
  • Particularly suitable carbonates are ammonium, alkali metal and alkaline earth metal carbonates and bicarbonates.
  • sodium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate and ammonium carbananate are particularly preferred.
  • compositions according to the invention may preferably also contain at least one carbonic acid monoester and / or at least one carbonic acid monoamide. These substances are described in detail below.
  • Agents preferred according to the invention are characterized in that they contain at least one carbonic acid monoester of the formula (C-I)
  • R represents a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.
  • R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents.
  • Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably R is a C-. 6- alkyl group.
  • C 1 -C 6 -alkyl groups are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.
  • compositions according to the invention may contain carbonic acid monoamides.
  • preferred agents according to the invention are characterized in that they contain at least one carbonic acid monoamide of the formula (C-II)
  • R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.
  • R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents.
  • Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably, R is a Ci_ 6 alkyl group.
  • C 1 -C 6 -alkyl groups are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.
  • radical R in formula (CI) is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl as well as hydroxymethyl and hydroxyethyl radicals.
  • the acidic H atom of the carbonic acid monoester or monoamide may also be in neutralized form, i. salts of carbonic acid monoesters or carbonic acid monoamides can also be used according to the invention.
  • agents according to the invention are preferred which contain the carbonic acid monoester or the carbonic acid monoamide in completely or partially neutralized form, preferably in the form of its alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt.
  • compositions according to the invention comprise one or more carbonic acid monoesters and / or one or more carbonic acid monoamides
  • agents according to the invention are preferred which contain the carbonic acid monoester and / or carbonic acid monoamides in amounts of from 0.1 to 20% by weight, preferably from 0 , 5 to 18 wt.%, Particularly preferably from 2 to 15 wt.% And in particular from 5 to 12 wt.%, Each based on the total agent.
  • the compositions according to the invention may preferably also contain at least one silyl carbonate and / or at least one silyl carbamate. These substances are described in detail below.
  • Agents preferred according to the invention are characterized in that they contain at least one silyl carbonate of the formula (C-III)
  • radicals R 1 , R 2 and R 3 independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted Aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino, imino groups and the radical R 4 is a chemical bond to the Si atom or to one of the radicals R 1 , R 2 or R 3 , a hydrogen atom, a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical or for a substituted or unsubstituted SiIyI or alumino group or for a substituted or unsubstituted aryl group or a
  • Preferred radicals R 1 , R 2 and R 3 in the abovementioned formula (C-III) are substituted or unsubstituted, straight-chain or branched alkyl radicals.
  • the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred agents according to the invention are characterized in that the radicals R 1 , R 2 and R 3 in formula (C-III) are selected from methyl, ethyl , n-propyl, iso-propyl, n-butyl, iso-butyl, terf-butyl and hydroxymethyl and hydroxyethyl radicals.
  • Preferred radicals R 4 in the abovementioned formula (C-III) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.
  • agents according to the invention are preferred which comprise at least one silyl carbonate in completely or partially neutralized form, preferably in the form of its alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt.
  • compositions of the invention may contain silyl carbamates.
  • Agents preferred according to the invention are characterized in that they contain a silyl carbamate of the formula C-IV)
  • radicals R 1 , R 2 and R 3 independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or for a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino groups and the radicals R 4 and R 5 independently of one another for a chemical bond to the Si atom or to a the radicals R 1 , R 2 or R 3 , a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted SiIyI or alumino group or a substituted or unsubstituted
  • Preferred radicals R 1 , R 2 and R 3 in the abovementioned formula (C-IV) are substituted or unsubstituted, straight-chain or branched alkyl radicals.
  • the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred agents according to the invention are characterized in that the radicals R 1 , R 2 and R 3 in formula (VII) are selected from methyl, ethyl, n Propyl, iso-propyl, n-butyl, iso-butyl, terf-butyl and hydroxymethyl and hydroxyethyl radicals.
  • Preferred radicals R 4 and R 5 in the abovementioned formula (C-IV) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.
  • compositions according to the invention contain one or more silyl carbonates and / or one or more silyl carbamates
  • agents according to the invention are preferred which contain the silyl carbonate (s) and / or silyl carbamate (s) in amounts of from 0.1 to 25% by weight .%, Preferably from 0.5 to 20 wt.%, Particularly preferably from 1 to 15 wt.% And in particular from 1, 5 to 10 wt.%, Each based on the total agent.
  • a further increase in the whitening power can be achieved by the addition of cyanates or "cyanate analogues" which, in combination with the use according to the invention of the polyol esters, make it possible to increase the activity formula
  • M + [OCN] "in which M + is K +, Na +, Li + or NH 4 +, or 1/2 Ca 2+, 1/2 Mg 2+ or 1/2 Zn 2+ and / or
  • cyanates according to the invention potassium cyanate, KOCN, and / or sodium cyanate, NaOCN, and / or lithium cyanate, LiOCN, and / or ammonium cyanate, NH 4 OCN, and / or calcium cyanate, Ca (OCN) 2 , and / or magnesium cyanate, Mg (OCN ) 2 , and / or zinc cyanate, Zn (OCN) 2 .
  • Agents preferred according to the invention are characterized in that they contain 0.075 to 4% by weight, preferably 0.1 to 2.5% by weight and in particular 0.2 to 1% by weight of sodium cyanate and / or potassium cyanate and / or ammonium cyanate with sodium cyanate being particularly preferred.
  • agents according to the invention can also be present in the agents according to the invention.
  • preferred agents according to the invention characterized in that they are 0.075 to 4 wt .-%, preferably 0.1 to 3.5 wt .-% and in particular 0.2 to 3 wt .-% of at least one compound of the formula
  • H 2 NC (O) -L in which L is selected from -S-CH 2 -COOH, -S- (CH 2 ) 3 SO 3 H, -S- (CH 2 ) 2 -NH 2 , -OCH 3 , -O- (C 6 H 4 ) -SO 3 M, -Q + , -NH-OH, -O-C (O) -R 1 , -O-C (O) -H, -O-CH (OH) 2 , -SO 3 M, -PH (O) OH, -P (O) (OH) 2 , - (NH-glucosamine) n , -NH-C (O) -NH 2 , -NH-NH 2 , -NH-CN, - P (OH) (O) -C (O) NH 2 , -SCN, -OCN, -SC (NH) NH 2 , OONa
  • M is -H, Na, K, NH4
  • Q is selected from quaternary ammonium radicals, heteroaryl radicals or nonaromatic heterocycles formed from tertiary amines, and R 1 is -H, -CH 3 , -CH 2 CH 3 , - ( CH 2 ) 2 CH 3 , -CH (CH 3 ) 2 or another alkyl group.
  • Particularly preferred agents according to the invention contain from 0.075 to 4% by weight, preferably from 0.1 to 3.5% by weight and in particular from 0.2 to 3% by weight of at least one of the compounds listed below:
  • Piperidones or their derivatives can also enhance the effects of the polyol esters, so that use of from 0.1 to 20% by weight of at least one piperidone and / or piperidone derivative in the agents according to the invention is preferred.
  • the agents according to the invention preferably contain from 0.5 to 15% by weight, more preferably from 1 to 12.5% by weight and in particular from 2.5 to 10% by weight, of at least one compound from the group
  • Piperidones are compounds having a keto function on a six-membered ring formed of five carbon atoms and one nitrogen atom. Depending on the position of the nitrogen atom it is called the keto group, the unsubstituted base body as 2-piperidone (piperidine-2-one, ⁇ -valerolactam, alpha-piperidone), 3-piperidone (piperidin-3-one, beta-piperidone) or 4- Piperidone (piperidin-4-one, gamma-piperidone).
  • 2-piperidone piperidine-2-one, ⁇ -valerolactam, alpha-piperidone
  • 3-piperidone piperidin-3-one, beta-piperidone
  • 4- Piperidone piperidin-4-one, gamma-piperidone
  • substituted piperidones are suitable both on the C-skeleton and on the nitrogen atom, the N-substituted piperidone derivatives being of great importance, since the nitrogen can be easily exchanged for nitrogen , Among these piperidone derivatives, the following have been found to be particularly preferred according to the invention:
  • N atom in the piperidones preferably used according to the invention may also be present in quaternized form, so that it is also possible according to the invention to use piperidinium salts.
  • particularly preferred agents according to the invention characterized in that they contain 3-piperidinium salts of the formula (VII) and / or 4-piperidinium salts of the formula (VIII)
  • the radicals or R 3 or R 4 or R 5 or R 6 may be a hydrogen atom.
  • these piperidinium salts the following have been found to be particularly preferred according to the invention:
  • compositions according to the invention may comprise at least one compound of amino acids and / or oligopeptides, these each having at least two amino groups and at least one -COOH or -SO H group and their 2.5% strength
  • Solution in water in each case has a pH greater than 9.0.
  • Preferred alkalizing agents are aminocarboxylic acids, in particular ⁇ -aminocarboxylic acids and omega-aminocarboxylic acids.
  • ⁇ -aminocarboxylic acids lysine and especially arginine are again particularly preferred.
  • amino acids can preferably be added to the agents according to the invention in free form. In a number of cases, however, it is also possible to use the amino acids in salt form. Preferred salts are then the compounds with hydrohalic acids, in particular the hydrochlorides and hydrobromides. Furthermore, the amino acids can also be used in the form of oligopeptides and protein hydrolysates, if it is ensured that the required amounts of the amino acids used according to the invention are contained therein.
  • a particularly preferred alkalizing agent is arginine.
  • Agents preferred according to the invention are characterized in that they additionally contain from 0.05 to 5% by weight, preferably from 0.1 to 2.5% by weight, particularly preferably from 0.15 to 1% by weight and in particular 0.2 to 0.5 wt .-% amino acid (s), preferably (one) amino acid (s) from the group glycine and / or alanine and / or valine and / or lysine and / or leucine and / or threonine and / or serine ,
  • agents according to the invention can also be prepared directly before use from two or more separately packaged preparations. This is particularly useful for the separation of incompatible ingredients to avoid premature reaction.
  • a common way is therefore to mix an agent A according to the invention with an oxidizing agent preparation B directly before use to form an application mixture.
  • Another object of the present invention is therefore an agent for dyeing and / or whitening keratinic fibers, in particular human hair, which immediately before application to the hair from a flowable preparation A, an oxidizing agent preparation B containing at least one oxidizing agent selected from hydrogen peroxide and whose addition compounds to solid carriers and a preparation C, which are mixed together to a dyeing and / or Aufhellansatz, is obtained, wherein the composition A and / or C is a composition according to the invention.
  • An oxidizer formulation B contains at least one oxidizer selected from hydrogen peroxide and its attachment compounds to solid supports.
  • hydrogen peroxide itself is preferably used.
  • the hydrogen peroxide is used as a solution or in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H 2 O 2 (n is a positive integer greater than 0), urea peroxide and melamine peroxide, used.
  • Very particularly preferred according to the invention are aqueous hydrogen peroxide solutions.
  • the concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6-12% solutions in water are used.
  • the oxidizing agent preparation B - based on their weight - 0.5 to 10 wt .-%, preferably 0.75 to 9.0 wt .-%, particularly preferably 1 to 8.0 wt .-%, more preferably 1, 25 to 7.0 wt .-% and in particular 1, 5 to 6.0 wt .-% hydrogen peroxide (calculated as 100% H 2 O 2 ) contains.
  • the oxidizer formulation B is preferably an aqueous, flowable oxidizer formulation. Accordingly, preferred agents for dyeing and / or lightening keratinic fibers according to the invention are characterized in that the flowable oxidizing agent preparation B - based on its weight - 40 to 90 wt .-%, preferably 50 to 85 wt .-%, particularly preferably 55 to 80 wt .-%, more preferably 60 to 77.5 wt .-% and in particular 65 to 75 wt .-% water.
  • agents according to the invention for dyeing and / or lightening keratinic fibers are preferred, which contain 0.5 to 15% by weight, preferably 1 to 12.5% by weight, particularly preferably 2.5 to 10% by weight. and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H 2 O 2 ) included.
  • an emulsifier or a surfactant is added to the flowable oxidizing agent preparation B, surfactants depending on the field of use being referred to as surfactants or as emulsifiers and being selected from anionic, cationic, zwitterionic, ampholytic and nonionic surfactants and emulsifiers. These substances are described in detail below.
  • this further peroxo compound is subject in principle to no restrictions, and conventional peroxo compounds known to the person skilled in the art are, for example, ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, ammonium persulfate, potassium persulfate, sodium persulfate, percarbonates, such as magnesium percarbonate.
  • Peroxides such as barium peroxide and also perborates, urea peroxide and melamine peroxide are among these peroxo compounds which can also be used in combination.
  • Partoxysulfates are particularly preferred according to the invention, in particular combinations of at least two peroxydisulfates and / or lightening keratinic fibers which additionally contain from 0.01 to 2% by weight of at least one solid peroxy compound selected from ammonium, alkali metal and alkaline earth metal persulfates, peroxomonosulfates and peroxydisulfates, preferred agents containing peroxydisulfates are preferably selected from sodium peroxydisulfate and / or potassium peroxydisulfate and / or ammonium peroxydisulfate and particularly preferred agents containing at least two different peroxide islfate.
  • persulfates in particular the mixture of potassium peroxosulfate, potassium hydrogen sulfate and potassium sulfate, referred to as Caro's salt.
  • the anhydrous compositions of the present invention may additionally contain at least one other bleaching enhancer other than the inorganic persalts.
  • bleach amplifiers it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • anhydrous compositions according to the invention may additionally contain as bleaching boosters at least one optionally hydrated SiO 2 compound.
  • the optionally hydrated SiO 2 compounds in amounts of 0.05 wt .-% to 15 wt .-%, particularly preferably in amounts of 0.15% by weight to 10% by weight and very particularly preferably in amounts of from 0.2% by weight to 5% by weight, based in each case on the anhydrous composition according to the invention.
  • the present invention is in principle subject to no restrictions. Preference is given to silicic acids, their oligomers and polymers and their salts. Preferred salts are the alkali salts, especially the potassium and sodium salts. The sodium salts are very particularly preferred.
  • the optionally hydrated SiO 2 compounds can be present in various forms.
  • the SiO 2 compounds are preferably used in the form of silica gels (silica gel) or particularly preferably as water glass. These SiO 2 compounds may be partially present in aqueous solution.
  • water glasses which are formed from a silicate of the formula (SiO 2 ) n (Na 2 O) m (K 2 O) p , where n is a positive rational number and m and p are each independently one positive rational number or 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1.
  • the water glasses in small amounts may contain other additives, such as phosphates or magnesium salts.
  • particularly preferred water glasses are sold among others by Henkel under the names Ferrosil® ® 119, soda water glass 40/42, Portil ® A, Portil ® AW and Portil ® W and by Akzo under the name Britesil® ® C20.
  • Agents preferred according to the invention are characterized in that they additionally contain 0.05 to 15% by weight, particularly preferably 0.15 to 10% by weight and in particular 0.2 to 5% by weight of at least one optionally hydrated SiO 2 compound
  • Preferred agents include water glasses formed from a silicate of the formula (SiO 2 ) n (Na 2 O) m (K 2 O) p , where n is a positive rational number and m and p are independently one positive rational number or 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1.
  • the dyeing and / or brightening agents according to the invention contain nonionic surfactants.
  • Such surfactants having an HLB of 5.0 and greater are preferred.
  • HLB value reference is explicitly made to the statements in Hugo Janistyn, Handbuch der Kosmetika und Riechstoffe, III. Volume: The personal care products, 2nd edition, Dr. med. Alfred Hüthig Verlag Heidelberg, 1973, pages 68-78 and Hugo Janistyn, Paperback of modern perfumery and cosmetics, 4th edition, Scientific Verlagsgesellschaft mbH Stuttgart, 1974, pages 466-474, as well as the original works cited therein reference.
  • non-ionic surface-active substances are substances that are commercially available as solids or liquids in pure form because of their ease of processing.
  • the definition of purity in this context does not refer to chemically pure compounds. Rather, especially when it comes to natural-based products, mixtures of different homologs can be used, for example, with different alkyl chain lengths, such as those obtained with products based on natural fats and oils. Even with alkoxylated products, mixtures of different degrees of alkoxylation are usually present.
  • purity in this context refers rather to the fact that the selected substances should preferably be free from solvents, adjuvants and other impurities.
  • Preferred nonionic surfactants are:
  • - alkoxylated fatty alcohols having 8 to 22, in particular 10 to 16, carbon atoms in the fatty alkyl group and 1 to 30, in particular 1 to 15, ethylene oxide and / or
  • Preferred fatty alkyl groups are, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl groups.
  • Particularly preferred compounds of this class are, for example, lauryl alcohol with 2 to 4 ethylene oxide units, oleyl and cetyl alcohol with 5 to 10 ethylene oxide, cetyl alcohol and stearyl alcohol and mixtures thereof with 10 to 30 ethylene oxide units and the commercial product Aethoxal ® B (Henkel), Lauryl alcohol with 5 ethylene oxide and 3 propylene oxide units.
  • alkoxylated fatty alcohols it is also possible to use so-called "end-capped” compounds according to the invention
  • the alkoxy group has no OH group at the end but is "closed” in the form of an ether, in particular a C 1 -C 4 -alkyl ether.
  • An example of such a compound is the commercially available product ® Dehypon LT 054, a C 2-18 -Fettalkoholol + 4.5 ethylene oxide-butyl ether.
  • - alkoxylated fatty acids having 8 to 22, in particular 10 to 16, carbon atoms in the fatty acid group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units.
  • Preferred fatty acids are, for example, lauric, myristic, palmitic, stearic, isostearic and oleic acids.
  • - alkoxylated, preferably propoxylated and especially ethoxylated, mono-, di- and triglycerides examples are glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide.
  • Polyglycerol esters and alkoxylated polyglycerol esters are for example poly (3) glycerol diisostearate (commercial product: Lamefornn ® TGI (Henkel)) and poly (2) glycerinpolyhydroxy stearate (commercial product: - Dehymuls ® PGPH (Henkel)).
  • Sorbitan fatty acid esters and alkoxylated sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monolaurate + 20 ethylene oxide (EO).
  • Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15, carbon atoms in the alkyl chain and 0 to 30 ethylene oxide and / or propylene oxide units.
  • Preferred representatives of this class are, for example, nonylphenol + 4 EO, nonylphenol + 9 EO, octylphenol + 3 EO and octylphenol + 8 EO.
  • nonionic surfactants are the alkoxylated fatty alcohols, the alkoxylated fatty acids and the alkylphenols and alkylphenol alkoxylates.
  • Agents according to the invention which contain non-ionic surface-active substances in amounts of 1 to 5% by weight have proved to be particularly advantageous.
  • the dyeing and / or brightening agents according to the invention may contain all known in such preparations active ingredients, additives and excipients.
  • the agents contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable.
  • anionic surfactants may be very particularly preferred.
  • Preferred anionic surfactants are alkyl sulfates, ether carboxylic acid salts having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule such as C 12 H 25 - (C 2 H 4 O) 6 -CH 2 -COONa and in particular salts of saturated and especially unsaturated C8-C22 carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.
  • anionic surfactants should preferably be present in solid, in particular powder form. Very particular preference is given to solid soaps, especially sodium stearate, at room temperature. These are preferably present in amounts of from 5 to 20% by weight, in particular from 10 to 15% by weight.
  • Suitable nonionic surfactants are in particular C 8 -C 22 -alkyl mono- and oligoglycosides and their ethoxylated analogs.
  • the nonethoxylated compounds have been found to be particularly suitable.
  • cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and
  • Trialkylmethylammonium chlorides e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride,
  • Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride are further cationic surfactants which can be used according to the invention.
  • Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.
  • Alkylamidoamines in particular fatty acid amidoamines, such as the stearylamidopropyldimethylamine obtainable under the name Tego Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.
  • esterquats such as the Distearoylethylhydroxyethylammoniummethosulfat available in a blend with Cetearylalkohle under the name Dehyquart® ® F 75 miles.
  • the compounds containing alkyl groups used as surfactants may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.
  • Other active ingredients, auxiliaries and additives are, for example
  • nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers
  • anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids and
  • Vinyl acetate / crotonic acid copolymers provided that they are stable as solids or preferably in
  • Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic,
  • Derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic
  • Hydrocolloids such as e.g. polyvinyl alcohol,
  • Structurants such as glucose, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example, soybean lecithin, egg lecithin and cephalins, and silicone oils
  • Protein hydrolysates in particular elastin, collagen, keratin, milk protein, soy protein and
  • Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their
  • Fats and waxes such as spermaceti, beeswax, montan wax, paraffins,
  • Complexing agents such as EDTA, NTA and phosphonic acids, Swelling and penetration substances such as carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
  • compositions according to the invention may contain at least one ammonium compound from the group consisting of ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate in an amount of from 0.5 to 10, preferably from 1 to 5,% by weight, based on the total composition of the composition ,
  • dyeing and / or brightening agents according to the invention may contain further active ingredients, auxiliaries and
  • Additives such as nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers,
  • Dimethyldiallylammonium chloride polymers acrylamide-dimethyldiallyl-ammonium chloride
  • Copolymers vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.
  • Butylaminoethyl methacrylate ⁇ -hydroxypropyl methacrylate copolymers anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids,
  • Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya
  • Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, such as soybean lecithin, egg lecithin and
  • Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2 -alkylimidazolinium methosulfate
  • Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
  • Light stabilizers in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
  • Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
  • Vitamins, provitamins and vitamin precursors in particular those of groups A, B 3 , B 5 , B 6 , C,
  • Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel,
  • Spruce needle horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime,
  • Ginger root Ginger root ,.
  • Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
  • Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
  • Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates,
  • Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
  • Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
  • Propellants such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air, Antioxidants, included
  • compositions according to the invention may contain the ingredients in a suitable aqueous, alcoholic or aqueous-alcoholic carrier.
  • a suitable aqueous, alcoholic or aqueous-alcoholic carrier for the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair.
  • a powdered or tablet-shaped formulation which is preferred for dyeing and / or brightening agents.
  • aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C 1 -C 4 -alkoxyethane, in particular ethanol or isopropanol.
  • the compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.
  • Preferred agents according to the invention are characterized in that they additionally contain a nonaqueous solvent, particularly preferred compositions according to the invention the solvent in a concentration of 0.1 to 30 weight percent, preferably in a concentration of 1 to 20 weight percent, most preferably in a concentration of 2 - 10 weight percent, each based on the agent included.
  • the solvent is selected from ethanol, n-propanol, isoropanol, n-butanol, propylene glycol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, phenoxyethanol and benzyl alcohol and mixtures thereof.
  • the pH of the compositions according to the invention can be adjusted within a wide range by suitable ingredients such as acidifying agent or alkalizing agent.
  • Oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen in the presence of oxidation dye precursors.
  • a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. This lightening effect may be desired regardless of the staining method.
  • oxidation dye precursors is therefore not a mandatory requirement for the use of oxidizing agents in the compositions of the invention.
  • Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate.
  • the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated.
  • catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.
  • Suitable metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Mn 4+ , Li + , Mg 2+ , Ca 2+ and Al 3+ . Particularly suitable are Zn 2+ , Cu 2+ and Mn 2+ .
  • the metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound.
  • Preferred salts are the acetates, sulfates, halides, lactates and tartrates.
  • Suitable enzymes are e.g. Peroxidases that can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g.
  • Pyruvate oxidase and pyruvic acid or its salts - alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and their salts, tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, Choline oxidase and choline, amino acid oxidase and amino acids.
  • the actual colorant is conveniently prepared immediately prior to use by mixing the preparation of the oxidizing agent with the preparation containing the compounds of formula I and optionally dye precursors.
  • the resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline medium.
  • the application temperatures can be in a range between 15 and 40 0 C.
  • the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.
  • an agent according to the invention may optionally be applied to the hair with additional dye precursors but also without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After a further exposure time of 10 to 20 minutes, the product is then rinsed and, if desired, shampooed again.
  • the corresponding agent is adjusted to a pH of about 4 to 7.
  • an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10.
  • the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent.
  • compositions of the invention are mixed immediately before application with a hydrogen peroxide solution.
  • concentration of this hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; As a rule, 6-12% solutions in water are used.
  • the proportions of dyeing and / or lightening agent and hydrogen peroxide solution are usually in the range 1: 1 to 1: 2, with an excess of hydrogen peroxide solution is particularly selected when no too pronounced Blondier Stil is desired.
  • the compositions according to the invention may contain further ingredients. For example, use of certain metal ions or complexes may be preferred to obtain intense colorations. Agents according to the invention which additionally contain Cu, Fe, Mn, Ru ions or complexes of these ions are preferred here.
  • Preferred agents according to the invention for dyeing and / or lightening keratinic fibers additionally contain Cu, Fe, Mn, Co, Ce, V, Ru ions or complexes of these ions, preferred agents being from 0.0001 to 2.5% by weight .-%, preferably 0.001 to 1 wt .-% of at least one compound from the group copper chloride (CuCl 2 ), copper sulfate (CuSO 4 ), iron (II) sulfate, manganese (II) sulfate, manganese (II) chloride, cobalt ( ll) chloride, cerium sulfate, cerium chloride, vanadium sulfate, manganese dioxide (MnO 2 ).
  • Complex images are substances that can complex metal ions.
  • Preferred complexing agents are so-called chelate complexing agents, ie substances which form cyclic compounds with metal ions, a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate".
  • chelate complexing agents ie substances which form cyclic compounds with metal ions, a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate”.
  • normally stretched compounds are closed by complex formation via an ion into rings.
  • the number of bound ligands depends on the coordination number of the central ion.
  • Customary and preferred chelate complex images in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and hydroxyethanediphosphonic acids or their alkali metal salts.
  • Complex-forming polymers ie polymers which carry functional groups either in the main chain themselves or in the side thereof, which can act as ligands and generally react with suitable metal atoms to form chelate complexes, can be used according to the invention.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1, 3-dicarbonyl - And crown ether residues with z. T. very specific. Activities towards ions of different metals.
  • Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, Polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.
  • polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA are preferred.
  • these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts.
  • alkali metal, ammonium or alkylammonium salts, in particular sodium salts are preferred.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the complexing agent used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. These substances will be described below.
  • phosphonates preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its hexasodium salt and / or diethylenetriaminepentamethylenephosphonate (DTPMP ) or its hepta- or octasodium salt.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • ETMP ethylenediamine tetramethylenephosphonate
  • DTPMP diethylenetriaminepentamethylenephosphonate
  • Particularly preferred agents according to the invention contain one or more substances from the group
  • NTA nitrilotriacetic acid
  • EDDG ethylenediamine-N-N'-diglutaric acid
  • polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, (ii) nitrogen-containing mono- or polycarboxylic acids,
  • cyclodextrins preferred agents being phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and especially 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its hexasodium salt and or diethylenetriaminepentamethylenephosphonate (DTPMP) or its hepta- or octasodium salt.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • ETMP ethylenediamine tetramethylenephosphonate
  • DTPMP diethylenetriaminepentamethylenephosphonate
  • Preferred agents according to the invention are formulated with little or no water.
  • Particularly preferred agents according to the invention are characterized in that they contain less than 5% by weight, preferably less than 2% by weight, more preferably less than 1% by weight and in particular less than 0.5% by weight of water, preferred agents being anhydrous.
  • the water content of the agent can be determined, for example, by means of titration according to Karl Fischer.
  • Another object of the present invention is a method for whitening keratin fibers, in particular human hair, characterized in that, if desired, a pretreatment agent M1 is applied to the fiber, then a means M2 on the fiber is used, wherein, if desired, the means M2 before the Application of a further agent M3 is added, this agent M2 is rinsed from the fiber after a time of 5-30 minutes and after treatment optionally a post-treatment agent M4 applied to the fiber and rinsed after a contact time of a few minutes, wherein at least one the agent M1, M2 or M3 is an agent according to the invention.
  • the agents according to the invention can accordingly be formulated as single-component agents (dyeing and whitening agents M2 or aftertreatment agents M4), as two-component agents (M2 + M3) or as three-component agents (M2 + M3 + M4) and used accordingly. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or feared; the agent to be used in such systems is manufactured by the consumer just prior to use by mixing the component. A dyeing and whitening process in which the whitening cream and the oxidizing agent are initially separate is preferred.
  • a further subject of the present invention is therefore a process for dyeing and lightening human hair, in which an aqueous-based composition containing hydrogen peroxide is mixed with an agent according to the invention to form a homogeneous composition and applied to the hair.
  • the aqueous composition contains from 1 to 20% by weight, preferably from 2 to 10% by weight and in particular from 3 to 6% by weight of hydrogen peroxide, calculated as 100% H 2 O 2 .
  • aqueous-based composition comprising hydrogen peroxide is mixed with an agent according to the invention in a weight ratio of 1: 5 to 10: 1, preferably 1: 2 to 5: 1 and in particular 1: 2 to 2: 1 is mixed to a homogeneous composition, and this is applied to the hair.
  • a further subject of the present invention is therefore a process for dyeing and lightening human hair, comprising an aqueous-based composition containing hydrogen peroxide with a further agent containing preferably at least one alkalinity donor and / or substantive hair dye and / or at least one oxidation dye precursor, and a composition according to the invention mixed to a homogeneous composition, and this is applied to the hair.
  • a further subject of the present invention is the use of polyol esters of the formula (I)
  • R 1 and R 2 independently of one another are -H or a straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 24 -alkyl or -alkenyl radical, preferably -H, -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
  • R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3 n is from 1 to 12, preferably from 2, 3, 4, 5, 6 in agents for dyeing and / or lightening keratinischer fibers.
  • the use of the compounds is the achievement of certain advantageous
  • Preferred according to the invention are uses for i. Increase in the whitening or bleaching performance and / or ii. Increasing the skin compatibility of brightening or bleaching agents and / or iii. Achieving neutral color results when bleaching and / or iv. Reduction of yellow shades when bleaching and / or v. Reduction of yellowing on keratin fibers.
  • the mutated mutandis applies to the preferred agents. Examples:
  • the concentrations of hydrogen peroxide were each 6.0%, the concentrations of the additives were z. T. varies between 1% and 10% (see table).
  • the solutions were additionally stabilized with 1.5% turpinal (60% solution of hydroxyethanediphosphonic acid) and 0.1% dipicolinic acid.

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Abstract

Performance-enhanced and irritation-reduced agents for the lightening and/or colouring of keratin fibres, in particular human hair, which in addition significantly minimise yellowing during bleaching, comprise - based on their weight - 0.5 to 15% by weight, preferably 1 to 12.5% by weight, particularly preferably 2.5 to 10% by weight and in particular 3 to 6% by weight, of hydrogen peroxide (calculated as 100% strength H2O2) and 0.001 to 15% by weight of at least one polyol ester of the formula (I) in which R1 and R2, independently of one another, are H or a straight-CHain or branched, saturated or mono- or polyunsaturated C1-24-alkyl or -alkenyl radical, preferably are -H, -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3, R3 and R4 independently of one another are -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3, n is values from 1 to 12, preferably 2, 3, 4, 5, 6. Moreover, 0.001 to 5% by weight of one or more oxidation dye precursors and/or direct dyes are preferably present.

Description

"Aufhell- und/oder Färbemittel mit Polyolestern" "Whitening and / or coloring agents with polyol esters"
Die vorliegende Erfindung betrifft Mittel zum Färben und/oder Aufhellen keratinischer Fasern, d.h. Mittel zur Anwendung auf Keratinfasern, insbesondere menschlichen Haaren, und deren Verwendung.The present invention relates to means for dyeing and / or whitening keratinic fibers, i. Agent for use on keratin fibers, in particular human hair, and their use.
Die Veränderung von Form und Farbe der Haare stellt einen wichtigen Bereich der modernen Kosmetik dar. Dadurch kann das Erscheinungsbild der Haare sowohl aktuellen Modeströmungen als auch den individuellen Wünschen der einzelnen Person angepaßt werden. Dabei können Dauerwell- und andere die Haarform verändernde Verfahren nahezu unabhängig vom Typ der zu behandelnden Haare eingesetzt werden. Dagegen sind Färbe- und Blondierverfahren auf bestimmte Ausgangshaarfarben begrenzt. Die Grundlagen der Blondierverfahren sind dem Fachmann bekannt und können in einschlägigen Monographien, z.B. von Kh. Schrader, Grundlagen und Rezepturen der Kosmetika, 2. Auflage, 1989, Dr. Alfred Hüthig Verlag, Heidelberg, oder W. Limbach (Hrg.), Kosmetik, 2. Auflage, 1995, Georg Thieme Verlag, Stuttgart, New York, nachgelesen werden.The change in shape and color of the hair is an important area of modern cosmetics dar. Thus, the appearance of the hair can be adapted to both current fashion trends and the individual desires of each person. In this case, permanent wave and other hair-changing methods can be used almost independently of the type of hair to be treated. In contrast, dyeing and bleaching processes are limited to certain initial hair colors. The basics of the bleaching processes are known to those skilled in the art and may be described in relevant monographs, e.g. by Kh. Schrader, Basics and Formulations of Cosmetics, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Limbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, be read.
Gleichzeitig besteht aber auch vielfach der Wunsch, die Haarfarbe zu ändern und zusammen mit der Haarfärbung auch eine Aufhellung des zu färbenden Haares zu erreichen.At the same time, however, there is often the desire to change the hair color and to achieve a brightening of the hair to be dyed together with the hair coloring.
Konventionelle Haarfärbemittel bestehen in der Regel aus mindestens einer Entwickler- und mindestens einer Kupplersubstanz und enthalten ggf. noch direktziehende Farbstoffe als Nuanceure. Kuppler- und Entwicklerkomponenten werden auch als Oxidationsfarbstoffvorprodukte bezeichnet.Conventional hair dyes usually consist of at least one developer and at least one coupler substance and possibly even contain direct dyes as Nuanceure. Coupler and developer components are also referred to as oxidation dye precursors.
Vor ihrer Anwendung auf menschliches Haar werden Haarfärbe- und/oder -aufhellungsmittel in fester oder pastöser Form mit verdünnter wäßriger Wasserstoffperoxid-Lösung vermischt. Diese Mischung wird dann auf das Haar aufgebracht und nach einer bestimmten Einwirkzeit wieder ausgespült. Die Einwirkungsdauer auf dem Haar zur Erzielung einer vollständigen Ausfärbung bzw. Aufhellung liegt zwischen etwa 30 und 40 Minuten. Es ist naheliegend, daß bei den Benutzern dieser Haarfarben oder Blondiermittel ein Bedürfnis besteht, diese Einwirkungszeit zu verringern.Before being applied to human hair, hair dyeing and / or lightening agents are mixed in solid or pasty form with dilute aqueous hydrogen peroxide solution. This mixture is then applied to the hair and rinsed again after a certain exposure time. The duration of exposure to the hair to achieve a complete coloration or whitening is between about 30 and 40 minutes. It is obvious that there is a need among users of these hair dyes or bleaching agents to reduce this exposure time.
Weder die pastenförmigen noch die pulverförmigen Färbe- und/oder Blondiermittel, die heute auf dem Markt sind, können als optimal angesehen werden. Während die Färbe- und/oder Blondierwirkung auf dem Haar als auf die Verbraucherbedürfnisse zugeschnitten bezeichnet werden kann, bestehen doch noch eine Reihe von Nachteilen und Problemen sowohl bei Herstellung als auch bei der Handhabung dieser Mittel.Neither the pasty nor the powdered dyeing and / or bleaching agents that are on the market today can be considered optimal. While the dyeing and / or bleaching effect on the hair may be said to be tailored to consumer needs, there are still a number of disadvantages and problems both in the manufacture and handling of these agents.
So verlaufen Colorations- und Blondierprozesse an keratinischen Fasern üblicherweise bei alkalischen pH-Werten, insbesondere zwischen 9,0 und 10,5. Diese pH-Werte sind notwendig, um eine Öffnung der äußeren Schuppenschicht (Cuticula) zu gewährleisten und eine Penetration der aktiven Spezies (Farbstoffvorprodukte und/oder Wasserstoffperoxid) in das Haar zu ermöglichen. Als Alkalisierungsmittel wird üblicherweise Ammoniak eingesetzt, der allerdings für die Anwender den Nachteil des intensiven Geruches und eventueller Reizung aufweist.Thus, coloration and bleaching processes on keratinic fibers usually proceed at alkaline pH values, in particular between 9.0 and 10.5. These pH values are necessary to ensure an opening of the outer cuticle (cuticle) and to allow a penetration of the active species (dye precursors and / or hydrogen peroxide) into the hair. The alkalizing agent used is usually ammonia, which however has the disadvantage of intense odor and possible irritation for the users.
In Marktprodukten werden als alternative Alkalisierungsmittel zu Ammoniak beispielsweise Aminomethylpropanol oder Monoethanolamin eingesetzt. Da sie in ihrer Leistung allerdings oft hinter Ammoniak zurückbleiben, werden sie üblicherweise in Abmischung mit Ammoniak eingesetzt. Aber auch hier wird die Leistung des Ammoniaks beeinträchtigt, insbesondere in Bezug auf die Parameter Graubadeckung, Aufhellleistung und Farbergebnis.In market products, for example, aminomethylpropanol or monoethanolamine are used as alternative alkalizing agents to ammonia. However, since they often lag behind ammonia in their performance, they are usually used in admixture with ammonia. But even here, the performance of the ammonia is impaired, especially with regard to the parameters gray covering, whitening performance and color result.
Es besteht daher weiterhin ein Bedarf nach Wirkstoffen bzw. Wirkstoffkombinationen für Aufhell- und Färbemittel mit reduziertem Ammoniakgehalt. Insbesondere sollte in ammoniakreduzierten oder gar -freien farbstoff- und/oder Wasserstoffperoxid haltigen Formulierungen eine mit herkömmlichen ammoniakbasierten Mitteln vergleichbare Leistung erzielt werden.There is therefore still a need for active ingredients or active substance combinations for brightening and coloring agents with reduced ammonia content. In particular, in ammonia-reduced or even-free dye and / or hydrogen peroxide-containing formulations, a performance comparable to conventional ammonia-based compositions should be achieved.
Ein weiteres Problem bei der Blondierung besteht darin, daß bei der gewünschten maximalen Aufhellleistung oft ein unerwünschter gelblicher Farbton resultiert. Dieses Problem tritt auch bei der oxidativen Färbung auf, dort wird der Gelbstich allerdings durch die Farbstoffe überlagert, so daß er weniger auffällt.Another problem with bleaching is that the desired maximum whitening performance often results in an undesirable yellowish hue. This problem also occurs in the oxidative dyeing, where the yellowing is, however, superimposed by the dyes, so that it is less noticeable.
Die Aufgabe der vorliegenden Erfindung bestand darin, Aufhell- bzw. Blondiermittel bereitzustellen, die in ihrer Aufhell- bzw. Blondierleistung gesteigert sind und dennoch eine gesteigerte Hautverträglichkeit aufweisen. Bei Blondiermitteln sollte darüber hinaus ein neutrales Farbergebnis erzielt und die Verringerung von gelben Farbtönen beim Blondieren und die Verringerung von Vergilbungen auf keratinischen Fasern ermöglicht werden.The object of the present invention was to provide lightening or bleaching agents which are increased in their whitening or bleaching performance and yet have an increased skin compatibility. Bleaching agents should also have a neutral color result and to reduce yellowing when bleaching and to reduce yellowing on keratinic fibers.
Es wurde nun gefunden, daß sich Polyolester mit besonderem Vorteil in Haarfärbe- und -aufhellungsmittel einarbeiten lassen und zu einer Leistungssteigerung dieser Mittel führen. Der Einsatz der Polyolester führt zu den gewünschten Vorteilen, wobei insbesondere die Kombination mit Azolen diese Vorteile zutage treten läßt.It has now been found that polyol esters can be incorporated with particular advantage into hair dyeing and whitening agents and lead to an increase in the performance of these agents. The use of the polyol ester leads to the desired advantages, wherein in particular the combination with azoles brings these advantages to light.
In der deutschen Offenlegungsschrift DE 23 44 990 A1 werden Mischungen zum Aktivieren anorganischer Peroxidbleichmittel offenbart, die mindestens einen Essigsäureester eines Monosaccharids oder eines Disaccharids oder eines Zuckeralkohols oder von Erythritol in Kombination mit mindestens einem Essigsäureester eines mehrwertigen Alkohols, insbesondere Glycerintriacetat, enthalten. Zusammensetzungen zur Behandlung keratinischer Fasern werden in dieser Schrift nicht offenbart.German Offenlegungsschrift DE 23 44 990 A1 discloses mixtures for activating inorganic peroxygen bleaches containing at least one acetic acid ester of a monosaccharide or a disaccharide or a sugar alcohol or of erythritol in combination with at least one acetic acid ester of a polyhydric alcohol, in particular glycerol triacetate. Compositions for treating keratinous fibers are not disclosed in this document.
Die WO00/77297 offenbart den Einsatz von Glycerinestern der Mono-, Di- oder Triameisensäure, der Essigsäure oder der Propionsäure als Bleichaktivatoren in der Papierbleiche. Auch hier werden Zusammensetzungen zur Behandlung keratinischer Fasern nicht offenbart.WO00 / 77297 discloses the use of glycerol esters of mono-, di- or tri-formic acid, acetic acid or propionic acid as bleach activators in paper bleaching. Again, compositions for treating keratinic fibers are not disclosed.
Die deutsche Gebrauchsmusterschrift DE 20 2006 002 355 U1 offenbart kosmetische oder dermatologische Zubereitungen, die Glyceroltriacetat enthalten. Die in dieser Schrift offenbarten Mittel sind vorzugsweise frei von Farbstoffen und dienen nicht der Farbveränderung keratinischer Fasern.German Utility Model DE 20 2006 002 355 U1 discloses cosmetic or dermatological preparations containing glycerol triacetate. The agents disclosed in this document are preferably free of dyes and do not serve the color change keratinischer fibers.
Gegenstand der vorliegenden Erfindung sind in einer ersten Ausführungsform Mittel zum Färben und/oder Aufhellen von Keratinfasern, insbesondere menschlichen Haaren, enthaltend -bezogen auf ihr Gewicht - a) 0,5 bis 15 Gew.-%, vorzugsweise 1 bis 12,5 Gew.-%, besonders bevorzugt 2,5 bis 10 Gew.-% und insbesondere 3 bis 6 Gew.-% Wasserstoffperoxid (berechnet als 100%iges H2O2), b) 0,001 bis 15 Gew.-% mindestens eines Polyolesters der Formel (I)
Figure imgf000006_0001
worinIn a first embodiment, the present invention relates to agents for dyeing and / or lightening keratin fibers, in particular human hair, containing-based on their weight-a) 0.5 to 15% by weight, preferably 1 to 12.5% by weight. -%, particularly preferably 2.5 to 10 wt .-% and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H 2 O 2 ), b) 0.001 to 15 wt .-% of at least one polyol ester of the formula (I)
Figure imgf000006_0001
wherein
R1 und R2 stehen unabhängig voneinander für -H oder einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C-ι-24-Alkyl- oder -Alkenylrest, vorzugsweise für -H, -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 R 1 and R 2 independently of one another are -H or a straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 24 -alkyl or -alkenyl radical, preferably -H, -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
R3 und R4 stehen unabhängig voneinander für -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 n steht für Werte von 1 bis 12, vorzugsweise für 2, 3, 4, 5, 6.R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3 n is from 1 to 12, preferably from 2, 3, 4, 5, 6.
Unter Keratinfasern sind dabei Pelze, Wolle, Federn und insbesondere menschliche Haare zu verstehen. Obwohl die erfindungsgemäßen Mittel in erster Linie zum Färben und/oder Aufhellen von Keratinfasern geeignet sind, steht prinzipiell einer Verwendung auch auf anderen Gebieten nichts entgegen.Keratin fibers mean furs, wool, feathers and in particular human hair. Although the compositions according to the invention are primarily suitable for dyeing and / or whitening keratin fibers, in principle, there is nothing to prevent their use in other fields as well.
Die erfindungsgemäßen Mittel enthalten als ersten wesentlichen Inhaltsstoff 0,5 bis 15 Gew.-%, vorzugsweise 1 bis 12,5 Gew.-%, besonders bevorzugt 2,5 bis 10 Gew.-% und insbesondere 3 bis 6 Gew.-% Wasserstoffperoxid (berechnet als 100%iges H2O2).The compositions of the invention contain as the first essential ingredient 0.5 to 15 wt .-%, preferably 1 to 12.5 wt .-%, particularly preferably 2.5 to 10 wt .-% and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H 2 O 2 ).
Das Wasserstoffperoxid kann auch in Form dessen Anlagerungsverbindungen an feste Träger eingesetzt werden, bevorzugt wird Wasserstoffperoxid selbst verwendet. Das Wasserstoffperoxid wird als Lösung oder in Form einer festen Anlagerungsverbindung von Wasserstoffperoxid an anorganische oder organische Verbindungen, wie beispielsweise Natriumperborat, Natriumpercarbonat, Magnesiumpercarbonat, Natriumpercarbamid, Polyvinylpyrrolidon n H2O2 (n ist eine positive ganze Zahl größer 0), Harnstoffperoxid und Melaminperoxid, eingesetzt. Erfindungsgemäß ganz besonders bevorzugt sind wässrige Wasserstoffperoxid-Lösungen. Die Konzentration einer Wasserstoffperoxid-Lösung wird einerseits von den gesetzlichen Vorgaben und andererseits von dem gewünschten Effekt bestimmt; vorzugsweise werden 6- bis 12-prozentige Lösungen in Wasser verwendet.The hydrogen peroxide may also be used in the form of its attachment compounds to solid supports, preferably hydrogen peroxide itself is used. The hydrogen peroxide is used as a solution or in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H 2 O 2 (n is a positive integer greater than 0), urea peroxide and melamine peroxide, used. Very particularly preferred according to the invention are aqueous hydrogen peroxide solutions. The concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6-12% solutions in water are used.
Die erfindungsgemäßen Mittel können zusätzlich weitere Oxidationsmittel enthalten, die auch als „Booster" bezeichnet werden. Die Auswahl dieser weiteren Peroxoverbindungen unterliegt prinzipiell keinen Beschränkungen; übliche, dem Fachmann bekannte Peroxoverbindungen sind beispielsweise Ammoniumperoxidisulfat, Kaliumperoxidisulfat, Natriumperoxidisulfat, Ammoniumpersulfat, Kaliumpersulfat, Natriumpersulfat, Percarbonate wie Magnesiumpercarbonat, Peroxide wie Bariumperoxid sowie Perborate, Harnstoffperoxid und Melaminperoxid. Unter diesen Peroxoverbindungen, die auch in Kombination eingesetzt werden können, sind erfindungsgemäß die anorganischen Verbindungen bevorzugt. Besonders bevorzugt sind die Peroxidisulfate, insbesondere Kombinationen aus mindestens zwei Peroxidisulfaten. Hier sind erfindungsgemäße Mittel zum Färben und/oder Aufhellen keratinischer Fasern bevorzugt, die zusätzlich 0,01 bis 2 Gew.-% mindestens einer festen Peroxoverbindung, die ausgewählt ist aus Ammonium-, Alkalimetall- und Erdalkalimetallpersulfaten, -peroxomonosulfaten und -peroxidisulfaten enthalten, wobei bevorzugte Mittel Peroxidisulfate enthalten, die vorzugsweise ausgewählt sind aus Natriumperoxidisulfat und/oder Kaliumperoxidisulfat und/oder Ammoniumperoxidisulfat und wobei besonders bevorzugte Mittel mindestens zwei verschiedene Peroxid islfate enthalten.The compositions according to the invention may additionally comprise further oxidizing agents, which are also referred to as "boosters." The usual peroxo compounds known to the person skilled in the art are, for example, ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, ammonium persulfate, potassium persulfate, sodium persulfate, percarbonates Magnesium percarbonate, peroxides such as barium peroxide and perborates, urea peroxide and melamine peroxide are among these peroxo compounds which can also be used in combination and / or lightening keratinic fibers which additionally comprise from 0.01 to 2% by weight of at least one solid peroxy compound selected from Am mono-, alkali metal and alkaline earth metal persulfates, peroxomonosulfates and peroxydisulfates, preferred agents containing peroxydisulfates, which are preferably selected from sodium peroxydisulfate and / or potassium peroxydisulfate and / or ammonium peroxydisulfate and particularly preferred agents containing at least two different peroxide islfates.
Weiterhin besonders bevorzugt sind Persulfate, insbesondere das als Carosche Salz bezeichnete Gemisch aus Kaliumperoxosulfat, Kaliumhydrogensulfat und Kaliumsulfat.Particular preference is furthermore given to persulfates, in particular the mixture of potassium peroxosulfate, potassium hydrogen sulfate and potassium sulfate, referred to as Caro's salt.
Die erfindungsgemäßen Mittel enthalten als zweiten wesentlichen Inhaltsstoff 0,001 bis 15 Gew.-% mindestens eines Polyolesters der Formel (I) The compositions according to the invention contain as the second essential ingredient 0.001 to 15% by weight of at least one polyol ester of the formula (I)
Figure imgf000008_0001
Figure imgf000008_0001
In der Formel (I) stehen die Reste R1 und R2 unabhängig voneinander für -H oder einen einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C-|.24-Alkyl- oder -Alkenylrest, vorzugsweise für -H, -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2- CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 In the formula (I), the radicals R 1 and R 2 independently of one another represent -H or one of a straight-chain or branched, saturated or mono- or polyunsaturated C 1-. 24 alkyl or alkenyl radical, preferably -H, -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
Der Index n steht für Werte von 1 bis 12, vorzugsweise für 2, 3, 4, 5, 6. Im Falle von n = 2 handelt es sich bei den Verbindungen der Formel (I) um Diester des Ethylenglycols (bei R1 = R2 = -H), bei n = 3 um Triester des Glycerins (bei R1 = R2 = -H). Bei n = 4 steht die Formel (I) für Tetraester der Tetrite (bei R1 = R2 = -H), beispielsweise für Tetraester des Erythrits (meso-1 ,2,3,4-Butantetrol). Bei n = 5 handelt es sich um Pentaester der Pentite (Pentitole) (bei R1 = R2 = -H), d.h. um Pentaester der die vier stereoisomeren 1 ,2,3,4,5-Pentanpentaole HO -CH2-(CHOH)3-CH2-OH. Bei n = 6 handelt es sich um Hexaester der Hexite (Hexitole) (bei R1 = R2 = -H), d.h. um Hexaester sechswertiger Alkohole der allg. Formel HO-CH2-(CHOH)4-CH2-OH, die mit den entsprechenden Hexosen verwandt u. durch Reduktion aus ihnen herzustellen sind. Die wichtigsten Hexit-hexaester sind Ester von Galactitol, Mannitol und Sorbitol.The index n stands for values from 1 to 12, preferably for 2, 3, 4, 5, 6. In the case of n = 2, the compounds of the formula (I) are diesters of the ethylene glycol (in the case of R 1 = R 2 = -H), at n = 3 to triester of glycerol (when R 1 = R 2 = -H). When n = 4, the formula (I) stands for tetraesters of tetrites (for R 1 = R 2 = -H), for example for tetraesters of erythritol (meso-1, 2,3,4-butanetetrol). N = 5 is a pentaester of pentitols (where R 1 = R 2 = -H), ie pentaester which is the four stereoisomeric 1,2,3,4,5-pentane-pentaols HO-CH 2 - ( CHOH) 3 -CH 2 -OH. N = 6 is hexaester of the hexites (hexitols) (in the case of R 1 = R 2 = -H), ie hexaesters of hexahydric alcohols of the general formula HO-CH 2 - (CHOH) 4 -CH 2 -OH, related to the corresponding hexoses u. to be made from them by reduction. The most important hexithexaesters are esters of galactitol, mannitol and sorbitol.
R3 und R4 stehen in Formel (I) unabhängig voneinander für -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 Bevorzugt sind Methyl- und Ethylgruppen, so daß die entsprechenden Essigsäure- bzw. Propionsäureester bevorzugt sind.R 3 and R 4 in formula (I) are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3 Preference is given to methyl and ethyl groups, so that the corresponding acetic or propionic acid esters are preferred.
Mit besonderem Vorzug steht n in Formel (I) für die Zahl 2, und die Reste R1 und R2 stehen für -H), d.h. es werden Ester des Glycerins eingesetzt. Hier sind erfindungsgemäß bevorzugte Mittel zum Färben und/oder Aufhellen keratinischer Fasern dadurch gekennzeichnet, daß sie 0,1 bis 15 Gew.-%, vorzugsweise 1 bis 12,5 Gew.-%, besonders bevorzugt 2,5 bis 10 Gew.-% und insbesondere 5 bis 7,5 Gew.-% mindestens eines Polyolesters der Formel (Ia)With particular preference n in formula (I) stands for the number 2, and the radicals R 1 and R 2 stand for -H), ie esters of glycerol are used. Here, according to the invention, preferred agents for dyeing and / or lightening keratinic fibers are characterized in that they contain 0.1 to 15% by weight, preferably 1 to 12.5% by weight, more preferably 2.5 to 10% by weight and in particular 5 to 7.5% by weight of at least one polyol ester of the formula (Ia)
Figure imgf000009_0001
enthalten, in der
Figure imgf000009_0001
included in the
R1 und R2 stehen unabhängig voneinander für -H oder einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C-i-24-Alkyl- oder -Alkenylrest, vorzugsweise für -H, -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 R 1 and R 2 independently represent -H or a straight or branched, saturated or mono- or polyunsaturated Ci- 24 alkyl or alkenyl group, preferably -H, -CH 3; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
R3 und R4 stehen unabhängig voneinander für -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
Bevorzugte Verbindungen der Formel (Ia) sindPreferred compounds of the formula (Ia) are
H3C-C(O)-O-CH2-CH(O-C(O)-CH3)-CH2-O-C(O)-CH3 H 3 CC (O) -O-CH 2 -CH (OC (O) -CH 3 ) -CH 2 -OC (O) -CH 3
H3C-CH2-C(O)-O-CH2-CH(O-C(O)-CH2CH3)-CH2-O-C(O)-CH2CH3 H 3 C-CH 2 -C (O) -O-CH 2 -CH (OC (O) -CH 2 CH 3 ) -CH 2 -OC (O) -CH 2 CH 3
H3C-(CH2)2-C(O)-O-CH2-CH(O-C(O)-CH2CH2CH3)-CH2-O-C(O)-CH2CH2CH3 H 3 C- (CH 2 ) 2 -C (O) -O-CH 2 -CH (OC (O) -CH 2 CH 2 CH 3 ) -CH 2 -OC (O) -CH 2 CH 2 CH 3
(H3C)2CH-C(O)-O-CH2-CH(O-C(O)-CH(CH3)2)-CH2-O-C(O)-CH(CH3)2 (H 3 C) 2 CH-C (O) -O-CH 2 -CH (OC (O) -CH (CH 3 ) 2 ) -CH 2 -OC (O) -CH (CH 3 ) 2
H3C-(CH2)3-C(O)-O-CH2-CH(O-C(O)-(CH2)3CH3)-CH2-O-C(O)-(CH2)3CH3 H 3 C- (CH 2 ) 3 -C (O) -O-CH 2 -CH (OC (O) - (CH 2 ) 3 CH 3 ) -CH 2 -OC (O) - (CH 2 ) 3 CH 3
(H3C)2CH-CH2-C(O)-O-CH2-CH(O-C(O)-CH2-CH(CH3)2)-CH2-O-C(O)-CH2-CH(CH3)2 (H 3 C) 2 CH-CH 2 -C (O) -O-CH 2 -CH (OC (O) -CH 2 -CH (CH 3 ) 2 ) -CH 2 -OC (O) -CH 2 - CH (CH 3 ) 2
H3C-CH2-CH(CH3)-C(O)-O-CH2-CH(O-C(O)-CH(CH3)CH2CH3)-CH2-O-C(O)-CH(CH3)CH2CH3 H 3 C-CH 2 -CH (CH 3 ) -C (O) -O-CH 2 -CH (OC (O) -CH (CH 3 ) CH 2 CH 3 ) -CH 2 -OC (O) -CH (CH 3 ) CH 2 CH 3
(H3C)3C-C(O)-O-CH2-CH(O-C(O)-CH(CH3)CH2CH3)-CH2-O-C(O)-CH(CH3)CH2CH3 (H 3 C) 3 CC (O) -O-CH 2 -CH (OC (O) -CH (CH 3 ) CH 2 CH 3 ) -CH 2 -OC (O) -CH (CH 3 ) CH 2 CH 3
Zusätzlich zu den Glycerinestern oder an ihrer Stelle können erfindungsgemäß Verbindungen der Formel (I) eingesetzt werden, in der n für die Zahl 3 steht und die Reste R1 und R2 für -H stehen, d.h. es werden Ester des 1 ,2,3,4-Butantetrols eingesetzt. Hier sind erfindungsgemäß bevorzugte Mittel zum Färben und/oder Aufhellen keratinischer Fasern dadurch gekennzeichnet, daß sie 0,1 bis 15 Gew.-%, vorzugsweise 1 bis 12,5 Gew.-%, besonders bevorzugt 2,5 bis 10 Gew.-% und insbesondere 5 bis 7,5 Gew.-% mindestens eines Polyolesters der Formel (Ib)In addition to the glycerol esters or in their place, compounds of the formula (I) according to the invention can be used in which n is the number 3 and the radicals R 1 and R 2 are -H, ie esters of 1, 2,3 , 4-butanetetrols used. Here are inventively preferred means for dyeing and / or whitening keratinic fibers, characterized in that they contain 0.1 to 15% by weight, preferably 1 to 12.5% by weight, more preferably 2.5 to 10% by weight and in particular 5 to 7 5% by weight of at least one polyol ester of the formula (Ib)
Figure imgf000010_0001
enthalten, in der
Figure imgf000010_0001
included in the
R1 und R2 stehen unabhängig voneinander für -H oder einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C-ι-24-Alkyl- oder -Alkenylrest, vorzugsweise für -H, -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 R 1 and R 2 independently of one another are -H or a straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 24 -alkyl or -alkenyl radical, preferably -H, -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
R3 und R4 stehen unabhängig voneinander für -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
Bevorzugte Verbindungen der Formel (Ib) sindPreferred compounds of the formula (Ib) are
H3C-C(O)-O-[CH2-CH(O-C(O)-CH3)I2-CH2-O-C(O)-CH3 H 3 CC (O) -O- [CH 2 -CH (OC (O) -CH 3 ) I 2 -CH 2 -OC (O) -CH 3
H3C-CH2-C(O)-O-[CH2-CH(O-C(O)-CH2CH3)I2-CH2-O-C(O)-CH2CH3 H 3 C-CH 2 -C (O) -O- [CH 2 -CH (OC (O) -CH 2 CH 3 ) I 2 -CH 2 -OC (O) -CH 2 CH 3
H3C-(CH2)2-C(O)-O-[CH2-CH(O-C(O)-CH2CH2CH3)]2-CH2-O-C(O)-CH2CH2CH3 H 3 C- (CH 2 ) 2 -C (O) -O- [CH 2 -CH (OC (O) -CH 2 CH 2 CH 3 )] 2 -CH 2 -OC (O) -CH 2 CH 2 CH 3
(H3C)2CH-C(O)-O-[CH2-CH(O-C(O)-CH(CH3)2)]2-CH2-O-C(O)-CH(CH3)2 (H 3 C) 2 CH-C (O) -O- [CH 2 -CH (OC (O) -CH (CH 3 ) 2 )] 2 -CH 2 -OC (O) -CH (CH 3 ) 2
H3C-(CH2)3-C(O)-O-[CH2-CH(O-C(O)-(CH2)3CH3)]2-CH2-O-C(O)-(CH2)3CH3 H 3 C- (CH 2 ) 3 -C (O) -O- [CH 2 -CH (OC (O) - (CH 2 ) 3 CH 3 )] 2 -CH 2 -OC (O) - (CH 2 ) 3 CH 3
(H3C)2CH-CH2-C(O)-O-[CH2-CH(O-C(O)-CH2-CH(CH3)2)]2-CH2-O-C(O)-CH2-CH(CH3)2 (H 3 C) 2 CH-CH 2 -C (O) -O- [CH 2 -CH (OC (O) -CH 2 -CH (CH 3 ) 2 )] 2 -CH 2 -OC (O) - CH 2 -CH (CH 3 ) 2
H3C-CH2-CH(CH3)-C(O)-O-[CH2-CH(O-C(O)-CH(CH3)CH2CH3)]2-CH2-O-C(O)-CH(CH3)CH2CH3 H 3 C-CH 2 -CH (CH 3 ) -C (O) -O- [CH 2 -CH (OC (O) -CH (CH 3 ) CH 2 CH 3 )] 2 -CH 2 -OC (O ) -CH (CH 3 ) CH 2 CH 3
(H3C)3C-C(O)-O-[CH2-CH(O-C(O)-CH(CH3)CH2CH3)I2-CH2-O-C(O)-CH(CH3)CH2CH3 (H 3 C) 3 CC (O) -O- [CH 2 -CH (OC (O) -CH (CH 3 ) CH 2 CH 3 ) I 2 -CH 2 -OC (O) -CH (CH 3 ) CH 2 CH 3
Verbindungen der Formel (I), in denen n für 4 bzw. für 5 steht, sind ebenfalls erfindungsgemäß mit Vorzug einsetzbar. Bevorzugte Vertreter dieser Ausführungsform sind: H3C-C(O)-O-[CH2-CH(O-C(O)-CH3)I3-CH2-O-C(O)-CH3 Compounds of the formula (I) in which n is 4 or 5 are likewise preferably usable according to the invention. Preferred representatives of this embodiment are: H 3 CC (O) -O- [CH 2 -CH (OC (O) -CH 3 ) I 3 -CH 2 -OC (O) -CH 3
H3C-CH2-C(O)-O-[CH2-CH(O-C(O)-CH2CH3)I3-CH2-O-C(O)-CH2CH3 H 3 C-CH 2 -C (O) -O- [CH 2 -CH (OC (O) -CH 2 CH 3 ) I 3 -CH 2 -OC (O) -CH 2 CH 3
H3C-(CH2)2-C(O)-O-[CH2-CH(O-C(O)-CH2CH2CH3)]3-CH2-O-C(O)-CH2CH2CH3 H 3 C- (CH 2 ) 2 -C (O) -O- [CH 2 -CH (OC (O) -CH 2 CH 2 CH 3 )] 3 -CH 2 -OC (O) -CH 2 CH 2 CH 3
(H3C)2CH-C(O)-O-[CH2-CH(O-C(O)-CH(CH3)2)]3-CH2-O-C(O)-CH(CH3)2 (H 3 C) 2 CH-C (O) -O- [CH 2 -CH (OC (O) -CH (CH 3 ) 2 )] 3 -CH 2 -OC (O) -CH (CH 3 ) 2
H3C-(CH2)3-C(O)-O-[CH2-CH(O-C(O)-(CH2)3CH3)]3-CH2-O-C(O)-(CH2)3CH3 H 3 C- (CH 2 ) 3 -C (O) -O- [CH 2 -CH (OC (O) - (CH 2 ) 3 CH 3 )] 3 -CH 2 -OC (O) - (CH 2 ) 3 CH 3
(H3C)2CH-CH2-C(O)-O-[CH2-CH(O-C(O)-CH2-CH(CH3)2)]3-CH2-O-C(O)-CH2-CH(CH3)2 (H 3 C) 2 CH-CH 2 -C (O) -O- [CH 2 -CH (OC (O) -CH 2 -CH (CH 3 ) 2 )] 3 -CH 2 -OC (O) - CH 2 -CH (CH 3 ) 2
H3C-CH2-CH(CH3)-C(O)-O-[CH2-CH(O-C(O)-CH(CH3)CH2CH3)]3-CH2-O-C(O)-CH(CH3)CH2CH3 H 3 C-CH 2 -CH (CH 3 ) -C (O) -O- [CH 2 -CH (OC (O) -CH (CH 3 ) CH 2 CH 3 )] 3 -CH 2 -OC (O ) -CH (CH 3 ) CH 2 CH 3
(H3C)3C-C(O)-O-[CH2-CH(O-C(O)-CH(CH3)CH2CH3)I3-CH2-O-C(O)-CH(CH3)CH2CH3 (H 3 C) 3 CC (O) -O- [CH 2 -CH (OC (O) -CH (CH 3 ) CH 2 CH 3 ) I 3 -CH 2 -OC (O) -CH (CH 3 ) CH 2 CH 3
H3C-C(O)-O-[CH2-CH(O-C(O)-CH3)I4-CH2-O-C(O)-CH3 H 3 CC (O) -O- [CH 2 -CH (OC (O) -CH 3 ) I 4 -CH 2 -OC (O) -CH 3
H3C-CH2-C(O)-O-[CH2-CH(O-C(O)-CH2CH3)I4-CH2-O-C(O)-CH2CH3 H 3 C-CH 2 -C (O) -O- [CH 2 -CH (OC (O) -CH 2 CH 3 ) I 4 -CH 2 -OC (O) -CH 2 CH 3
H3C-(CH2)2-C(O)-O-[CH2-CH(O-C(O)-CH2CH2CH3)]4-CH2-O-C(O)-CH2CH2CH3 H 3 C- (CH 2 ) 2 -C (O) -O- [CH 2 -CH (OC (O) -CH 2 CH 2 CH 3 )] 4 -CH 2 -OC (O) -CH 2 CH 2 CH 3
(H3C)2CH-C(O)-O-[CH2-CH(O-C(O)-CH(CH3)2)]4-CH2-O-C(O)-CH(CH3)2 (H 3 C) 2 CH-C (O) -O- [CH 2 -CH (OC (O) -CH (CH 3 ) 2 )] 4 -CH 2 -OC (O) -CH (CH 3 ) 2
H3C-(CH2)3-C(O)-O-[CH2-CH(O-C(O)-(CH2)3CH3)]4-CH2-O-C(O)-(CH2)3CH3 H 3 C- (CH 2 ) 3 -C (O) -O- [CH 2 -CH (OC (O) - (CH 2 ) 3 CH 3 )] 4 -CH 2 -OC (O) - (CH 2 ) 3 CH 3
(H3C)2CH-CH2-C(O)-O-[CH2-CH(O-C(O)-CH2-CH(CH3)2)]4-CH2-O-C(O)-CH2-CH(CH3)2 (H 3 C) 2 CH-CH 2 -C (O) -O- [CH 2 -CH (OC (O) -CH 2 -CH (CH 3 ) 2 )] 4 -CH 2 -OC (O) - CH 2 -CH (CH 3 ) 2
H3C-CH2-CH(CH3)-C(O)-O-[CH2-CH(O-C(O)-CH(CH3)CH2CH3)]4-CH2-O-C(O)-CH(CH3)CH2CH3 H 3 C-CH 2 -CH (CH 3 ) -C (O) -O- [CH 2 -CH (OC (O) -CH (CH 3 ) CH 2 CH 3 )] 4 -CH 2 -OC (O ) -CH (CH 3 ) CH 2 CH 3
(H3C)3C-C(O)-O-[CH2-CH(O-C(O)-CH(CH3)CH2CH3)I4-CH2-O-C(O)-CH(CH3)CH2CH3 (H 3 C) 3 CC (O) -O- [CH 2 -CH (OC (O) -CH (CH 3 ) CH 2 CH 3 ) I 4 -CH 2 -OC (O) -CH (CH 3 ) CH 2 CH 3
Die erfindungsgemäßen Mittel dienen als Mittel zum Färben und/oder Aufhellen keratinischer Fasern. Reine Aufhellmittel, die auch als Blondiermittel bezeichnet werden, enthalten zusätzlich vorzugsweise Oxidationsmittel (siehe unten). Vorzugsweise werden die erfindungsgemäßen Mittel als Färbemittel bereitgestellt, die dienen nicht (nur) einer Aufhellung, sondern auch oder ausschließlich einer Farbveränderung der mit ihnen behandelten keratinischen Fasern. Mittel, welche gleichzeitig färbend und aufhellend wirken, werden auch als aufhellende Färbemittel bezeichnet.The agents according to the invention serve as agents for dyeing and / or lightening keratinic fibers. Pure brighteners, which are also referred to as Blondiermittel, additionally preferably contain oxidizing agents (see below). Preferably, the agents according to the invention are provided as colorants which do not serve (only) to lighten, but also or exclusively to a color change of the keratinic fibers treated with them. Agents which simultaneously dye and brighten are also referred to as lightening dyes.
Bevorzugte erfindungsgemäße Mittel zum Färben und/oder Aufhellen keratinischer Fasern sind dadurch gekennzeichnet, daß sie zusätzlich - bezogen auf ihr Gewicht - 0,001 bis 5 Gew.-% eines oder mehrerer Oxidationsfarbstoffvorprodukte und/oder direktziehender Farbstoffe enthalten.Preferred agents for dyeing and / or lightening keratinic fibers according to the invention are characterized in that they additionally contain, based on their weight, from 0.001 to 5% by weight of one or more oxidation dye precursors and / or direct dyes.
Die erfindungsgemäßen Mittel sind vorzugsweise Färbemittel, d.h. Mittel zur Veränderung der Farbe keratinischer Fasern. Unter diesen sind insbesondere die so genannten Oxidationsfärbemittel bevorzugt. Erfindungsgemäße Oxidationsfärbemittel enthalten mindestens eine Kuppler- und mindestens eine Entwicklerkomponente. Kuppler- und Entwicklerkomponenten werden auch als Oxidationsfarbstoffvorprodukte bezeichnet. Zudem können die erfindungsgemäßen Oxidationsfärbemittel auch noch direktziehende Farbstoffe als Nuanceure enthalten. Erfindungsgemäß bevorzugte Mittel zum Färben und/oder Aufhellen keratinischer Fasern sind demnach dadurch gekennzeichnet, daß sie mindestens ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp und/oder Kupplertyp enthalten.The agents according to the invention are preferably colorants, ie agents for changing the color of keratinic fibers. Among these are in particular the so-called oxidation colorants prefers. Oxidation colorants according to the invention contain at least one coupler and at least one developer component. Coupler and developer components are also referred to as oxidation dye precursors. In addition, the oxidation colorants according to the invention may also contain substantive dyes as nuances. According to preferred means for dyeing and / or lightening keratinischer fibers are therefore characterized in that they contain at least one oxidation dye precursor of the developer type and / or coupler type.
Als Entwicklerkomponenten werden üblicherweise primäre aromatische Amine mit einer weiteren, in para- oder ortho-Position befindlichen freien oder substituierten Hydroxy- oder Aminogruppe, Diaminopyridinderivate, heterocyclische Hydrazone, 4-Aminopyrazolonderivate sowie 2,4,5,6- Tetraaminopyrimidin und dessen Derivate eingesetzt.The developer components are usually primary aromatic amines with a further, located in the para or ortho position free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone and 2,4,5,6-tetraaminopyrimidine and its derivatives used.
Spezielle Vertreter sind beispielsweise p-Phenylendiamin, p-Toluylendiamin, 2,4,5,6-Tetraamino- pyrimidin, p-Aminophenol, N,N-Bis-(2-hydroxyethyl)-p-phenylendiamin, 2-(2,5-Diaminophenyl)- ethanol, 2-(2,5-Diaminophenoxy)-ethanol, 1-Phenyl-3-carboxyamido-4-amino-pyrazol-5-on, 4-Amino- 3-methylphenol, 2-Aminomethyl-4-aminophenol, 2-Hydroxymethyl-4-aminophenol, 2-Hydroxy-4,5,6- triaminopyrimidin, 2,4-Dihydroxy-5,6-diaminopyrimidin und 2,5,6-Triamino-4-hydroxypyrimidin. Als Kupplerkomponenten werden in der Regel m-Phenylendiaminderivate, Naphthole, Resorcin und Resorcinderivate, Pyrazolone, m-Aminophenole und substituierte Pyridinderivate verwendet. AlsSpecific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5 Diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxamido-4-amino-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4- aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine. As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used. When
Kupplersubstanzen eignen sich insbesondere CC-Naphthol, 1 ,5-, 2,7- und 1 ,7-Dihydroxynaphthalin, 5- Amino-2-methylphenol, m-Aminophenol, Resorcin, Resorcinmonomethylether, m-Phenylendiamin, 2,4-Diaminophenoxyethanol, 2-Amino-4-(2-hydroxyethylamino)-anisol (Lehmanns Blau), 1-Phenyl-3- methyl-pyrazol-5-on, 2,4-Dichlor-3-aminophenol, 1 ,3-Bis-(2,4-diaminophenoxy)-propan, 2-Chlorresor- cin, 4-Chlorresorcin, 2-Chlor-6-methyl-3-aminophenol, 2-Methylresorcin, 5-Methylresorcin, 3-Amino-6- methoxy-2-methylamino-pyridin und 3,5-Diamino-2,6-dimethoxypyridin.Coupler substances are in particular CC-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-Amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1, 3-bis (2 , 4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylamino pyridine and 3,5-diamino-2,6-dimethoxypyridine.
Hinsichtlich der in den erfindungsgemäßen Färbemitteln einsetzbaren weiteren Farbstoffvorprodukte unterliegt die vorliegende Erfindung keinerlei Einschränkungen. Die erfindungsgemäßen Färbemittel können als weitere FarbstoffvorprodukteWith regard to the further dyestuff precursors which can be used in the dyestuffs according to the invention, the present invention is not subject to any restrictions. The colorants according to the invention can be used as further dye precursors
Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kuppler-Typ, undDeveloper and / or coupler type oxidation dye precursors, and
Vorstufen naturanaloger Farbstoffe, wie Indol- und Indolin-Derivate, sowie Mischungen von Vertretern dieser Gruppen enthalten.Precursors of natural analog dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups.
In einer ersten bevorzugten Ausführungsform enthält das Färbemittel weiterhin mindestens eine Entwicklerkomponente. Als Entwicklerkomponenten werden üblicherweise primäre aromatische Amine mit einer weiteren, in para- oder ortho-Position befindlichen, freien oder substituierten Hydroxy- oder Aminogruppe, Diaminopyridinderivate, heterozyklische Hydrazone, 4-Amino- pyrazolderivate sowie 2,4,5,6-Tetraaminopyrimidin und dessen Derivate eingesetzt.In a first preferred embodiment, the colorant further contains at least one developer component. As developer components are usually primary aromatic Amines with a further, located in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine, heterocyclic hydrazones, 4-amino pyrazolderivate and 2,4,5,6-tetraaminopyrimidine and its derivatives used.
Es kann erfindungsgemäß bevorzugt sein, als Entwicklerkomponente ein p-Phenylendiaminderivat oder eines seiner physiologisch verträglichen Salze einzusetzen. Besonders bevorzugt sind p- Phenylendiaminderivate der Formel (E1 )It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)
Figure imgf000013_0001
Figure imgf000013_0001
wobeiin which
G1 steht für ein Wasserstoffatom, einen C1- bis C4-Alkylrest, einen C1- bis C4-G 1 is a hydrogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -
Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (C1- bis C4)-Alkoxy-(C-ι- bisMonohydroxyalkyl, a C 2 - to C 4 -polyhydroxyalkyl, a (C 1 - to C 4 ) -alkoxy- (C-ι- bis
C4)-alkylrest, einen 4'-Aminophenylrest oder einen C1- bis C4-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;C 4 ) -alkyl radical, a 4'-aminophenyl radical or a C 1 - to C 4 -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
G2 steht für ein Wasserstoffatom, einen C1- bis C4-Alkylrest, einen C1- bis C4-G 2 is a hydrogen atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -
Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (C1- bis C4)-Alkoxy-(C-ι- bisMonohydroxyalkyl, a C 2 - to C 4 -polyhydroxyalkyl, a (C 1 - to C 4 ) -alkoxy- (C-ι- bis
C4)-alkylrest oder einen C1- bis C4-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;C 4 ) -alkyl radical or a C 1 - to C 4 -alkyl radical which is substituted by a nitrogen-containing group;
G3 steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, lod- oder Fluoratom, einen C1- bis C4-Alkylrest, einen C1- bis C4-Monohydroxyalkylrest, einen C2- bis C4-G 3 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C 1 - to C 4 -alkyl radical, a C 1 - to C 4 -monohydroxyalkyl radical, a C 2 - to C 4 -
Polyhydroxyalkylrest, einen C1- bis C4-Hydroxyalkoxyrest, einen C1- bis C4-Polyhydroxyalkyl radical, a C 1 - to C 4 -hydroxyalkoxy radical, a C 1 - to C 4 -
Acetylaminoalkoxyrest, einen C1- bis C4- Mesylaminoalkoxyrest oder einen C1- bis C4-Acetylaminoalkoxy radical, a C 1 - to C 4 -mesylaminoalkoxy radical or a C 1 - to C 4 -
Carbamoylaminoalkoxyrest;Carbamoylaminoalkoxyrest;
G4 steht für ein Wasserstoffatom, ein Halogenatom oder einen C1- bis C4-Alkylrest oder wenn G3 und G4 in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.G 4 represents a hydrogen atom, a halogen atom or a C 1 - to C 4 -alkyl radical or when G 3 and G 4 are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.
Beispiele für die als Substituenten in den erfindungsgemäßen Verbindungen genannten C1- bis C4- Alkylreste sind die Gruppen Methyl, Ethyl, Propyl, Isopropyl und Butyl. Ethyl und Methyl sind bevorzugte Alkylreste. Erfindungsgemäß bevorzugte C1- bis C4-Al koxyreste sind beispielsweise eine Methoxy- oder eine Ethoxygruppe. Weiterhin können als bevorzugte Beispiele für eine d- bis C4- Hydroxyalkylgruppe eine Hydroxymethyl-, eine 2-Hydroxyethyl-, eine 3-Hydroxypropyl- oder eine A- Hydroxybutylgruppe genannt werden. Eine 2-Hydroxyethylgruppe ist besonders bevorzugt. Eine besonders bevorzugte C2- bis C4-Polyhydroxyalkylgruppe ist die 1 ,2-Dihydroxyethylgruppe. Beispiele für Halogenatome sind erfindungsgemäß F-, Cl- oder Br-Atome, Cl-Atome sind ganz besonders bevorzugt. Die weiteren verwendeten Begriffe leiten sich erfindungsgemäß von den hier gegebenen Definitionen ab. Beispiele für stickstoffhaltige Gruppen der Formel (E1 ) sind insbesondere die Aminogruppen, C1- bis C4-Monoalkylaminogruppen, C1- bis C4-Dialkylaminogruppen, C1- bis C4- Trialkylammoniumgruppen, C1- bis C4-Monohydroxyalkylaminogruppen, Imidazolinium und Ammonium.Examples of the C 1 - to C 4 -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C 1 -C 4 -alkoxy radicals which are preferred according to the invention are, for example, one Methoxy or ethoxy group. Furthermore, as preferred examples of a C 1 -C 4 -hydroxyalkyl group, there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or an A-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C 2 to C 4 polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are in particular the amino groups, C 1 to C 4 monoalkylamino groups, C 1 to C 4 dialkylamino groups, C 1 to C 4 trialkylammonium groups, C 1 to C 4 monohydroxyalkylamino groups, Imidazolinium and ammonium.
Besonders bevorzugte p-Phenylendiamine der Formel (E1 ) sind ausgewählt aus p-Phenylendiamin, p-Toluylendiamin, 2-Chlor-p-phenylendiamin, 2,3-Dimethyl-p-phenylendiamin, 2,6-Dimethyl-p- phenylendiamin, 2,6-Diethyl-p-phenylendiamin, 2,5-Dimethyl-p-phenylendiamin, N,N-Dimethyl-p- phenylendiamin, N,N-Diethyl-p-phenylendiamin, N,N-Dipropyl-p-phenylendiamin, 4-Amino-3-methyl- (N,N-diethyl)-anilin, N,N-Bis-(ß-hydroxyethyl)-p-phenylendiamin, 4-N,N-Bis-(ß-hydroxyethyl)amino-2- methylanilin, 4-N,N-Bis-(ß-hydroxyethyl)amino-2-chloranilin, 2-(ß-Hydroxyethyl)-p-phenylendiamin, 2- (α,ß-Dihydroxyethyl)-p-phenylendiamin, 2-Fluor-p-phenylendiamin, 2-lsopropyl-p-phenylendiamin, N- (ß-Hydroxypropyl)-p-phenylendiamin, 2-Hydroxymethyl-p-phenylendiamin, N,N-Dimethyl-3-methyl-p- phenylendiamin, N,N-(Ethyl,ß-hydroxyethyl)-p-phenylendiamin, N-(ß,γ-Dihydroxypropyl)-p- phenylendiamin, N-(4'-Aminophenyl)-p-phenylendiamin, N-Phenyl-p-phenylendiamin, 2-(ß- Hydroxyethyloxy)-p-phenylendiamin, 2-(ß-Acetylaminoethyloxy)-p-phenylendiamin, N-(ß-Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro -p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N - (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetyl aminoethyloxy) -p-phenylenediamine, N- (β-
Methoxyethyl)-p-phenylendiamin und 5,8-Diaminobenzo-1 ,4-dioxan sowie ihren physiologisch verträglichen Salzen.Methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.
Erfindungsgemäß ganz besonders bevorzugte p-Phenylendiaminderivate der Formel (E1 ) sind p- Phenylendiamin, p-Toluylendiamin, 2-(ß-Hydroxyethyl)-p-phenylendiamin, 2-(α,ß-Dihydroxyethyl)-p- phenylendiamin und N,N-Bis-(ß-hydroxyethyl)-p-phenylendiamin.Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.
Es kann erfindungsgemäß weiterhin bevorzugt sein, als Entwicklerkomponente Verbindungen einzusetzen, die mindestens zwei aromatische Kerne enthalten, die mit Amino- und/oder Hydroxylgruppen substituiert sind.It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
Unter den zweikernigen Entwicklerkomponenten, die in den Färbemitteln gemäß der Erfindung verwendet werden können, kann man insbesondere die Verbindungen nennen, die der folgenden Formel (E2) entsprechen, sowie ihre physiologisch verträglichen Salze:
Figure imgf000015_0001
wobei:Among the binuclear developer components which can be used in the colorants according to the invention, mention may be made in particular of the compounds which correspond to the following formula (E2) and their physiologically tolerated salts:
Figure imgf000015_0001
in which:
Z1 und Z2 stehen unabhängig voneinander für einen Hydroxyl- oder NH2-ReSt, der gegebenenfalls durch einen d- bis C4-Alkylrest, durch einen d- bis C4-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist, die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wieZ 1 and Z 2 independently of one another represent a hydroxyl or NH 2 -ReSt which is optionally substituted by a C 1 -C 4 -alkyl radical, by a C 1 -C 4 -hydroxyalkyl radical and / or by a bridging Y or which optionally represents part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, of one or more nitrogen-containing groups and / or one or more heteroatoms such
Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C1- bis C8-Al koxyreste substituiert sein kann, oder eine direkte Bindung,Oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or C 1 - to C 8 -Al koxyreste, or a direct bond,
G5 und G6 stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C1- bisG 5 and G 6 independently represent a hydrogen or halogen atom, a C 1 - to
C4-Alkylrest, einen C1- bis C4-Monohydroxyalkylrest, einen C2- bis C4- Polyhydroxyalkylrest, einen C1- bis C4-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,C 4 alkyl, C 1 - to C 4 monohydroxyalkyl radical, a C 2 - to C 4 - polyhydroxyalkyl radical, a C 1 - to C 4 -aminoalkyl radical or a direct bond to the bridge Y,
G7, G8, G9, G10, G11 und G12 stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C1- bis C4-Alkylrest, mit den Maßgaben, dass die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.G 7 , G 8 , G 9 , G 10 , G 11 and G 12 independently represent a hydrogen atom, a direct bond to the bridge Y or a C 1 - to C 4 -alkyl radical, with the provisos that the compounds of the formula (E2) contain only one bridging Y per molecule and the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom.
Die in Formel (E2) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.The substituents used in formula (E2) are defined according to the invention analogously to the above statements.
Bevorzugte zweikernige Entwicklerkomponenten der Formel (E2) sind insbesondere: N,N'-Bis-(ß- hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1 ,3-diamino-propan-2-ol, N,N'-Bis-(ß-hydroxyethyl)-N,N'-bis- (4'-aminophenyl)-ethylendiamin, N,N'-Bis-(4-aminophenyl)-tetramethylendiamin, N,N'-Bis-(ß- hydroxyethyl)-N,N'-bis-(4-anninophenyl)-tetrannethylendiannin, N,N'-Bis-(4-methyl-aminophenyl)- tetramethylendiannin, N,N'-Diethyl-N,N'-bis-(4'-amino-3'-nnethylphenyl)-ethylendiannin, Bis-(2-hydroxy- 5-aminophenyl)-nnethan, 1 ,3-Bis-(2,5-diaminophenoxy)-propan-2-ol, N,N'-Bis-(4'-aminophenyl)-1 ,4- diazacycloheptan, N,N'-Bis-(2-hydroxy-5-aminobenzyl)-piperazin, N-(4'-Aminophenyl)-p- phenylendiamin und 1 ,10-Bis-(2',5'-diaminophenyl)-1 ,4,7,10-tetraoxadecan und ihre physiologisch verträglichen Salze.Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - (.beta. hydroxyethyl) -N, N'-bis (4-anninophenyl) tetrannethylenediannine, N, N'-bis (4-methylaminophenyl) tetramethylenediannine, N, N'-diethyl-N, N'-bis ( 4'-amino-3'-methylphenyl) ethylenediannine, bis (2-hydroxy-5-aminophenyl) ethane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N '-Bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1 , 10-bis (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane and their physiologically acceptable salts.
Ganz besonders bevorzugte zweikernige Entwicklerkomponenten der Formel (E2) sind N,N'-Bis-(ß- hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1 ,3-diamino-propan-2-ol, Bis-(2-hydroxy-5-aminophenyl)- methan, 1 ,3-Bis-(2,5-diaminophenoxy)-propan-2-ol, N,N'-Bis-(4'-aminophenyl)-1 ,4-diazacycloheptan und 1 ,10-Bis-(2',5'-diaminophenyl)-1 ,4,7,10-tetraoxadecan oder eines ihrer physiologisch verträglichen Salze.Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiologically acceptable salts.
Weiterhin kann es erfindungsgemäß bevorzugt sein, als Entwicklerkomponente ein p- Aminophenolderivat oder eines seiner physiologisch verträglichen Salze einzusetzen. Besonders bevorzugt sind p-Aminophenolderivate der Formel (E3)Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)
Figure imgf000016_0001
Figure imgf000016_0001
wobei:in which:
G13 steht für ein Wasserstoffatom, ein Halogenatom, einen C1- bis C4-Alkylrest, einen C1- bis C4- Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (C1- bis C4)-Alkoxy-(C-ι- bis C4)-alkylrest, einen C1- bis C4-Aminoalkylrest, einen Hydroxy-(C-ι- bis C4)-alkylaminorest, einen C1- bis C4-Hydroxyalkoxyrest, einen C1- bis C4-Hydroxyalkyl-(C-ι-bis C4)-aminoalkylrest oder einen (Di-C1- bis C4-Alkylamino)-(C-ι- bis C4)-alkylrest, undG 13 represents a hydrogen atom, a halogen atom, a C 1 - to C 4 alkyl, C 1 - to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (C 1 - to C 4) - Alkoxy- (C-ι- to C 4 ) -alkyl radical, a C 1 - to C 4 -Aminoalkylrest, a hydroxy (C-ι- to C 4 ) -alkylamino, a C 1 - to C 4 -Hydroxyalkoxyrest, a C 1 - to C 4 -hydroxyalkyl- (C 1 -C 4 ) -aminoalkyl or a (di-C 1 - to C 4 -alkylamino) - (C 1 -C 4 ) -alkyl, and
G14 steht für ein Wasserstoff- oder Halogenatom, einen C1- bis C4-Alkylrest, einen C1- bis C4- Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (C1- bis C4)-Alkoxy-(C-ι- bis C4)-alkylrest, einen C1- bis C4-Aminoalkylrest oder einen C1- bis C4-Cyanoalkylrest,G 14 represents a hydrogen or halogen atom, a C 1 - to C 4 alkyl, C 1 - to C 4 - monohydroxyalkyl radical, a C 2 - to C 4 polyhydroxyalkyl radical, a (C 1 - to C 4) - Alkoxy (C 1 -C 4 ) -alkyl radical, a C 1 -C 4 -aminoalkyl radical or a C 1 -C 4 -cyanoalkyl radical,
G15 steht für Wasserstoff, einen C1- bis C4-Alkylrest, einen C1- bis C4-Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und G16 steht für Wasserstoff oder ein Halogenatom.G 15 is hydrogen, C 1 - to C 4 -alkyl, C 1 - to C 4 -monohydroxyalkyl, C 2 - to C 4 -polyhydroxyalkyl, phenyl or benzyl, and G 16 is hydrogen or a halogen atom.
Die in Formel (E3) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.The substituents used in formula (E3) are defined according to the invention analogously to the above statements.
Bevorzugte p-Aminophenole der Formel (E3) sind insbesondere p-Aminophenol, N-Methyl-p- aminophenol, 4-Amino-3-methyl-phenol, 4-Amino-3-fluorphenol, 2-Hydroxymethylamino-4- aminophenol, 4-Amino-3-hydroxymethylphenol, 4-Amino-2-(ß-hydroxyethoxy)-phenol, 4-Amino-2- methylphenol, 4-Amino-2-hydroxymethylphenol, 4-Amino-2-methoxymethyl-phenol, 4-Amino-2- aminomethylphenol, 4-Amino-2-(ß-hydroxyethyl-aminomethyl)-phenol, 4-Amino-2-(α,ß- dihydroxyethyl)-phenol, 4-Amino-2-fluorphenol, 4-Amino-2-chlorphenol, 4-Amino-2,6-dichlorphenol, A- Amino-2-(diethyl-aminomethyl)-phenol sowie ihre physiologisch verträglichen Salze.Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, A-amino-2- (diethyl-aminomethyl) -phenol and their physiologically acceptable salts.
Ganz besonders bevorzugte Verbindungen der Formel (E3) sind p-Aminophenol, 4-Amino-3- methylphenol, 4-Amino-2-aminomethylphenol, 4-Amino-2-(α,ß-dihydroxyethyl)-phenol und 4-Amino-2- (diethyl-aminomethyl)-phenol.Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and 4-amino 2- (diethylaminomethyl) phenol.
Ferner kann die Entwicklerkomponente ausgewählt sein aus o-Aminophenol und seinen Derivaten, wie beispielsweise 2-Amino-4-methylphenol, 2-Amino-5-methylphenol oder 2-Amino-4-chlorphenol.Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
Weiterhin kann die Entwicklerkomponente ausgewählt sein aus heterozyklischen Entwicklerkomponenten, wie beispielsweise den Pyridin-, Pyrimidin-, Pyrazol-, Pyrazol-Pyrimidin- Derivaten und ihren physiologisch verträglichen Salzen.Further, the developer component may be selected from heterocyclic developer components, such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.
Bevorzugte Pyridin-Derivate sind insbesondere die Verbindungen 2,5-Diamino-pyridin, 2-(4'- Methoxyphenyl)amino-3-amino-pyridin, 2,3-Diamino-6-methoxy-pyridin, 2-(ß-Methoxyethyl)amino-3- amino-6-methoxy-pyridin und 3,4-Diamino-pyridin.Preferred pyridine derivatives are in particular the compounds 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxypyridine, 2- (β-methoxyethyl ) amino-3-amino-6-methoxypyridine and 3,4-diamino-pyridine.
Bevorzugte Pyrimidin-Derivate sind insbesondere 2,4,5,6-Tetraaminopyrimidin, 4-Hydroxy-2,5,6- triaminopyrimidin, 2-Hydroxy-4,5,6-triaminopyrimidin, 2-Dimethylamino-4,5,6-triaminopyrimidin, 2,4- Dihydroxy-5,6-diaminopyrimidin und 2,5,6-Triaminopyrimidin.Preferred pyrimidine derivatives are in particular 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6- triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.
Bevorzugte Pyrazol-Derivate sind insbesondere 4,5-Diamino-1-methylpyrazol, 4,5-Diamino-1-(ß- hydroxyethyl)-pyrazol, 3,4-Diaminopyrazol, 4,5-Diamino-1-(4'-chlorbenzyl)-pyrazol, 4,5-Diamino-1 ,3- dimethyl pyrazol, 4,5-Diamino-3-methyl-1-phenylpyrazol, 4,5-Diamino-1-methyl-3-phenylpyrazol, 4- Amino-1 ,3-dimethyl-5-hydrazinopyrazol, 1-Benzyl-4,5-diamino-3-methylpyrazol, 4,5-Diamino-3-tert.- butyl-1-methylpyrazol, 4,5-Diamino-1-tert.-butyl-3-nnethylpyrazol, 4,5-Diamino-1-(ß-hydroxyethyl)-3- methylpyrazol, 4,5-Diamino-1-ethyl-3-nnethylpyrazol, 4,5-Diamino-1-ethyl-3-(4'-nnethoxyphenyl)- pyrazol, 4,5-Diamino-1-ethyl-3-hydroxynnethylpyrazol, 4,5-Diamino-3-hydroxymethyl-1-methylpyrazol, 4,5-Diamino-3-hydroxynnethyl-1-isopropylpyrazol, 4,5-Diamino-3-nnethyl-1-isopropylpyrazol, 4-Amino- 5-(ß-aminoethyl)annino-1 ,3-dinnethylpyrazol, 3,4,5-Triaminopyrazol, 1-Methyl-3,4,5-triaminopyrazol, 3,5-Diamino-1-nnethyl-4-nnethylanninopyrazol und 3,5-Diamino-4-(ß-hydroxyethyl)annino-1- methylpyrazol.Preferred pyrazole derivatives are in particular 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'- chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4- Amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1 tert-butyl-3-naphthylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-naphthylpyrazole, 4,5-diamino-1-one ethyl 3- (4'-n-ethoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxynethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxyethyl 1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) -annino-1,3-dinethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl- 3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-ni-methylanninopyrazole and 3,5-diamino-4- (β-hydroxyethyl) -annino-1-methylpyrazole.
Bevorzugte Pyrazol-Pyrimidin-Derivate sind insbesondere die Derivate des Pyrazol-[1 ,5-a]-pyrimidin der folgenden Formel (E4) und dessen tautomeren Formen, sofern ein tautomeres Gleichgewicht besteht:Preferred pyrazole-pyrimidine derivatives are in particular the derivatives of pyrazolo [1, 5-a] -pyrimidine of the following formula (E4) and its tautomeric forms, provided that a tautomeric equilibrium exists:
Figure imgf000018_0001
wobei:
Figure imgf000018_0001
in which:
G17, G18, G19 und G20 unabhängig voneinander stehen für ein Wasserstoffatom, einen C1- bis C4- Alkylrest, einen Aryl-Rest, einen d- bis C4-Hydroxyalkylrest, einen C2- bis C4- Polyhydroxyalkylrest einen (d- bis C4)-Alkoxy-(d- bis C4)-alkylrest, einen d- bis C4- Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (d- bis C4)-Alkylamino-(d- bis C4)-alkylrest, einen Di-[(Cr bis C4)-alkyl]-(d- bis C4)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen d- bis C4-Hydroxyalkyl- oder einen Di-(Cr bis C4)-[Hydroxyalkyl]-(Ci- bis C4)-aminoalkylrest, die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen d- bis C4-Alkylrest, einen Aryl-Rest, einen C1- bis C4-Hydroxyalkylrest, einen C2- bis C4- Polyhydroxyalkylrest, einen C1- bis C4-Aminoalkylrest, einen (C1- bis C4)-Alkylamino-(d- bis C4)-alkylrest, einen Di-[(C-ι- bis C4)alkyl]- (C1- bis C4)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C1- bis C4- Hydroxyalkyl- oder einen Di-(C1- bis C4-hydroxyalkyl)aminoalkylrest, einen Aminorest, einen C1- bis C4-Alkyl- oder Di-(C1- bis C4-hydroxyalkyl)aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe, i hat den Wert 0, 1 , 2 oder 3, p hat den Wert O oder 1 , q hat den Wert 0 oder 1 und n hat den Wert 0 oder 1 , mit der Maßgabe, dass die Summe aus p + q ungleich 0 ist, wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG17G18 und NG19G20 belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7); wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG17G18 (oder NG19G20) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);G 17 , G 18 , G 19 and G 20 independently of one another represent a hydrogen atom, a C 1 - to C 4 -alkyl radical, an aryl radical, a C 1 - to C 4 -hydroxyalkyl radical, a C 2 - to C 4 - polyhydroxyalkyl a (d- to C 4) alkoxy (d- to C 4) alkyl, a d- to C 4 - aminoalkyl radical, which may be optionally protected by an acetyl ureide or a sulfonyl residue, a ( d- to C 4 ) -alkylamino (C 1 to C 4 ) -alkyl radical, a di - [(C 1 to C 4 ) -alkyl] - (C 1 to C 4 ) -aminoalkyl radical, where the dialkyl radicals optionally have a form carbocycle or a heterocycle with 5 or 6 chain links, a d- to C 4 hydroxyalkyl or a di (Cr to C 4) - aminoalkyl (Ci to C 4), are the residues X - [hydroxyalkyl] independently represent a hydrogen atom, a d- to C4-alkyl radical, an aryl radical, a C 1 - to C 4 -hydroxyalkyl group, a C 2 - to C 4 - polyhydroxyalkyl radical, a C 1 - to C 4 aminoalkyl radical, a (C 1 - to C 4 ) -alkyl amino- (d- to C 4) alkyl, a di - [(C-ι- to C 4) alkyl] - (C 1 - to C 4) aminoalkyl, wherein the dialkyl residues optionally, a carbocycle or a heterocycle form a C 1 - to C 4 - hydroxyalkyl or a di- (C 1 - to C 4 -hydroxyalkyl) aminoalkyl radical, an amino radical, a C 1 - to C 4 -alkyl or di- ( C 1 - to C 4 -hydroxyalkyl) amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value O or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0, if p + q equals 2, n is the value 0, and the groups NG 17 G 18 and NG 19 G 20 occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG 17 G 18 (or NG 19 G 20 ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);
Die in Formel (E4) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.The substituents used in formula (E4) are defined according to the invention analogously to the above statements.
Wenn das Pyrazol-[1 ,5-a]-pyrimidin der obenstehenden Formel (E4) eine Hydroxygruppe an einer der Positionen 2, 5 oder 7 des Ringsystems enthält, besteht ein tautomeres Gleichgewicht, das zum Beispiel im folgenden Schema dargestellt wird:When the pyrazole [1,5-a] pyrimidine of the above formula (E4) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium shown, for example, in the following scheme:
Figure imgf000019_0001
Figure imgf000019_0001
Unter den Pyrazol-[1 ,5-a]-pyrimidinen der obenstehenden Formel (E4) kann man insbesondere nennen:Among the pyrazolo [1, 5-a] -pyrimidines of the above formula (E4) may be mentioned in particular:
Pyrazol-[1 ,5-a]-pyrimidin-3,7-diamin;Pyrazolo [1,5-a] pyrimidine-3,7-diamine;
2,5-Dimethyl-pyrazol-[1 ,5-a]-pyrimidin-3,7-diamin;2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine;
Pyrazol-[1 ,5-a]-pyrimidin-3,5-diamin;Pyrazolo [1,5-a] pyrimidine-3,5-diamine;
2,7-Dimethyl-pyrazol-[1 ,5-a]-pyrimidin-3,5-diamin;2,7-dimethyl-pyrazolo [1,5-a] -pyrimidine-3,5-diamine;
3-Aminopyrazol-[1 ,5-a]-pyrimidin-7-ol;3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
3-Aminopyrazol-[1 ,5-a]-pyrimidin-5-ol;3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
2-(3-Aminopyrazol-[1 ,5-a]-pyrimidin-7-ylamino)-ethanol;2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
2-(7-Aminopyrazol-[1 ,5-a]-pyrimidin-3-ylamino)-ethanol;2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
2-[(3-Aminopyrazol-[1 ,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)amino]-ethanol;2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) (2-hydroxyethyl) amino] ethanol;
2-[(7-Aminopyrazol-[1 ,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)amino]-ethanol; 5,6-Dimethylpyrazol-[1 ,5-a]-pyrimidin-3,7-diannin;2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) amino] -ethanol; 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diannine;
2,6-Dimethylpyrazol-[1 ,5-a]-pyrimidin-3,7-diannin;2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diannine;
3-Amino-7-dinnethylannino-2,5-dinnethylpyrazol-[1 ,5-a]-pyrinnidin; sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.3-amino-7-dinethylannino-2,5-dinethylpyrazolo [1,5-a] -pyrinnidine; and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.
Die Pyrazol-[1 ,5-a]-pyrimidine der obenstehenden Formel (E4) können wie in der Literatur beschrieben durch Zyklisierung ausgehend von einem Aminopyrazol oder von Hydrazin hergestellt werden.The pyrazolo [1, 5-a] -pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization from an aminopyrazole or from hydrazine.
Erfindungsgemäß besonders bevorzugte Oxidationsfärbemittel sind dadurch gekennzeichnet, daß die Entwicklerkomponente ausgewählt ist aus 3-Methyl-1 ,4-diaminobenzol, 1-(2'-Hydroxyethyl)-2,5- diaminobenzol, 2-(2,5-Diaminophenoxy)-ethanol, N,N-Bis(2'-Hydroxyethyl)-1 ,4-diaminobenzol, 3- Methyl-4-aminophenol und 2-Methylamino-4-aminophenol, p-Phenylendiamin, 2-(ß-Hydroxyethyl)-p- phenylendiamin, N,N-Bis-(ß-hydroxyethyl)-p-phenylendiamin, N,N'-bis-(ß- Hydroxyethyl)-N,N'-bis- (4'- aminophenyl)-1 ,3-diamino-propan-2-ol, Bis-(2-hydroxy-5- aminophenyl)- methan, N,N'-Bis-(4'- aminophenyl)-1 ,4-diazacycloheptan, 1 ,10-Bis-(2',5'- diaminophenyl)-1 ,4,7,10-tetraoxadecan, p- Aminophenol, A- Amino-3-fluorphenol, 4-Amino-2-aminomethylphenol, A- Amino-2- ((diethylamino)methyl)phenol, o-Aminophenol, 2-Amino-4- methylphenol, 2-Amino-5- methylphenol, 2-Amino-4-chlorphenol, 2,4,5,6- Tetraaminopyrimidin, 4-Hydroxy-2,5,6- triaminopyrimidin, 2-Hydroxy- 4,5,6- triaminopyrimidin, 2-Dimethylamino-4,5,6- triaminopyrimidin, 2,4- Dihydroxy-5,6- diaminopyrimidin, 2,5,6-Triaminopyrimidin, 1-(2'- Hydroxy- 5'-aminobenzyl)-imidazolidin-2-on, 4,5- Diamino-1-(2'-hydroxyethyl) pyrazol und Λ/-(4-Amino-3-methylphenyl)-Λ/-[3-(1/-/-imidazol-1- yl)propyl]amin trihydrochlorid.Oxidation colorants particularly preferred according to the invention are characterized in that the developer component is selected from 3-methyl-1,4-diaminobenzene, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 2- (2,5-diaminophenoxy) ethanol , N, N-bis (2'-hydroxyethyl) -1, 4-diaminobenzene, 3-methyl-4-aminophenol and 2-methylamino-4-aminophenol, p-phenylenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine , N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino propan-2-ol, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane, p-aminophenol, A-amino-3-fluorophenol, 4-amino-2-aminomethylphenol, A-amino-2- ((diethylamino) methyl) phenol, o-aminophenol, 2-amino-4-methylphenol, 2-amino-5-methylphenol, 2-amino-4-chlorophenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6- triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, 1- (2'-hydroxy-5'-aminobenzyl) -imidazolidin-2-one, 4,5-diamino-1 (2'-hydroxyethyl) pyrazole and Λ / - (4-amino-3-methylphenyl) -Λ / - [3- (1 / - / - imidazol-1-yl) propyl] amine trihydrochloride.
Bevorzugte erfindungsgemäße Mittel enthalten als Oxidationsfarbstoffvorprodukt mindestens eine Entwicklerkomponente, wobei bevorzugte Entwicklerkomponenten ausgewählt sind aus p- Phenylendiamin, p-Toluylendiamin, 1-(2'-Hydroxyethyl)-2,5-diaminobenzol, N,N-Bis-(2- hydroxyethyl)amino-p-phenylendiamin, 1 ,3-Bis-[(2-hydroxyethyl-4'-aminophenyl)amino]-propan-2-ol, 1 , 10-Bis-(2',5'-diaminophenyl)-1 ,4,7,10-tetraoxadecan, 4-Aminophenol, 4-Amino-3-methylphenol, Bis- (5-amino-2-hydroxyphenyl)methan, 2,4,5,6-Tetraaminopyrimidin, 2-Hydroxy-4,5,6-triaminopyrimidin, 4,5-Diamino-1-(2-hydroxyethyl)-pyrazol.Preferred agents according to the invention comprise as oxidation dye precursor at least one developer component, preferred developer components being selected from p-phenylenediamine, p-toluenediamine, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (2-hydroxyethyl) amino-p-phenylenediamine, 1, 3-bis - [(2-hydroxyethyl-4 'aminophenyl) amino] -propan-2-ol, 1, 10-bis (2', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane, 4-aminophenol, 4-amino-3-methylphenol, bis (5-amino-2-hydroxyphenyl) methane, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5 , 6-triaminopyrimidine, 4,5-diamino-1- (2-hydroxyethyl) pyrazole.
Die erfindungsgemäßen Färbemittel können weiterhin mindestens eine Kupplerkomponente enthalten. Als Kupplerkomponenten werden in der Regel m-Phenylendiaminderivate, Naphthole, Resorcin und Resorcinderivate, Pyrazolone und m-Aminophenolderivate verwendet. Als Kupplersubstanzen eignen sich insbesondere 1-Naphthol, 1 ,5-, 2,7- und 1 ,7-Dihydroxynaphthalin, 5-Amino-2-nnethylphenol, m- Aminophenol, Resorcin, Resorcinmonomethylether, m-Phenylendiamin, 1-Phenyl-3-methyl- pyrazolon-5, 2,4-Dichlor-3-aminophenol, 1 ,3-Bis-(2',4'-diaminophenoxy)-propan, 2-Chlor-resorcin, A- Chlor-resorcin, 2-Chlor-6-methyl-3-anninophenol, 2-Amino-3-hydroxypyridin, 2-Methylresorcin, 5- Methylresorcin und 2-Methyl-4-chlor-5-aminophenol.The colorants of the invention may further contain at least one coupler component. As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Suitable coupler substances are in particular 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-nnethylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3 -methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, A-chloro-resorcinol, 2-chloro 6-methyl-3-anninophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.
Erfindungsgemäß bevorzugte Kupplerkomponenten sind m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-nnethylphenol, N- Cyclopentyl-3-aminophenol, S-Amino^-chlor-θ-methylphenol, 2-Hydroxy-4- aminophenoxyethanol, 2,6-Dimethyl-3-anninophenol, 3-Trifluoroacetylamino-2-chlor-6- methylphenol, 5-Amino-4-chlor-2-nnethylphenol, 5-Amino-4-nnethoxy-2-nnethylphenol, 5-(2'- Hydroxyethyl)amino-2-nnethylphenol, 3-(Diethylamino)-phenol, N-Cyclopentyl-3-aminophenol, 1 ,3-Dihydroxy-5-(methylannino)-benzol, 3-Ethylamino-4-nnethylphenol und 2,4-Dichlor-3- aminophenol, o-Aminophenol und dessen Derivate, m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxyethanol, 1 ,3-Bis- (2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylannino)benzol, 1 ,3-Bis- (2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-nnethylbenzol und 1-Amino-3-bis- (2'-hydroxyethyl)aminobenzol, o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3- Diamino-1-nnethylbenzol,Coupler components preferred according to the invention are m-aminophenol and its derivatives such as, for example, 5-amino-2-naphthylphenol, N-cyclopentyl-3-aminophenol, S-amino-1-chloro-θ-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6 -Dimethyl-3-anninophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-naphthylphenol, 5-amino-4-nethoxy-2-naphthylphenol, 5- (2'-hydroxyethyl ) amino-2-naphthylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylannino) benzene, 3-ethylamino-4-naphthylphenol and 2,4-dichloro 3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1, 3-bis (2 ', 4'-diaminophenoxy) -propane, 1-methoxy-2- amino-4- (2'-hydroxyethyl-amino) -benzene, 1, 3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethyl-amino) -1-ethylbenzene and 1-amino 3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2 , 3-diamino-1-ethylbenzene,
Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2- Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1 ,2,4-Trihydroxybenzol,Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5- chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4- dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6- methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4 dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1- naphthol, 2-Hydroxyethyl-1-naphthol, 1 ,5-Dihydroxynaphthalin, 1 ,6-Dihydroxynaphthalin, 1 ,7- Dihydroxynaphthalin, 1 ,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3- Dihydroxynaphthalin,Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1 , 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Amino-benzomorpholin, Chinoxalinderivate wie beispielsweise 6-Methyl-1 ,2,3,4-tetrahydrochinoxalin, Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on, Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol, Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrinnidin, 4-Amino-2,6-dihydroxypyrinnidin, 2,4- Diamino-6-hydroxypyrinnidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-nnethylpyrinnidin, 2-Amino-4- hydroxy-6-methylpyrinnidin und 4,6-Dihydroxy-2-methylpyrinnidin, oderMorpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine, quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as 4,6-diaminopyrinnidine, 4-amino-2,6-dihydroxypyrinnidine, 2,4-diamino-6-hydroxypyrinnidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrinnidine, 2-amino-4-hydroxy-6-methylpyrinnidine and 4,6-dihydroxy-2-methylpyrinnidine, or
Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino- 3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)amino-3,4-methylendioxybenzol.Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.
Erfindungsgemäß besonders bevorzugte Kupplerkomponenten sind 1-Naphthol, 1 ,5-, 2,7- und 1 ,7- Dihydroxynaphthalin, 3-Aminophenol, 5-Amino-2-nnethylphenol, 2-Amino-3-hydroxypyridin, Resorcin, 4-Chlorresorcin, 2-Chlor-6-methyl-3-anninophenol, 2-Methylresorcin, 5-Methylresorcin, 2,5- Dimethylresorcin und 2,6-Dihydroxy-3,4-dimethylpyridin.Particularly preferred coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-naphthylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-anninophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
Als Vorstufen naturanaloger Farbstoffe werden bevorzugt solche Indole und Indoline eingesetzt, die mindestens eine Hydroxy- oder Aminogruppe, bevorzugt als Substituent am Sechsring, aufweisen. Diese Gruppen können weitere Substituenten tragen, z. B. in Form einer Veretherung oder Veresterung der Hydroxygruppe oder eine Alkylierung der Aminogruppe. In einer zweiten bevorzugten Ausführungsform enthalten die Färbemittel mindestens ein Indol- und/oder Indolinderivat.As precursors of naturally-analogous dyes such indoles and indolines are preferably used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.
Besonders gut als Vorstufen naturanaloger Haarfarbstoffe geeignet sind Derivate des 5,6- Dihydroxyindolins der Formel (RN-Ia),Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (RN-Ia),
Figure imgf000022_0001
in der unabhängig voneinander
Figure imgf000022_0001
in the independently of each other
R1 steht für Wasserstoff, eine C-ι-C4-Alkylgruppe oder eine C-ι-C4-Hydroxy-alkylgruppe, R2 steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann, R3 steht für Wasserstoff oder eine C-ι-C4-Alkylgruppe,R 1 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxy-alkyl group, R 2 is hydrogen or a -COOH group, where the -COOH group is also present as a salt may be a physiologically compatible cation, R 3 is hydrogen or a C 1 -C 4 -alkyl group,
R4 steht für Wasserstoff, eine C-ι-C4-Alkylgruppe oder eine Gruppe -CO-R6, in der R6 steht für eine d-C4-Alkylgruppe, und R5 steht für eine der unter R4 genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.R 4 is hydrogen, a C 1 -C 4 -alkyl group or a group -CO-R 6 , in which R 6 is a C 1 -C 4 -alkyl group, and R 5 is one of the groups mentioned under R 4 , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.
Besonders bevorzugte Derivate des Indolins sind das 5,6-Dihydroxyindolin, N-Methyl-5,6- dihydroxyindolin, N-Ethyl-5,6-dihydroxyindolin, N-Propyl-5,6-dihydroxyindolin, N-Butyl-5,6- dihydroxyindolin, 5,6-Dihydroxyindolin-2-carbonsäure sowie das 6-Hydroxyindolin, das 6- Aminoindolin und das 4-Aminoindolin.Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.
Besonders hervorzuheben sind innerhalb dieser Gruppe N-Methyl-5,6-dihydroxyindolin, N-Ethyl-5,6- dihydroxyindolin, N-Propyl-5,6-dihydroxyindolin, N-Butyl-5,6-dihydroxyindolin und insbesondere das 5,6-Dihydroxyindolin.Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.
Als Vorstufen naturanaloger Haarfarbstoffe hervorragend geeignet sind weiterhin Derivate des 5,6- Dihydroxyindols der Formel (RN-I b),Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (RN-I b),
Figure imgf000023_0001
Figure imgf000023_0001
R1 (RN-I b) in der unabhängig voneinanderR 1 (RN-I b) in the independently
R1 steht für Wasserstoff, eine C-ι-C4-Alkylgruppe oder eine C-ι-C4-Hydroxyalkylgruppe,R 1 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxyalkyl group,
R2 steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,R 2 is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
R3 steht für Wasserstoff oder eine C-ι-C4-Alkylgruppe,R 3 is hydrogen or a C 1 -C 4 -alkyl group,
R4 steht für Wasserstoff, eine C-ι-C4-Alkylgruppe oder eine Gruppe -CO-R6, in der R6 steht für eine d-C4-Alkylgruppe, undR 4 is hydrogen, a C 1 -C 4 -alkyl group or a group -CO-R 6 , in which R 6 is a C 1 -C 4 -alkyl group, and
R5 steht für eine der unter R4 genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.R 5 is one of the groups mentioned under R 4 , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.
Besonders bevorzugte Derivate des Indols sind 5,6-Dihydroxyindol, N-Methyl-5,6-dihydroxyindol, N- Ethyl-5,6-dihydroxyindol, N-Propyl-5,6-dihydroxyindol, N-Butyl-5,6-dihydroxyindol, 5,6-Dihydroxyindol- 2-carbonsäure, 6-Hydroxyindol, 6-Aminoindol und 4-Aminoindol. Innerhalb dieser Gruppe hervorzuheben sind N-Methyl-5,6-dihydroxyindol, N-Ethyl-5,6- dihydroxyindol, N-Propyl-5,6-dihydroxyindol, N-Butyl-5,6-dihydroxyindol sowie insbesondere das 5,6- Dihydroxyindol.Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 - Dihydroxyindole.
Die Indolin- und Indol-Derivate können in den im Rahmen des erfindungsgemäßen Verfahrens eingesetzten Färbemitteln sowohl als freie Basen als auch in Form ihrer physiologisch verträglichen Salze mit anorganischen oder organischen Säuren, z. B. der Hydrochloride, der Sulfate und Hy- drobromide, eingesetzt werden. Die Indol- oder Indolin-Derivate sind in diesen üblicherweise in Mengen von 0,05-10 Gew.-%, vorzugsweise 0,2-5 Gew.-% enthalten.The indoline and indole derivatives can be used in the colorants used in the process according to the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for. As the hydrochlorides, the sulfates and Hydrobromide used. The indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.
In einer weiteren Ausführungsform kann es erfindungsgemäß bevorzugt sein, das Indolin- oder Indolderivat in Haarfärbemitteln in Kombination mit mindestens einer Aminosäure oder einem Oligopeptid einzusetzen. Die Aminosäure ist vorteilhafterweise eine α-Aminosäure; ganz besonders bevorzugte α-Aminosäuren sind Arginin, Ornithin, Lysin, Serin und Histidin, insbesondere Arginin.In a further embodiment, it may be preferred according to the invention to use the indoline or indole derivative in hair dyes in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; Very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.
Erfindungsgemäß besonders bevorzugte Oxidationsfärbemittel sind dadurch gekennzeichnet, daß die Kupplerkomponente ausgewählt ist aus m-Phenylendiaminderivaten, Naphtholen, Resorcin und Resorcinderivaten, Pyrazolonen, m-Aminophenolen und substituierten Pyridinderivaten, wobei bevorzugte Mittel Resorcin, 3-Amino-2-methylamino-6-methoxypyridin, 3-Amino-6-methylphenol, 3- Amino-2-hydroxypyridin, 1 ,3-Bis-(2,4-diaminophenoxy)propan, 2,7-Dihydroxynaphthalin, 2- Methylresorcin, 5-Methyl-resorcin, 2,5-Dimethylresorcin und 4-Chlorresorcin 1-Naphthol, 1 ,5-, 2,7- und 1 ,7-Dihydroxynaphthalin, 3-Aminophenol, 5-Amino-2-methylphenol, 2-Amino-3-hydroxypyridin, Resorcin, 4-Chlorresorcin, 2-Chlor-6-methyl-3-aminophenol, 2-Methylresorcin, 5-Methylresorcin, 2,5- Dimethylresorcin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5- methylphenyl}amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]-2-methoxy-5- methylphenyl}amino)ethanol, 3-Amino-4-(2-methoxyethoxy)-5-methylphenylamin und/oder 2-[(3- Morpholin-4-ylphenyl)amino]ethanol dihydrochlorid enthalten.Particularly preferred oxidation colorants according to the invention are characterized in that the coupler component is selected from m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives, preferred agents being resorcinol, 3-amino-2-methylamino-6-methoxypyridine, 3-amino-6-methylphenol, 3-amino-2-hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 5-methyl-resorcinol, 2.5 Dimethyl resorcinol and 4-chlororesorcinol 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine, 2 - ({3 - [(2- Hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylami n and / or 2 - [(3-morpholin-4-yl-phenyl) -amino] -ethanol dihydrochloride.
Erfindungsgemäß bevorzugte Mittel zum Färben und/oder Aufhellen keratinischer Fasern sind dadurch gekennzeichnet, daß sie als Oxidationsfarbstoffvorprodukt mindestens eine Kupplerkomponente enthalten, wobei bevorzugte Kupplerkomponenten ausgewählt sind aus Resorcin, 2-Methylresorcin, 5-Methyl-resorcin, 2,5-Dimethylresorcin, 4-Chlorresorcin, Resorcinmonomethylether, 5-Aminophenol, 5-Amino-2-methylphenol, 5-(2-Hydroxyethyl)amino-2- methylphenol, 3- Amino-4-chlor-2-methylphenol, 3-Amino-2-chlor-6-methylphenol, 3-Amino-2,4- Dichlorphenol, 2,4-Diaminophenoxyethanol, 2-Amino-4-(2'-hydroxyethyl)amino-anisolsulfat, 1 ,3-Bis- (2,4-diaminophenoxy)propan, 2-Amino-3-hydroxypyridin, 2-Methylamino-3-annino-6-nnethoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 3,5-Diamino-2,6-dinnethoxypyridin, 1-Naphthol, 2-Methyl-1- naphthol, 1 ,5-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin, 1-Phenyl-3-methylpyrazol-5-on, 2,6-Bis- [(2'-hydroxyethyl)amino]-toluol, 4-Hydroxyindol, 6-Hydroxyindol, 6-Hydroxybenzomorpholin.Preferred agents for dyeing and / or lightening keratinic fibers according to the invention are characterized in that they contain at least one coupler component as the oxidation dye precursor, preferred coupler components being selected from resorcinol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 4- Chlororesorcinol, resorcinol monomethyl ether, 5-aminophenol, 5-amino-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 3-amino-4-chloro-2-methylphenol, 3-amino-2-chloro-6 -methylphenol, 3-amino-2,4-dichlorophenol, 2,4-diaminophenoxyethanol, 2-amino-4- (2 '-hydroxyethyl) amino-anisolsulfat, 1, 3-bis- (2,4-diaminophenoxy) propane, 2-amino-3-hydroxypyridine, 2-methylamino-3-annino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6 -dinethoxypyridine, 1-naphthol, 2-methyl-1-naphthol, 1, 5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-phenyl-3-methylpyrazol-5-one, 2,6-bis- [(2 ' - hydroxyethyl) amino] -toluene, 4-hydroxyindole, 6-hydroxyindole, 6-hydroxybenzomorpholine.
Vorzugsweise werden Kuppler- und Entwicklerkomponenten in einem bestimmten Verhältnis zueinander eingesetzt. Hier sind erfindungsgemäße Oxidationsfärbemittel bevorzugt, die die Kupplerkomponente(n) in einer Menge von 0,01 bis 20 Gew.-%, vorzugsweise von 0,5 bis 5 Gew.-%, und die Entwicklerkomponente(n) in einer Menge von 0,01 bis 20 Gew.-%, vorzugsweise von 0,5 bis 5 Gew.-%, jeweils bezogen auf das gesamte Oxidationsfärbemittel, enthalten.Preferably, coupler and developer components are used in a particular ratio to each other. Here, oxidation colorants of the present invention containing the coupler component (s) in an amount of 0.01 to 20 wt%, preferably 0.5 to 5 wt%, and the developer component (n) in an amount of 0, are preferable. 01 to 20 wt .-%, preferably from 0.5 to 5 wt .-%, each based on the total oxidation colorant included.
Zusätzlich können die Färbemittel zur Nuancierung einen oder mehrere direktziehende Farbstoffe enthalten. Direktziehende Farbstoffe sind üblicherweise Nitrophenylendiamine, Nitroaminophenole, Azofarbstoffe, Anthrachinone oder Indophenole, Triphenylmethanfarbstoffe, saure Farbstoffe, basische Farbstoffe, vorzugsweise aus der Gruppe der unter den internationalen Bezeichnungen bzw. Handelsnamen HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Yellow 13, Acid Yellow 1 , Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1 , Disperse Orange 3, Acid Orange 7, HC Red 1 , HC Red 3, HC Red 10, HC Red 11 , HC Red 13, Acid Red 33, Acid Red 52, Acid Red 92, HC Red BN, Pigment Red 57:1 , HC Blue 2, HC Blue 12, Disperse Blue 3, Disperse Red 17, Acid Blue 7, Acid Green 50, HC Violet 1 , Disperse Violet 1 , Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1 , und Acid Black 52 bekannten Verbindungen sowie 1 ,4-Diamino-2- nitrobenzol, 2-Amino-4-nitrophenol, 1 ,4-Bis-(ß-hydroxyethyl)-amino-2-nitrobenzol, 3-Nitro-4-(ß- hydroxyethyl)-aminophenol, 2-(2-Hydroxyethyl)amino-4,6-dinitrophenol, 1-(2'-Hydroxyethyl)amino-4- methyl-2-nitrobenzol, 1-Amino-4-(2-hydroxyethyl)-amino-5-chlor-2-nitrobenzol, 4-Amino-3-nitrophenol, 1-(2-Ureidoethyl)amino-4-nitrobenzol, 4-Amino-2-nitrodiphenylamin-2'-carbonsäure, 6-Nitro-1 , 2,3,4- tetrahydrochinoxalin, 2-Hydroxy-1 ,4-naphthochinon, Pikraminsäure und deren Salze, 2-Amino-6- chloro-4-nitrophenol, 4-Ethylamino-3-nitrobenzoesäure und 2-Chloro-6-ethylamino-1-hydroxy-4- nitrobenzol, 3-(2',6'-Diaminopyridyl-3'-azo)-pyridin; 2-((4-(Ethyl(2-hydroxyethy1 )-amino)-2- methylphenyl )azo)-5-nitro-l,3-thiazol; Nl N-Di(2-hydroxyethy1 )-3-methyl-4-((4-nitropheny1 )azo)-anilin; 3-Diethylamino-7-(4-dimethylaminophenylazO)-5-phenyl-phenaziniumchlorid; 4-(2-Thiazolylazo)- resorcin;4-(((4-Phenylamino)azo)benzosulfonsäure-natriumsalz; 1 -((3-Aminopropyl)amino)-9,IO- anthracendion; 3',3",4,5,5',5",6,7-Octabromphenolsulfonphtalein;1-((4-Amino-3,5-dimethylpheny1 )- (2,6-dichlorphenyl)methylen)-3,5-dimethyl-4-imino-2,5-cyclohexadien-Phosphorsäure(1 :l) (Basic Blue 77); 3',3",5',5"-Tetrabrom-m-kresolsulfonphthalein;2,4-Dinitro-l -naphthol-7-sulfonsäure-Additionally, the colorants may contain one or more substantive dyes for shade. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, triphenylmethane dyes, acid dyes, basic dyes, preferably from the group of the international trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 1, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, Acid Red 92, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Disperse Red 17, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds and 1, 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol , 1,4-Bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4- Amino-3-nitrophenol, 1- (2-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy 1, 4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene, 3- ( 2 ', 6'-Diaminopyridyl-3'-azo) pyridine; 2 - ((4- (ethyl (2-hydroxyethyl) amino) -2-methylphenyl) azo) -5-nitro-1,3-thiazole; N, N-di (2-hydroxyethyl) -3-methyl-4 - ((4-nitrophenyl) azo) aniline; 3-diethylamino-7- (4-dimethylaminophenylazo) -5-phenyl-phenazinium chloride; 4- (2-thiazolylazo) resorcinol, 4 - (((4-phenylamino) azo) benzosulfonic acid, sodium salt, 1 - ((3-aminopropyl) amino) -9, 10-anthracendione, 3 ', 3 ", 4, 5,5 ', 5 ", 6,7-Octabromophenolsulphonphthalein; 1 - ((4-Amino-3,5-dimethylpheny1) - (2,6-dichlorophenyl) methylene) -3,5-dimethyl-4-imino-2 , 5-cyclohexadiene-phosphoric acid (1: 1) (Basic Blue 77); 3 ', 3 ", 5', 5" -tetrabromo-m-cresolsulfonephthalein; 2,4-dinitro-1-naphthol-7-sulfonic acid
Dinatriumsalz;4-[2'-Hydroxy-1 '-naphthyl)azo]-benzolsulfonsäure-Natriumsalz;3',6'-Dihydroxy-Disodium salt, 4- [2'-hydroxy-1'-naphthyl) azo] -benzenesulfonic acid sodium salt; 3 ', 6'-dihydroxy-
2',41 l51 l71-tetraiodospiro-[isobenzo-furan-l (3H), g1(9H)-xanthenl-3-on-Dinatriumsalz; 6-Hydroxy-5- ((2-nnethoxy-5-nnethyl-4-sulfophenyl)azo)-2-Naphthalin-sulfonsäure-dinatriunnsalz; 2,4-Dinitro-2 ', 41 l51 l71-tetraiodospiro- [isobenzo-furan-1 (3H), g1 (9H) -xanthenl-3-one disodium salt; 6-hydroxy-5- ((2-nnethoxy-5-nnethyl-4-sulfophenyl) azo) -2-naphthalene-sulfonic acid dinatriunnsalz; 2,4-dinitro-
Inaphthol-Natriumsalz; 2',4',5',7'-tetrabrom-4151617-tetrachlor-3'16'-dihydroxy-Spiro[isobenzofuran-l (3H),9'[9H]xanthen]-3-on-dinatriunnsalz;4-(2-Hydroxy-l-naphthylazo)-3-nnethyl-benzolsulfonsäurena- triumsalz; Basic Orange 31 , Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41 , Basic Blue 99, Basic Brown 4, Basic, Brown 16, Basic Brown 17, Natural Brown 7, Basic Green 1 , Basic Red 2, Basic Red 12 Basic Red 22, Basic Red 51 , Basic Red 76, Basic Violet 1 , Basic Violet 2, Basic Violet 3, Basic Violet 10, Basic Violet 14 , Basic Yellow 57, Basic Yellow 87, Basic Red 46.Inaphthol sodium salt; 2 ', 4', 5 ', 7'-tetrabromo-4151617-tetrachloro-3'16'-dihydroxy-spiro [isobenzofuran-1 (3H), 9' [9H] xanthene] -3-one-dinatrium salt; 4- (2-hydroxy-1-naphthylazo) -3-methylbenzenesulfonic acid sodium salt; Basic Orange 31, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic, Brown 16, Basic Brown 17, Natural Brown 7, Basic Green 1, Basic Red 2, Basic Red 12 Basic Red 22, Basic Red 51, Basic Red 76, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 10, Basic Violet 14, Basic Yellow 57, Basic Yellow 87, Basic Red 46.
Erfindungsgemäß bevorzugte Mittel zum Färben und/oder Aufhellen keratinischer Fasern sind dadurch gekennzeichnet, daß sie mindestens einen direktziehenden Farbstoff enthalten, der ausgewählt ist aus Nitrophenylendiaminen, Nitroaminophenolen, Azofarbstoffen, Anthrachinonen oder Indophenolen, vorzugsweise aus der Gruppe der unter den internationalen Bezeichnungen bzw. Handelsnamen bekannten Farbstoffe HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1 , Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1 , Disperse Orange 3, Acid Orange 7, HC Red 1 , HC Red 3, HC Red 10, HC Red 11 , HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57:1 , HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1 , Disperse Violet 1 , Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1 , Acid Black 52, Basic Yellow 87, Basic Orange 31 und Basic Red 51 bekannten Verbindungen sowie 1 ,4-Diamino-2-nitrobenzol, 2-Amino-4-nitrophenol, 1 ,4-Bis-(ß-hydroxyethyl)- amino-2-nitrobenzol, 3-Nitro-4-(ß-hydroxyethyl)-aminophenol, 2-(2-Hydroxyethyl)amino-4,6- dinitrophenol, 1-(2'-Hydroxyethyl)amino-4-methyl-2-nitrobenzol, 1-Amino-4-(2-hydroxyethyl)-amino-5- chlor-2-nitrobenzol, 4-Amino-3-nitrophenol, 1-(2-Ureidoethyl)amino-4-nitrobenzol, 4-Amino-2- nitrodiphenylamin-2'-carbonsäure, 6-Nitro-1 ,2,3,4-tetrahydrochinoxalin, 2-Hydroxy-1 ,4- naphthochinon, Pikraminsäure und deren Salze, 2-Amino-6-chloro-4-nitrophenol, 4-Ethylamino-3- nitrobenzoesäure und 2-Chloro-6-ethylamino-1-hydroxy-4-nitrobenzol.Agents preferred according to the invention for dyeing and / or brightening keratinic fibers are characterized in that they contain at least one substantive dye selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group known by the international names or trade names Dye HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, Acid Black 52, Basic Yellow 87, Basic Orange 31 and Basic Red 51 known compounds as well as 1 , 4-diamino-2-nitrobenzene, 2-amino-4-n itrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 1 - (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- ( 2-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, picramic acid, and the like Salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.
Ferner können die erfindungsgemäßen Mittel einen kationischen direktziehenden Farbstoff enthalten. Besonders bevorzugt sind dabeiFurthermore, the agents according to the invention may contain a cationic substantive dye. Particularly preferred are
(a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,(a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
(b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie(b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
(c) direktziehende Farbstoffe, die einen Heterozyklus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2- 998 908, auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.(c) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as described, for example, in EP-A2- 998 908, to which reference is explicitly made at this point, may be mentioned in claims 6 to 11.
Bevorzugte kationische direktziehende Farbstoffe der Gruppe (c) sind insbesondere die folgenden Verbindungen:Preferred cationic substantive dyes of group (c) are in particular the following compounds:
Figure imgf000027_0001
Figure imgf000027_0001
CH3SO4 " CH 3 SO 4 "
Figure imgf000027_0002
Figure imgf000027_0002
Cl" Cl "
Figure imgf000027_0003
Figure imgf000028_0001
Die Verbindungen der Formeln (DZ1 ), (DZ3) und (DZ5), die auch unter den Bezeichnungen Basic Yellow 87, Basic Orange 31 und Basic Red 51 bekannt sind, sind ganz besonders bevorzugte kationische direktziehende Farbstoffe der Gruppe (c).
Figure imgf000027_0003
Figure imgf000028_0001
The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).
Die kationischen direktziehenden Farbstoffe, die unter dem Warenzeichen Arianor® vertrieben werden, sind erfindungsgemäß ebenfalls ganz besonders bevorzugte kationische direktziehende Farbstoffe.The cationic direct dyes, which are sold under the trademark Arianor ®, according to the invention are also very particularly preferred cationic direct dyes.
Die erfindungsgemäßen Mittel gemäß dieser Ausführungsform enthalten die direktziehenden Farbstoffe bevorzugt in einer Menge von 0,01 bis 20 Gew.-%, bezogen auf das gesamte Färbemittel.The agents according to the invention according to this embodiment preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the total colorant.
Weiterhin können die erfindungsgemäßen Zubereitungen auch in der Natur vorkommende Farbstoffe wie sie beispielsweise in Henna rot, Henna neutral, Henna schwarz, Kamillenblüte, Sandelholz, schwarzem Tee, Faulbaumrinde, Salbei, Blauholz, Krappwurzel, Catechu, Sedre und Alkannawurzel enthalten sind, enthalten.Furthermore, the preparations of the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.
Es ist nicht erforderlich, dass die Oxidationsfarbstoffvorprodukte oder die direktziehenden Farbstoffe jeweils einheitliche Verbindungen darstellen. Vielmehr können in den erfindungsgemäßen Haarfärbemitteln, bedingt durch die Herstellungsverfahren für die einzelnen Farbstoffe, in untergeordneten Mengen noch weitere Komponenten enthalten sein, soweit diese nicht das Färbeergebnis nachteilig beeinflussen oder aus anderen Gründen, z.B. toxikologischen, ausgeschlossen werden müssen.It is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, further components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.
Bezüglich der in den erfindungsgemäßen Haarfärbe- und -tönungsmitteln einsetzbaren Farbstoffe wird weiterhin ausdrücklich auf die Monographie Ch. Zviak, The Science of Hair Care, Kapitel 7 (Seiten 248-250; direktziehende Farbstoffe) sowie Kapitel 8, Seiten 264-267; Oxidationsfarbstoffvorprodukte), erschienen als Band 7 der Reihe "Dermatology" (Hrg.: Ch., Culnan und H. Maibach), Verlag Marcel Dekker Inc., New York, Basel, 1986, sowie das "Europäische Inventar der Kosmetik-Rohstoffe", herausgegeben von der Europäischen Gemeinschaft, erhältlich in Diskettenform vom Bundesverband Deutscher Industrie- und Handelsunternehmen für Arzneimittel, Reformwaren und Körperpflegemittel e.V., Mannheim, Bezug genommen.With regard to the dyes which can be used in the hair-dyeing and tinting compositions according to the invention, reference is expressly made to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250, direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the series "Dermatology" (Editor: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials", Issued by the European Community, available in disk form from the Federal Association of German industrial and commercial enterprises for pharmaceuticals, health products and personal care registered association, Mannheim, reference is made.
Eine Färbung keratinischer Fasern kann auch mittels Farbstoffen erfolgen, die in einer oxidativ katalysierten Reaktion von C,H-aciden Verbindungen mit reaktiven Carbonylverbindungen gebildet werden. In einer weiteren Ausführungsform enthält das erfindungsgemäße Mittel daher eine Kombination ausStaining of keratinic fibers can also be accomplished by dyes formed in an oxidatively catalyzed reaction of C, H-acidic compounds with reactive carbonyl compounds. In a further embodiment, the agent according to the invention therefore contains a combination of
Komponentecomponent
A Verbindungen, die eine reaktive Carbonylgruppe enthalten mit KomponenteA compounds containing a reactive carbonyl group with component
B Verbindungen, ausgewählt aus (a) CH-aciden Verbindungen, (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hy- droxyverbindungen, (c) Aminosäuren, (d) aus 2 bis 9 Aminosäuren aufgebauten Oligopeptiden.B compounds selected from (a) CH-acidic compounds, (b) compounds having a primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (c) amino acids, (d) from 2 to 9 amino acids constructed oligopeptides.
Erfindungsgemäße Verbindungen mit einer reaktiven Carbonylgruppe (im Folgenden auch reaktive Carbonylverbindungen oder Komponente A genannt) besitzen mindestens eine Carbonylgruppe als reaktive Gruppe, welche mit den Verbindungen der Komponente B unter Ausbildung einer beide Komponenten verknüpfenden chemischen Bindung reagiert. Ferner sind erfindungsgemäß auch solche Verbindungen als Komponente A umfaßt, in denen die reaktive Carbonylgruppe derart derivatisiert bzw. maskiert ist, daß die Reaktivität des Kohlenstoffatoms der derivatisierten bzw. maskierten Carbonylgruppe gegenüber der Komponente B stets vorhanden ist. Diese Derivate sind bevorzugt Kondensationsverbindungen von reaktiven Carbonylverbindungen mit a) Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Kondensationsverbindung b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Kondensationsverbindung c) von Wasser unter Bildung von Hydraten als Additionsverbindung.Compounds according to the invention having a reactive carbonyl group (also referred to below as reactive carbonyl compounds or component A) have at least one carbonyl group as reactive group which reacts with the compounds of component B to form a chemical bond linking both components. Furthermore, those compounds according to the invention are also included as component A in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to component B is always present. These derivatives are preferably condensation compounds of reactive carbonyl compounds with a) amines and derivatives thereof to form imines or oximes as condensation compound b) of alcohols to form acetals or ketals as condensation compound c) of water to form hydrates as addition compound.
Die Komponente A wird bevorzugt ausgewählt aus der Gruppe, die gebildet wird aus Acetophenon, Propiophenon, 2-Hydroxyacetophenon, 3-Hydroxyacetophenon, 4-Hydroxyacetophenon, 2- Hydroxypropiophenon, 3-Hydroxypropiophenon, 4-Hydroxypropiophenon, 2-Hydroxybutyrophenon, 3- Hydroxybutyrophenon, 4-Hydroxybutyrophenon, 2,4-Dihydroxyacetophenon, 2,5-Component A is preferably selected from the group formed from acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2.5-
Dihydroxyacetophenon, 2,6-Dihydroxyacetophenon, 2,3,4-Trihydroxyacetophenon, 3,4,5- Trihydroxyacetophenon, 2,4,6-Trihydroxyacetophenon, 2,4,6-Trimethoxyacetophenon, 3,4,5- Trimethoxyacetophenon, 3,4,5-Trimethoxy-acetophenon-diethylketal, 4-Hydroxy-3-methoxy- acetophenon, 3,5-Dimethoxy-4-hydroxyacetophenon, 4-Aminoacetophenon, A-Dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3, 4,5-trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxyacetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, A-
Dimethylaminoacetophenon, 4-Morpholinoacetophenon, 4-Piperidinoacetophenon, A-Dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, A-
Imidazolinoacetophenon, 2-Hydroxy-5-brom-acetophenon, 4-Hydroxy-3-nitroacetophenon,Imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone,
Acetophenon-2-carbonsäure, Acetophenon-4-carbonsäure, Benzophenon, 4-Hydroxybenzophenon, 2-Aminobenzophenon, 4,4'-Dihydroxybenzophenon, 2,4-Dihydroxy-benzophenon, 2,4,4'-Trihy- droxybenzophenon, 2,3,4-Trihydroxybenzophenon, 2-Hydroxy-1-acetonaphthon, 1-Hydroxy-2- acetonaphthon, Chromon, Chromon-2-carbonsäure, Flavon, 3-Hydroxyflavon, 3,5,7-Trihydroxyflavon, 4',5,7-Trihydroxyflavon, 5,6,7-Trihydroxyflavon, Quercetin, 1-lndanon, 9-Fluorenon, 3- Hydroxyfluorenon, Anthron, 1 ,8-Dihydroxyanthron, Vanillin, Coniferylaldehyd, 2-Methoxybenzaldehyd, 3-Methoxybenzaldehyd, 4-Methoxybenzaldehyd, 2-Ethoxybenzaldehyd, 3-Ethoxybenzaldehyd, 4-Ethoxybenzaldehyd, 4-Hydroxy-2,3-dimethoxy- benzaldehyd, 4-Hydroxy-2,5-dimethoxy-benzaldehyd, 4-Hydroxy-2,6-dimethoxy-benzaldehyd, A- Hydroxy-2-methyl-benzaldehyd, 4-Hydroxy-3-methyl-benzaldehyd, 4-Hydroxy-2,3-dimethyl- benzaldehyd, 4-Hydroxy-2,5-dimethyl-benzaldehyd, 4-Hydroxy-2,6-dimethyl-benzaldehyd, 4-Hydroxy- 3,5-dimethoxy-benzaldehyd, 4-Hydroxy-3,5-dimethyl-benzaldehyd, 3,5-Diethoxy-4-hydroxy- benzaldehyd, 2,6-Diethoxy-4-hydroxy-benzaldehyd, 3-Hydroxy-4-methoxy-benzaldehyd, 2-Hydroxy-4- methoxy-benzaldehyd, 2-Ethoxy-4-hydroxy-benzaldehyd, 3-Ethoxy-4-hydroxy-benzaldehyd, A- Ethoxy-2-hydroxy-benzaldehyd, 4-Ethoxy-3-hydroxy-benzaldehyd, 2,3-Dimethoxybenzaldehyd, 2,4- Dimethoxybenzaldehyd, 2,5-Dimethoxybenzaldehyd, 2,6-Dimethoxybenzaldehyd, 3,4- Dimethoxybenzaldehyd, 3,5-Dimethoxybenzaldehyd, 2,3,4-Trimethoxybenzaldehyd, 2,3,5- Trimethoxybenzaldehyd, 2,3,6-Trimethoxybenzaldehyd, 2,4,6-Trimethoxybenzaldehyd, 2,4,5- Trimethoxybenzaldehyd, 2,5,6-Trimethoxybenzaldehyd, 2-Hydroxybenzaldehyd, 3-Acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2, 3,4-trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1-hydroxy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7-trihydroxyflavone, 4 ', 5,7 Trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1, 8-dihydroxyanthrone, Vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxy- benzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, A-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxybenzaldehyde 2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy 4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3 Ethoxy-4-hydroxybenzaldehyde, A-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6- Dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde d, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-
Hydroxybenzaldehyd, 4-Hydroxybenzaldehyd, 2,3-Dihydroxybenzaldehyd, 2,4-Hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-
Dihydroxybenzaldehyd, 2,5-Dihydroxybenzaldehyd, 2,6-Dihydroxybenzaldehyd, 3,4-Dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-
Dihydroxybenzaldehyd, 3,5-Dihydroxybenzaldehyd, 2,3,4-Trihydroxybenzaldehyd, 2,3,5- Trihydroxybenzaldehyd, 2,3,6-Trihydroxybenzaldehyd, 2,4,6-Trihydroxybenzaldehyd, 2,4,5- Trihydroxybenzaldehyd, 2,5,6-Trihydroxybenzaldehyd, 4-Hydroxy-2-methoxybenzaldehyd, 4-Dime- thylaminobenzaldehyd, 4-Diethylaminobenzaldehyd, 4-Dimethylannino-2-hydroxybenzaldehyd, A- Diethylamino-2-hydroxybenzaldehyd, 4-Pyrrolidinobenzaldehyd, 4-Morpholinobenzaldehyd, 2-Mor- pholinobenzaldehyd, 4-Piperidinobenzaldehyd, 2-Methoxy-1-naphthaldehyd, 4-Methoxy-1- naphthaldehyd, 2-Hydroxy-1-naphthaldehyd, 2,4-Dihydroxy-1-napthaldehyd, 4-Hydroxy-3-methoxy-1- naphthaldehyd, 2-Hydroxy-4-methoxy-1-naphthaldehyd, 3-Hydroxy-4-methoxy-1-naphthaldehyd, 2,4- Dimethoxy-1-naphthaldehyd, 3,4-Dimethoxy-1-naphthaldehyd, 4-Hydroxy-1-naphthaldehyd, A- Dimethylannino-1-naphthaldehyd, 2-Methoxy-zimtaldehyd, 4-Methoxy-zimtaldehyd, 4-Hydroxy-3- methoxy-zinntaldehyd, 3,5-Dimethoxy-4-hydroxy-zinntaldehyd, 4-Dimethylanninozinntaldehyd, 2- Dimethylanninobenzaldehyd, 2-Chlor-4-dimethylanninobenzaldehyd, 4-Dimethylannino-2- methylbenzaldehyd, 4-Diethylamino-zinntaldehyd, 4-Dibutylamino-benzaldehyd, 4-Diphenylamino- benzaldehyd, 4-Dimethylamino-2-methoxybenzaldehyd, 4-(1-lmidazolyl)-benzaldehyd, Piperonal, 2,3,6,7-Tetrahydro-1 H,5H-benzo[ij]chinolizin-9-carboxaldehyd, 2,3,6,7-Tetrahydro-8-hydroxy-1 H,5H- benzo[ij]chinolizin-9-carboxaldehyd, N-Ethylcarbazol-3-aldehyd, 2-Formylnnethylen-1 ,3,3-trinnethylin- dolin (Fischers Aldehyd oder Tribasen Aldehyd), 2-lndolaldehyd, 3-lndolaldehyd, 1-Methylindol-3- aldehyd, 2-Methylindol-3-aldehyd, 1-Acetylindol-3-aldehyd, 3-Acetylindol, 1-Methyl-3-acetylindol, 2- (1',3',3'-Trimethyl-2-indolinyliden)-acetaldehyd, 1-Methylpyrrol-2-aldehyd, 1-Methyl-2-acetylpyrrol, A- Pyridinaldehyd, 2-Pyridinaldehyd, 3-Pyridinaldehyd, 4-Acetylpyridin, 2-Acetylpyridin, 3-Acetylpyridin, Pyridoxal, Chinolin-3-aldehyd, Chinolin-4-aldehyd, Antipyrin-4-aldehyd, Furfural, 5-Nitrofurfural, 2- Thenoyl-trifluor-aceton, Chromon-3-aldehyd, 3-(5'-Nitro-2'-furyl)-acrolein, 3-(2'-Furyl)-acrolein und Imi- dazol-2-aldehyd, 1 ,3-Diacetylbenzol, 1 ,4-Diacetylbenzol, 1 ,3,5-Triacetylbenzol, 2-Benzoyl-aceto- phenon , 2-(4'-Methoxybenzoyl)-acetophenon , 2-(2'-Furoyl)-acetophenon , 2-(2'-Pyridoyl)-acetophenon und 2-(3'-Pyridoyl)-acetophenon, Benzylidenaceton, 4-Hydroxybenzylidenaceton, 2- Hydroxybenzylidenaceton, 4-Methoxybenzylidenaceton, 4-Hydroxy-3-methoxybenzylidenaceton, A- Dimethylaminobenzylidenaceton, 3,4-Methylendioxybenzylidenaceton, A-Dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2, 5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylannino-2-hydroxybenzaldehyde, A-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2- Morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy- 1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4- Hydroxy-1-naphthaldehyde, A-dimethylannino-1-naphthaldehyde, 2-methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3-methoxy-cinnamaldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 4- Dimethylannino-tin-aldehyde, 2-Dimeth ylanolbenzaldehyde, 2-chloro-4-dimethylanninobenzaldehyde, 4-dimethylannino-2-methylbenzaldehyde, 4-diethylamino-tinaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl ) -benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H- benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formyln-ethylene-1,3,3-trinnethylindoline (Fischer's aldehyde or tribasic aldehyde), 2-indolaldehyde, 3-indolaldehyde, 1-methylindole 3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene ) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, A-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3 aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2- Thenoyl trifluoroacetone, chromone-3-aldehyde, 3- (5'-nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein and imidazole-2-aldehyde, 1, 3 Diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- 2'-pyridoyl) acetophenone and 2- (3'-pyridoyl) acetophenone, benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, A-dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone , A-
Pyrrolidinobenzylidenaceton, 4-Piperidinobenzylidenaceton, 4-Morpholinobenzylidenaceton, A- Diethylaminobenzylidenaceton, 3-Benzyliden-2,4-pentandion, 3-(4'-Hydroxybenzyliden)-2,4- pentandion, 3-(4'-Dimethylanninobenzyliden)-2,4-pentandion, 2-Benzylidencyclohexanon, 2-(4'- Hydroxybenzyliden)-cyclohexanon, 2-(4'-Dimethylanninobenzyliden)-cyclohexanon, 2-Benzyliden-1 ,3- cyclohexandion, 2-(4'-Hydroxybenzyliden)-1 ,3-cyclohexandion, 3-(4'-Dimethylanninobenzyliden)-1 ,3- cyclohexandion, 2-Benzyliden-5,5-dimethyl-1 ,3-cyclohexandion, 2-(4'-Hydroxybenzyliden)-5,5- dimethyl-1 ,3-cyclohexandion, 2-(4'-Hydroxy-3-methoxybenzyliden)-5,5-dinnethyl-1 ,3-cyclohexandion, 2-(4'-Dimethylanninobenzyliden)-5,5-dinnethyl-1 ,3-cyclohexandion, 2-Benzylidencyclopentanon, 2'-(4- Hydroxybenzyliden)-cyclopentanon, 2-(4'-Dimethylanninobenzyliden)-cyclopentanon, 5-(4-Pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, A-diethylaminobenzylideneacetone, 3-benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylanninobenzylidene) -2, 4-pentanedione, 2-benzylidenecyclohexanone, 2- (4'-hydroxybenzylidene) -cyclohexanone, 2- (4'-dimethylanninobenzylidene) -cyclohexanone, 2-benzylidene-1, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1 , 3-cyclohexanedione, 3- (4'-dimethylanninobenzylidene) -1, 3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl -1, 3-cyclohexanedione, 2- (4'-hydroxy-3-methoxybenzylidene) -5,5-dinethyl-1, 3-cyclohexanedione, 2- (4'-dimethylanninobenzylidene) -5,5-dinethyl-1, 3 cyclohexanedione, 2-benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene) cyclopentanone, 2- (4'-dimethylanninobenzylidene) cyclopentanone, 5- (4-
Dimethylanninophenyl)penta-2,4-dienal, 5-(4-Diethylaminophenyl)penta-2,4-dienal, 5-(4-Methoxy- phenyl)penta-2,4-dienal, 5-(3,4-Dimethoxyphenyl)penta-2,4-dienal, 5-(2,4-Dimethoxyphenyl)penta- 2,4-dienal, 5-(4-Piperidinophenyl)penta-2,4-dienal, 5-(4-Morpholinophenyl)penta-2,4-dienal, 5-(4- Pyrrolidinophenyl)penta-2,4-dienal, 6-(4-Dimethylanninophenyl)hexa-3,5-dien-2-on, 6-(4-Dimethylanninophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4-dimethoxyphenyl ) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) penta- 2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal, 6- (4-dimethylanninophenyl) hexa-3,5-dien-2-one, 6- (4-
Diethylaminophenyl)hexa-3,5-dien-2-on, 6-(4-Methoxyphenyl)hexa-3,5-dien-2-on, 6-(3,4-Diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5-dien-2-one, 6- (3,4-
Dimethoxyphenyl)hexa-3,5-dien-2-on, 6-(2,4-Dimethoxyphenyl)hexa-3,5-dien-2-on, 6-(4-Dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (4-
Piperidinophenyl)hexa-3,5-dien-2-on, 6-(4-Morpholinophenyl)hexa-3,5-dien-2-on, 6-(4-Piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- (4-
Pyrrolidinophenyl)hexa-3,5-dien-2-on, 5-(4-Dimethylannino-1-naphthyl)penta-3,5-dienal, 2-Pyrrolidinophenyl) hexa-3,5-dien-2-one, 5- (4-dimethylannino-1-naphthyl) penta-3,5-dienal, 2-
Nitrobenzaldehyd, 3-Nitrobenzaldehyd, 4-Nitrobenzaldehyd, 4-Methyl-3-nitrobenzaldehyd, 3-Hydroxy- 4-nitrobenzaldehyd, 4-Hydroxy-3-nitrobenzaldehyd, 5-Hydroxy-2-nitrobenzaldehyd, 2-Hydroxy-5- nitrobenzaldehyd, 2-Hydroxy-3-nitrobenzaldehyd, 2-Fluor-3-nitrobenzaldehyd, 3-Methoxy-2- nitrobenzaldehyd, 4-Chlor-3-nitrobenzaldehyd, 2-Chlor-6-nitrobenzaldehyd, 5-Chlor-2- nitrobenzaldehyd, 4-Chlor-2-nitrobenzaldehyd, 2,4-Dinitrobenzaldehyd, 2,6-Dinitrobenzaldehyd, 2- Hydroxy-3-methoxy-5-nitrobenzaldehyd, 4,5-Dimethoxy-2-nitrobenzaldehyd, 6-Nitropiperonal, 2-Nitro- piperonal, 5-Nitrovanillin, 2,5-Dinitrosalicylaldehyd, 5-Brom-3-nitrosalicylaldehyd, 3-Nitro-4-formyl- benzolsulfonsäure, 4-Nitro-1-naphthaldehyd, 2-Nitrozimtaldehyd, 3-Nitrozimtaldehyd, A- Nitrozimtaldehyd, 9-Methyl-3-carbazolaldehyd, 9-Ethyl-3-carbazolaldehyd, 3-Acetylcarbazol, 3,6- Diacetyl-9-ethylcarbazol, S-Acetyl-θ-nnethylcarbazol, 1 ,4-Dimethyl-3-carbazolaldehyd, 1 ,4,9-Trimethyl- 3-carbazolaldehyd, 4-Formyl-1-nnethylpyridiniunn-, 2-Formyl-1-nnethylpyridiniunn-, 4-Formyl-1- ethylpyridinium-, 2-Formyl-1-ethylpyridiniunn-, 4-Formyl-1-benzylpyridiniunn-, 2-Formyl-1- benzylpyridinium-, 4-Formyl-1 ,2-dimethylpyridiniunn-, 4-Formyl-1 ,3-dimethylpyridiniunn-, 4-Formyl-1- methylchinolinium-, 2-Formyl-1-methylchinolinium-, 4-Acetyl-i-nnethylpyridiniunn-, 2-Acetyl-1-methyl- pyridinium-, 4-Acetyl-1 -methylchinolinium-, 5-Formyl-1 -methylchinolinium-, 6-Formyl-1- methylchinolinium-, 7-Formyl-i-methylchinolinium-, 8-Formyl-1-methylchinolinium, 5-Formyl-1- ethylchinolinium-, 6-Formyl-i-ethylchinolinium-, 7-Formyl-i-ethylchinolinium-, 8-Formyl-1- ethylchinolinium, 5-Formyl-i-benzylchinolinium-, 6-Formyl-i-benzylchinolinium-, 7-Formyl-1- benzylchinolinium-, 8-Formyl-1-benzylchinolinium, 5-Formyl-i-allylchinolinium-, 6-Formyl-1- allylchinolinium-, 7-Formyl-i-allylchinolinium- und 8-Formyl-i-allylchinolinium-, 5-Acetyl-1- methylchinolinium-, 6-Acetyl-1 -methylchinolinium-, 7-Acetyl-1 -methylchinolinium-, 8-Acetyl-1- methylchinolinium, 5-Acetyl-i-ethylchinolinium-, 6-Acetyl-i-ethylchinolinium-, 7-Acetyl-1- ethylchinolinium-, δ-Acetyl-1-ethylchinolinium, 5-Acetyl-i-benzylchinolinium-, 6-Acetyl-1- benzylchinolinium-, 7-Acetyl-1-benzylchinolinium-, δ-Acetyl-1-benzylchinolinium, 5-Acetyl-1- allylchinolinium-, 6-Acetyl-i-allylchinolinium-, 7-Acetyl-1-allylchinolinium- und 8-Acetyl-1- allylchinolinium, 9-Formyl-IO-methylacridinium-, 4-(2'-Formylvinyl)-1-methylpyridinium-, 1 ,3-Dimethyl- 2-(4'-formylphenyl)-benzimidazolium-, 1 ,3-Dimethyl-2-(4'-formylphenyl)-imidazolium-, 2-(4'-Nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4- Chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitro-piperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, A-nitrocinnamaldehyde, 9- Methyl 3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, S-acetyl-θ-ethylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1,4, 9-trimethyl-3-carbazolaldehyde, 4-formyl-1-naphthylpyridiniu n-, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl Formyl 1, 2-dimethylpyridinium, 4-formyl-1, 3-dimethylpyridinium, 4-formyl-1 methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1-methylpyridinium, 2-acetyl-1-methyl-pyridinium, 4-acetyl-1-methyl-quinolinium, 5-formyl-1-methyl-quinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-one ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl- i-allyl quinolinium, 6-formyl-1-allyl quinolinium, 7-formyl-i-allyl quinolinium and 8-formyl-i-allyl quinolinium, 5-acetyl-1-methyl quinolinium, 6-acetyl-1-methyl quinolinium, 7-acetyl-1-methylquinolinium, 8-acetyl-1-methylquinolinium, 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 6-acetyl-1 ethylquinolinium, 5-acetyl-1-benzylquinolinium, 6-acetyl-1-benzylquinolinium, 7-acetyl-1-benzylquinolinium, 6-acetyl-1-benzyl 1-quinolinium, 5-acetyl-1-allyl-quinolinium, 6-acetyl-1-allyl-quinolinium, 7-acetyl-1-allyl-quinolinium and 8-acetyl-1-allyl-quinolinium, 9-formyl-1-methylacridinium, 4- (2 '-Formylvinyl) -1-methylpyridinium, 1, 3-dimethyl-2- (4'-formylphenyl) -benzimidazolium, 1, 3-dimethyl-2- (4'-formylphenyl) -imidazolium, 2- (4 '-
Formylphenyl)-3-methylbenzothiazolium-, 2-(4'-Acetylphenyl)-3-methylbenzothiazolium-, 2-(4'- Formylphenyl)-3-methylbenzoxazolium-, 2-(5'-Formyl-2'-furyl)-3-methylbenzothiazolium-, 2-(5'-Formyl- 2'-furyl)-3-methylbenzothiazolium-, 2-(5'-Formyl-2'-thienyl)-3-methylbenzothiazolium-, 2-(3'-For- mylphenyl)-3-methylbenzothiazolium-, 2-(4'-Formyl-1-naphthyl)-3-methylbenzothiazolium-, 5-Chlor-2- (4'-formylphenyl)-3-methylbenzothiazolium-, 2-(4'-Formylphenyl)-3,5-dimethylbenzothiazolium- benzolsulfonat, -p-toluolsulfonat, -methansulfonat, -Perchlorat, -sulfat, -chlorid, -bromid, -iodid, - tetrachlorozinkat, -methylsulfat-, trifluormethansulfonat, -tetrafluoroborat, lsatin, 1-Methyl-isatin, 1- Allyl-isatin, 1-Hydroxymethyl-isatin, 5-Chlor-isatin, 5-Methoxy-isatin, 5-Nitroisatin, 6-Nitro-isatin, 5- Sulfo-isatin, 5-Carboxy-isatin, Chinisatin, 1-Methylchinisatin, sowie beliebigen Gemischen der voranstehenden Verbindungen.Formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) - 3-methylbenzothiazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3'-For - methylphenyl) -3-methylbenzothiazolium, 2- (4'-formyl-1-naphthyl) -3-methylbenzothiazolium, 5-chloro-2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4 ' -Formylphenyl) -3,5-dimethylbenzothiazolium benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1 -Methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carboxy-isatin , Quinisatin, 1-methylquinisatin, as well as any mixtures of the above compounds.
Ganz besonders bevorzugt werden in den erfindungsgemäßen Mitteln Benzaldehyd, Zimtaldehyd und Naphthaldehyd sowie deren Derivate, insbesondere mit einem oder mehreren Hydroxy-, Alkoxy- oder Aminosubstituenten, als reaktive Carbonylverbindung verwendet. Dabei werden wiederum die Verbindungen gemäß Formel (Ca-1 ) bevorzugt, Benzaldehyde, cinnamic aldehyde and naphthaldehyde and their derivatives, in particular having one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl compound in the agents according to the invention. Again, the compounds according to formula (Ca-1) are preferred,
Figure imgf000034_0001
) worin
Figure imgf000034_0001
in which
• R1 , R2 und R3 stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C-ι-C6-Alkylgruppe, eine Hydroxygruppe, eine d-C6-Alkoxygruppe, eine C-ι-C6-Dialkylanninogruppe, eine Di(C2-C6-hydroxyalkyl)anninogruppe, eine Di(C-i-C6-alkoxy-C-i-C6-alkyl)anninoguppe, eine C1-C6- Hydroxyalkyloxygruppe, eine Sulfonylgruppe, eine Carboxygruppe, eine Sulfonsäuregruppe, eine Sulfonamidogruppe, eine Sulfonamidgruppe, eine Carbamoylgruppe, eine C2-C6-Acylgruppe oder eine Nitrogruppe,• R 1, R 2 and R 3 are independently a hydrogen atom, a halogen atom, a C-ι-C6 alkyl group, a hydroxy group, a dC 6 alkoxy group, a C-ι-C 6 -Dialkylanninogruppe, a di (C 2 -C 6 -hydroxyalkyl) -annino group, a di (C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl) -annino group, a C 1 -C 6 -hydroxyalkyloxy group, a sulfonyl group, a carboxy group, a sulfonic acid group, a sulfonamido group, a sulfonamide group, a carbamoyl group, a C 2 -C 6 acyl group or a nitro group,
• Z' steht für eine direkte Bindung oder eine Vinylengruppe,Z 'is a direct bond or a vinylene group,
• R4* und R5* stehen für ein Wasserstoffatom oder bilden gemeinsam, zusammen mit dem Restmolekül einen 5- oder 6-gliederigen aromatischen oder aliphatischen Ring.• R 4 * and R 5 * represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.
Die Derivate der Benzaldehyde, Naphthaldehyde bzw. Zimtaldehyde der reaktiven Carbonylverbindung gemäß Komponente C werden besonders bevorzugt ausgewählt aus bestimmten Aldehyden. Hier sind erfindungsgemäße Mittel bevorzugt, die zusätzlich mindestens eine reaktive Carbonylverbindung enthalten, die ausgewählt wird, aus der Gruppe, bestehend aus A- Hydroxy-3-methoxybenzaldehyd, 3,5-Dimethoxy-4-hydroxybenzaldehyd, 4-Hydroxy-1-naphthaldehyd, 4-Hydroxy-2-methoxybenzaldehyd, 3,4-Dihydroxy-5-methoxybenzaldehyd, 3,4,5-The derivatives of the benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component C are particularly preferably selected from certain aldehydes. Preferred herein are agents which additionally contain at least one reactive carbonyl compound selected from the group consisting of A-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-
Trihydroxybenzaldehyd, 3,5-Dibrom-4-hydroxybenzaldehyd, 4-Hydroxy-3-nitrobenzaldehyd, 3-Brom- 4-hydroxybenzaldehyd, 4-Hydroxy-3-methylbenzaldehyd, 3,5-Dimethyl-4-hydroxy-benzaldehyd, 5- Brom-4-hydroxy-3-methoxybenzaldehyd, 4-Diethylamino-2-hydroxybenzaldehyd, 4-Dimethylamino-2- methoxybenzaldehyd, Coniferylaldehyd, 2-Methoxybenzaldehyd, 3-Methoxybenzaldehyd, A- Methoxybenzaldehyd, 2-Ethoxybenzaldehyd, 3-Ethoxybenzaldehyd, 4-Ethoxybenzaldehyd, A- Hydroxy-2,3-dimethoxy-benzaldehyd, 4-Hydroxy-2,5-dimethoxy-benzaldehyd, 4-Hydroxy-2,6- dimethoxy-benzaldehyd, 4-Hydroxy-2-methyl-benzaldehyd, 4-Hydroxy-2,3-dimethyl-benzaldehyd, A- Hydroxy-2,5-dimethyl-benzaldehyd, 4-Hydroxy-2,6-dimethyl-benzaldehyd, 3,5-Diethoxy-4-hydroxy- benzaldehyd, 2,6-Diethoxy-4-hydroxy-benzaldehyd, 3-Hydroxy-4-methoxy-benzaldehyd, 2-Hydroxy-4- methoxy-benzaldehyd, 2-Ethoxy-4-hydroxy-benzaldehyd, 3-Ethoxy-4-hydroxy-benzaldehyd, A- Ethoxy-2-hydroxy-benzaldehyd, 4-Ethoxy-3-hydroxy-benzaldehyd, 2,3-Dimethoxybenzaldehyd, 2,4- Dimethoxybenzaldehyd, 2,5-Dimethoxybenzaldehyd, 2,6-Dimethoxybenzaldehyd, 3,4- Dimethoxybenzaldehyd, 3,5-Dimethoxybenzaldehyd, 2,3,4-Trimethoxybenzaldehyd, 2,3,5- Trimethoxybenzaldehyd, 2,3,6-Trimethoxybenzaldehyd, 2,4,6-Trimethoxybenzaldehyd, 2,4,5- Trimethoxybenzaldehyd, 2,5,6-Trimethoxybenzaldehyd, 2-Hydroxybenzaldehyd, 3-Trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5- Bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, A-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4- Ethoxybenzaldehyde, A-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4- Hydroxy-2,3-dimethylbenzaldehyde, A-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6- Diethoxy-4-hydroxy-benzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxy-benzaldehyde, A- Ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxy-benzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4- Dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4- Dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2, 5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3
Hydroxybenzaldehyd, 4-Hydroxybenzaldehyd, 2,3-Dihydroxybenzaldehyd, 2,4-Hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-
Dihydroxybenzaldehyd, 2,4-Dihydroxy-3-methyl-benzaldehyd, 2,4-Dihydroxy-5-methyl-benzaldehyd, 2,4-Dihydroxy-6-methyl-benzaldehyd, 2,4-Dihydroxy-3-methoxy-benzaldehyd, 2,4-Dihydroxy-5- methoxy-benzaldehyd, 2,4-Dihydroxy-6-methoxy-benzaldehyd, 2,5-Dihydroxybenzaldehyd, 2,6- Dihydroxybenzaldehyd, 3,4-Dihydroxybenzaldehyd, 3,4-Dihydroxy-2-methyl-benzaldehyd, 3,4- Dihydroxy-5-methyl-benzaldehyd, 3,4-Dihydroxy-6-methyl-benzaldehyd, 3,4-Dihydroxy-2-methoxy- benzaldehyd, 3,5-Dihydroxybenzaldehyd, 2,3,4-Trihydroxybenzaldehyd, 2,3,5-Dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-one methyl-benzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3, 4-trihydroxybenzaldehyde, 2,3,5-
Trihydroxybenzaldehyd, 2,3,6-Trihydroxybenzaldehyd, 2,4,6-Trihydroxybenzaldehyd, 2,4,5- Trihydroxybenzaldehyd, 2,5,6-Trihydroxybenzaldehyd, 4-Dimethylanninobenzaldehyd, A- Diethylaminobenzaldehyd, 4-Dimethylamino-2-hydroxybenzaldehyd, 4-Pyrrolidinobenzaldehyd, A- Morpholinobenzaldehyd, 2-Morpholinobenzaldehyd, 4-Piperidinobenzaldehyd, 3,5-Dichlor-4- hydroxybenzaldehyd, 4-Hydroxy-3,5-diiod-benzaldehyd, 3-Chlor-4-hydroxybenzaldehyd, 5-Chlor-3,4- dihydroxybenzaldehyd, 5-Brom-3,4-dihydroxybenzaldehyd, 3-Chlor-4-hydroxy-5- methoxybenzaldehyd, 4-Hydroxy-3-iod-5-methoxybenzaldehyd, 2-Methoxy-1-naphthaldehyd, A- Methoxy-1-naphthaldehyd, 2-Hydroxy-1-naphthaldehyd, 2,4-Dihydroxy-1-napthaldehyd, 4-Hydroxy-3- methoxy-1-naphthaldehyd, 2-Hydroxy-4-methoxy-1-naphthaldehyd, 3-Hydroxy-4-methoxy-1- naphthaldehyd, 2,4-Dimethoxy-1-naphthaldehyd, 3,4-Dimethoxy-1-naphthaldehyd, 4-Dimethylannino- 1-naphthaldehyd, 2-Nitrobenzaldehyd, 3-Nitrobenzaldehyd, 4-Nitrobenzaldehyd, 4-Methyl-3- nitrobenzaldehyd, 3-Hydroxy-4-nitrobenzaldehyd, 5-Hydroxy-2-nitrobenzaldehyd, 2-Hydroxy-5- nitrobenzaldehyd, 2-Hydroxy-3-nitrobenzaldehyd, 2-Fluor-3-nitrobenzaldehyd, 3-Methoxy-2- nitrobenzaldehyd, 4-Chlor-3-nitrobenzaldehyd, 2-Chlor-6-nitrobenzaldehyd, 5-Chlor-2- nitrobenzaldehyd, 4-Chlor-2-nitrobenzaldehyd, 2,4-Dinitrobenzaldehyd, 2,6-Dinitrobenzaldehyd, 2- Hydroxy-3-methoxy-5-nitrobenzaldehyd, 4,5-Dimethoxy-2-nitrobenzaldehyd, 6-Nitropiperonal, 2-Nitro- piperonal, 5-Nitrovanillin, 2,5-Dinitrosalicylaldehyd, 5-Brom-3-nitrosalicylaldehyd, 4-Nitro-1- naphthaldehyd, 2-Nitrozimtaldehyd, 3-Nitrozimtaldehyd, 4-Nitrozimtaldehyd, 4-Dimethyl- aminoziimtaldehyd, 2-Dimethylanninobenzaldehyd, 2-Chlor-4-dimethylanninobenzaldehyd, A- Dimethylannino-2-nnethylbenzaldehyd, 4-Diethylamino-zinntaldehyd, 4-Dibutylamino-benzaldehyd, A- Diphenylamino-benzaldehyd, 4-(1-lmidazolyl)-benzaldehyd und Piperonal.Trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethylanninobenzaldehyde, A-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, A-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro 3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, A- Methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3 Hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylannino-1-naphthaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydr oxy-4-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro 3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5- nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitro-piperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 4-nitro-1-naphthaldehyde, 2- Nitrozimtaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylanninobenzaldehyde, 2-chloro-4-dimethylanninobenzaldehyde, A-dimethylannino-2-methylbenzaldehyde, 4-diethylamino-tinaldehyde, 4-dibutylaminobenzaldehyde, A- Diphenylaminobenzaldehyde, 4- (1-imidazolyl) benzaldehyde and piperonal.
Erfindungsgemäß bevorzugte Mittel sind dadurch gekennzeichnet, dass sie als Haarfärbemittel formuliert sind, die bezogen auf ihr Gewicht 0,01 bis 20 Gew.-%, vorzugsweise 0,05 bis 15 Gew.-%, besonders bevorzugt 0,1 bis 12,5 Gew.-% und insbesondere 0,2 bis 10 Gew.-% einer oder mehrerer reaktive Carbonylverbindung(en) enthalten. Als CH-acide werden im allgemeinen solche Verbindungen angesehen, die ein an ein aliphatisches Kohlenstoffatom gebundenes Wasserstoffatom tragen, wobei aufgrund von Elektronen-ziehenden Substituenten eine Aktivierung der entsprechenden Kohlenstoff-Wasserstoff-Bindung bewirkt wird. Unter CH-acide Verbindungen fallen erfindungsgemäß auch Enamine, die durch alkalische Behandlung von quaternierten N-Heterozyklen mit einer in Konjugation zum quartären Stickstoff stehenden CH-aciden Alkylgruppe entstehen.Agents preferred according to the invention are characterized in that they are formulated as hair colorants, based on their weight from 0.01 to 20 wt .-%, preferably 0.05 to 15 wt .-%, particularly preferably 0.1 to 12.5 wt .-% and in particular 0.2 to 10 wt .-% of one or more reactive carbonyl compound (s). As CH-acidic compounds are generally considered to carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents activation of the corresponding carbon-hydrogen bond is effected. According to the invention, CH-acidic compounds also include enamines which are formed by alkaline treatment of quaternized N-heterocycles with a CH-acidic alkyl group in conjugation with the quaternary nitrogen.
Die CH-aciden Verbindungen der Komponente B sind bevorzugt ausgewählt aus der Gruppe bestehend aus 1 ,2,3,3-Tetramethyl-3H-indoliumiodid, 1 ,2,3,3-Tetramethyl-3H-indolium-p- toluolsulfonat, 1 ,2,3,3-Tetramethyl-3H-indolium-methansulfonat, 1 ,3,3-Trimethyl-2-methylenindolin (Fischersche Base), 2,3-Dimethyl-benzothiazoliumiodid, 2,3-Dimethyl-benzothiazolium-p-toluolsul- fonat, 2,3-Dimethyl-naphtho[1 ,2-d]thiazolium-p-toluolsulfonat, 3-Ethyl-2-methyl-naphtho[1 ,2-d]thiazo- lium-p-toluolsulfonat, Rhodanin, Rhodanin-3-essigsäure, 1 ,4-Dimethylchinolinium-iodid, 1 ,2- Dimethylchinolinium-iodid, Barbitursäure, Thiobarbitursäure, 1 ,3-Dimethylthiobarbitursäure, 1 ,3- Diethylthiobarbitursäure, 1 ,3-Diethylbarbitursäure, Oxindol, 3-lndoxylacetat, 2-Cumaranon, 5- Hydroxy-2-cumaranon, 6-Hydroxy-2-cumaranon, 3-Methyl-1-phenyl-pyrazolin-5-on, lndan-1 ,2-dion, lndan-1 ,3-dion, lndan-1-on, Benzoylacetonitril, 3-Dicyanmethylenindan-1-on, 2-Amino-4-imino-1 ,3- thiazolin-hydrochlorid, 5,5-Dimethylcyclohexan-1 ,3-dion, 2H-1 ,4-Benzoxazin-4H-3-on, 3-Ethyl-2- methyl-benzoxazoliumiodid, 3-Ethyl-2-methyl-benzothiazoliumiodid, 1-Ethyl-4-methyl- chinoliniumiodid, 1-Ethyl-2-methylchinoliniumiodid, 1 ,2,3-Trimethylchinoxaliniumiodid, 3-Ethyl-2- methyl-benzoxazolium-p-toluolsulfonat, 3-Ethyl-2-methyl-benzothiazolium-p-toluolsulfonat, 1-Ethyl-4- methyl-chinolinium-p-toluolsulfonat, 1-Ethyl-2-methylchinolinium-p-toluolsulfonat, und 1 ,2,3- Trimethylchinoxalinium-p-toluolsulfonat.The CH-acidic compounds of component B are preferably selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium-p-toluenesulfonate Fonate, 2,3-dimethylnaphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methylnaphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine 3-acetic acid, 1, 4-dimethylquinolinium iodide, 1, 2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-indoxylacetate, 2- Coumaranone, 5-hydroxy-2-cumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenyl-pyrazolin-5-one, indan-1, 2-dione, indan-1, 3-dione, indanine 1-one, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5-dimethyl cyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methyl-benzoxazolium iodide, 3-ethyl-2-methyl-benzothiazolium iodide, 1-ethyl-4-methyl quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1, 2,3-trimethylquinoxaluminum iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl 4-methylquinolinium p-toluenesulfonate, 1-ethyl-2-methylquinolinium p-toluenesulfonate, and 1,2,3-trimethylquinoxaluminum p-toluenesulfonate.
Geeignete Verbindungen mit primärer oder sekundärer Aminogruppe als Komponente B sind z.B. primäre aromatische Amine wie N,N-Dimethyl-, N,N-Diethyl-, N- (2- Hydroxyethyl)-N-ethyl-, N,N-Bis- (2-hydroxyethyl)-, N-(2-Methoxyethyl-), 2,3-, 2,4-, 2,5- Dichlor-p-phenylendiamin, 2-Chlor-p- phenylendiamin, 2,5-Dihydroxy-4- morpholinoanilin- dihydrobromid, 2-, 3-, 4-Aminophenol, 2- Aminomethyl-4-aminophenoi, 2- Hydroxymethyl- 4-aminophenoi, o-, p-Phenylendiamin, o- Toluyiendiamin, 2,5-Diaminotoluol, -phenot, - phenethol, 4-Amino-3-methylphenoi, 2-(2,5- Diaminophenyl)-ethanoi, 2,4- Diaminophen- oxyethanoi, 2-(2,5-Diaminophenoxy)-ethanol, 4- Methylamino-, 3-Amino-4- (2'- hydroxyethyloxy)-, 3,4-Methylendiamino-, 3,4-Methylendioxyanilin, 3- Amino-2,4-dichlor-, 4-Methylamino-, 2-Methyl-5-amino-, 3-Methyl-4-amino-, 2-Methyl-5-(2- hydro- xyethylamino)-, 6-Methyl-3-amino-2-chlor-, 2-Methyl-5-amino-4-chlor-, 3, 4-Methylendi- oxy-, 5-(2- Hydroxyethylamino)-4-methoxy-2-nnethyl-, 4-Amino-2- hydroxymethylphenol, 1 ,3-Diamino-2,4- dimethoxybenzol, 2-, 3-, 4-Aminobenzoesäure, - phenylessigsäure, 2,3-, 2,4-, 2,5-, 3,4-, 3,5- Diaminobenzoesäure, A-, 5-Aminosalicyisäure, 3- Amino-4-hydroxy-, 4-Amino-3-hydroxy- benzoesäure, 2-, 3-, 4-Aminobenzolsulfonsäure, 3-Amino- A- hydroxybenzolsulfonsäure, 4-Amino-3- hydroxynaphthalin-1 -sulfonsäure, 6- Amino-7- hydroxynaphthalin-2-sulfonsäure, 7-Amino-4- hydroxynaphthalin-2- sulfonsäure, 4-Amino- 5-hydroxynaphthalin-2,7-disulfonsäure, 3-Amino-2- naphthoesäure, 3- Aminophthalsäure, 5-Aminoisophthalsäure, 1 ,3,5-, 1 ,2,4-Triaminobenzol, 1 ,2,4,5- Tetraaminobenzol, 2,4,5- Triaminophenol, Pentaaminobenzol, Hexaaminobenzol, 2,4,6- Triaminoresorcin, 4,5- Diaminobrenzcatechin, 4,6-Diaminopyrogaliol, 3,5-Diamino-4- hydroxybrenzcatechin, aromatische Aniline bzw. Phenole mit einem weiteren aromatischen Rest, wie sie in der nachstehenden Formel dargestellt sindSuitable compounds having primary or secondary amino group as component B are, for example, primary aromatic amines such as N, N-dimethyl, N, N-diethyl, N- (2-hydroxyethyl) -N-ethyl, N, N-bis ( 2-hydroxyethyl) -, N- (2-methoxyethyl), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4 - morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenoi, 2-hydroxymethyl-4-aminophenoi, o-, p-phenylenediamine, o-toluenediamine, 2,5-diaminotoluene, -phenot , - phenethole, 4-amino-3-methylphenoi, 2- (2,5-diaminophenyl) -ethanoi, 2,4-diaminophenoxyethanoi, 2- (2,5-diaminophenoxy) ethanol, 4-methylamino, 3 -Amino-4- (2'-hydroxyethyloxy) -, 3,4-methylenediamino, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro, 4-methylamino, 2-methyl-5-amino , 3-methyl-4-amino, 2-methyl-5- (2-hydroxyethylamino) -, 6-methyl-3-amino-2-chloro, 2-methyl-5-amino-4-chloro , 3, 4-methylenedioxy, 5- (2- Hydroxyethylamino) -4-methoxy-2-methyl, 4-amino-2-hydroxymethylphenol, 1, 3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, - phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, A-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxybenzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-A-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid , 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3,5-, 1, 2,4-triaminobenzene, 1, 2, 4,5-tetraaminobenzene, 2,4,5-triaminophenol, penta-aminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobrencatechol, 4,6-diaminopyrogaliol, 3,5-diamino-4-hydroxy-catechol, aromatic anilines or phenols with a further aromatic radical, as shown in the formula below
Figure imgf000037_0001
in der
Figure imgf000037_0001
in the
• R7 für eine Hydroxy- oder eine Aminogruppe, die durch Ci_4-Alkyl-, Ci.4-Hydroxyalkyl-, d-4- Alkoxy- oder Ci.4-Alkoxy-Ci.4-alkylgruppen substituiert sein kann, steht,• R 7 represents a hydroxy or an amino group represented by CI_ 4 alkyl, Ci. 4 -Hydroxyalkyl-, d- 4 - alkoxy- or Ci. 4- alkoxy-Ci. 4- alkyl groups may be substituted,
• R8, R9, R10, R11 und R12 unabhängig voneinander für ein Wasserstoffatom, eine Hydroxy- oder eine Aminogruppe, die durch d-C4-Alkyl-, C-ι-C4-Hydroxyalkyl, C1-C4-AIkOXy-, d-C4-Aminoalkyl- oder C-ι-C4-Alkoxy-C-ι-C4-alkylgruppen substituiert sein kann, stehen, und• R 8, R 9, R 10, R 11 and R 12 independently represent a hydrogen atom, a hydroxy or an amino group by C 4 alkyl, C-ι-C 4 hydroxyalkyl, C 1 -C 4 -Aikoxy, C 1 -C 4 -aminoalkyl or C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl groups may be substituted, and
• P für eine direkte Bindung, eine gesättigte oder ungesättigte, ggf. durch Hydroxygruppen substituierte Kohlenstoffkette mit 1 bis 4 Kohlenstoffatomen, eine Carbonyl-, Sulfoxy-, Sulfonyl- oder Iminogruppe, ein Sauerstoff- oder Schwefelatom, oder eine GruppeP is a direct bond, a saturated or unsaturated, optionally substituted by hydroxy groups carbon chain having 1 to 4 carbon atoms, a carbonyl, sulfoxy, sulfonyl or imino group, an oxygen or sulfur atom, or a group
-Q'-(CH2-Q-CH2-Q")O--Q '- (CH 2 -Q-CH 2 -Q ") O -
in derin the
• Q eine direkte Bindung, eine CH2- oder CHOH-Gruppe bedeutet,Q signifies a direct bond, a CH 2 or CHOH group,
• Q' und Q" unabhängig voneinander für ein Sauerstoffatom, eine NR13-Gruppe, worin R13 ein Wasserstoffatom, eine d-4-Alkyl- oder eine Hydroxy-Ci_4-alkylgruppe, wobei auch beide Gruppen zusammen mit dem Restmolekül einen 5-, 6- oder 7-Ring bilden können, bedeutet, die Gruppe O-(CH2)P-NH oder NH-(CH2)P-O, worin p und p' 2 oder 3 sind, stehen und • o eine Zahl von 1 bis 4 bedeutet,• Q 'and Q "are each independently an oxygen atom, an NR 13 group, wherein R 13 is a hydrogen atom alkyl group, a C 4 alkyl or a hydroxy-CI_ 4, wherein both groups together with the remainder of the molecule is a 5 , 6- or 7-membered ring, means the group O- (CH 2 ) P -NH or NH- (CH 2 ) P -O, wherein p and p 'are 2 or 3, and O is a number from 1 to 4,
wie beispielsweise 4,4'-Diaminostilben, 4,4'-Diaminostilben-2,2'- disulfonsäure-mono- oder -di-Na- SaIz, 4-Amino-4'-dimethylanninostilben, 4,4'- Diaminodiphenylmethan, -sulfid, -sulfoxid, -amin, 4,4'- Diaminodiphenyiamin-2-sulfonsäure, 4,4'- Diaminobenzophenon, - diphenylether, 3, 3', 4,4'- Tetraaminodiphenyl, 3,3',4,4'-Tetraamino- benzophenon, 1 ,3-Bis- (2,4-diaminophenoxy)-propan, 1 ,8- Bis-(2,5-diaminophenoxy)-3,6-dioxaoctan, 1 ,3-Bis-(4- aminophenylamino)-propan, -2-propanoi, 1 ,3- Bis-[N-(4-aminophenyl)-2- hydroxyethyla- mino]-2-propanol, N,N-Bis-[2-(4-aminophenoxy)-ethyl]- methylamin, N- Phenyl-1 ,4-phenylendiamin.for example 4,4'-diaminostilbene, 4,4'-diaminostilbene-2,2'-disulphonic acid mono- or di-Na-salt, 4-amino-4'-dimethylanninostilbene, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4'-diaminodiphenyiamine-2-sulfonic acid, 4,4'-diaminobenzophenone, - diphenyl ether, 3, 3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4 ' Tetraaminobenzophenone, 1,3-bis- (2,4-diaminophenoxy) -propane, 1, 8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane, 1, 3-bis- (4- aminophenylamino) -propane, -2-propanoi, 1,3-bis [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis [2- (4-aminophenoxy) -ethyl] - methylamine, N-phenyl-1, 4-phenylenediamine.
Die vorgenannten Verbindungen können sowohl in freier Form als auch in Form ihrer physiologisch verträglichen Salze, insbesondere als Salze anorganischer Säuren, wie Salz- oder Schwefelsäure, eingesetzt werden.The abovementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid.
Geeignete stickstoffhaltige heterocyclische Verbindungen sind z.B. 2-, 3-, 4-Amino-, 2- Amino-3- hydroxy-, 2,6-Diamino-, 2,5-Diamino-, 2,3-Diamino-, 2- Dimethylamino-5-amino-, 2-Methylamino-3- amino-6-methoxy-, 2,3-Diamino-6-methoxy-, 2,6-Dimethoxy- 3,5-dia- mino-, 2,4,5-Triamino-, 2,6- Dihydroxy-3,4-dimethylpyridin, 2,4-Dihydroxy- 5,6-diamino-, 4,5,6-Triamino-, 4-Hydroxy-2,5,6- triamino-, 2-Hydroxy-4,5,6-triamino-, 2, 4,5,6-Tetraamino-, 2-Methylamino-4,5,6-triamino-, 2,4-, 4,5- Diamino-, 2-Amino-4- methoxy-6-methyl- pyrimidin, 3,5-Diaminopyrazol, -1 ,2,4-triazol, 3-Amino-, 3- Amino-5- hydroxypyrazol, 2-,3-, 8-Aminochinolin, 4-Amino-chinaidin, 2-, 6-Aminonicotinsäure, 5- Aminoisochinolin, 5-, 6- Aminoindazol, 5-, 7-Amino-benzimidazol, -benzothiazol, 2,5-Dihydroxy-4- morpholinoani- lin sowie Indole und Indoline, sowie deren physiologisch verträgliche Salze, sein. Bevorzugte Beispiele für Indol- bzw. Indolinderivate 5,6-Dihydroxyindol, N- Methyl-5,6-dihy- droxyindol, N-Ethyl-5,6-dihydroxyindol, N-Propyl-5,6-dihydroxyindol, N- Butyl-5,6-dihy- droxyindol, 5,6-Dihydroxyindol-2-carbonsäure, 6-Hydroxyindol, 6- Aminoindol und 4-Aminoindol. Weiterhin bevorzugt sind 5,6-Dihydroxyindolin, N-Methyl-5,6- dihydroxyindolin, N-Ethyl-5,6-dihydroxyindolin, N- Propyl-5,6-dihydroxyindolin, N-Butyl-5,6- dihydroxyindolin, 5,6-Dihydroxyindolin-2-carbonsäure. 6- Hydroxyindolin, 6-Aminoindolin und 4-Aminoindolin. Die vorgenannten Verbindungen können sowohl in freier Form als auch in Form ihrer physiologisch verträglichen Salze, z. B. als Salze anorganischer Säuren, wie Salz- oder Schwefelsäure, eingesetzt werden.Suitable nitrogen-containing heterocyclic compounds are e.g. 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5-amino, 2-methylamino-3-amino-6-methoxy, 2,3-diamino-6-methoxy, 2,6-dimethoxy-3,5-diamino, 2,4,5-triamino, 2, 6-Dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino, 4,5,6-triamino, 4-hydroxy-2,5,6-triamino, 2-hydroxy-4 , 5,6-triamino, 2, 4,5,6-tetraamino, 2-methylamino-4,5,6-triamino, 2,4-, 4,5-diamino, 2-amino-4- methoxy-6-methyl-pyrimidine, 3,5-diaminopyrazole, -1, 2,4-triazole, 3-amino, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-amino chinaidine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-aminobenzimidazole, benzothiazole, 2,5-dihydroxy-4-morpholinoaniline, and indoles and indolines, and theirs physiologically acceptable salts. Preferred examples of indole or indoline derivatives 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Further preferred are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5 , 6-dihydroxyindoline-2-carboxylic acid. 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline. The aforementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, for. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid, are used.
Als Aminosäuren kommen bevorzugt alle natürlich vorkommenden und synthetischen (alpha- Aminosäuren in Frage, z.B. die durch Hydrolyse aus pflanzlichen oder tierischen Proteinen, z.B. Kollagen, Keratin, Casein, Elastin, Sojaprotein, Weizengluten oder Mandelprotein, zugänglichen Aminosäuren. Dabei können sowohl sauer als auch alkalisch reagierende Aminosäuren eingesetzt werden. Bevorzugte Aminosäuren sind Arginin, Histidin, Tyrosin, Phenylalanin, DOPA (Dihydroxyphenylalanin), Ornithin, Lysin und Tryptophan. Es können aber auch andere Aminosäuren verwendet werden, wie z. B. 6- Aminocapronsäure.Preferred amino acids are all naturally occurring and synthetic (alpha-amino acids, eg the amino acids obtainable by hydrolysis from vegetable or animal proteins, eg collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (Dihydroxyphenylalanine), ornithine, lysine and tryptophan. But it can also be used other amino acids, such as. B. 6-aminocaproic acid.
Die Oligopeptide können dabei natürlich vorkommende oder synthetische Oligopeptide, aber auch die in Polypeptid- oder Proteinhydrolysaten enthaltenen Oligopeptide sein, sofern sie über eine für die Anwendung in den erfindungsgemäßen Färbemitteln ausreichende Wasserlöslichkeit verfügen. Als Beispiele sind z.B. Glutathion oder die in den Hydrolysaten von Kollagen, Keratin, Casein, Elastin, Sojaprotein, Weizengluten oder Mandelprotein enthaltenen Oligopeptide zu nennen. Bevorzugt ist dabei die Verwendung gemeinsam mit Verbindungen mit primärer oder sekundärer Aminogruppe oder mit aromatischen Hydroxyverbindungen.The oligopeptides may be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolysates, provided that they have sufficient water solubility for use in the inventive colorants. As examples, e.g. Glutathione or the oligopeptides contained in the hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Preferred is the use together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds.
Geeignete aromatische Hydroxyverbindungen sind z.B. 2-, A-, 5- Methylresorcin, 2,5- Dimethylresorcin, Resorcin, 3-Methoxyphenol, Brenzkatechin, Hydrochinon, Pyrogallol, Phloroglucin, Hydroxyhydrochinon, 2-, 3-, 4-Methoxy-, 3-Dimethylamino-, 2-(2- Hydroxyethyl)-, 3,4- Methylendioxyphenol, 2,4-, 3,4-Dihydroxybenzoesäure, - phenylessigsäure, Gallussäure, 2,4,6- Trihydroxybenzoesäure, -acetophenon, 2-, A- Chlorresorcin, 1-Naphthol, 1 ,5-, 2,3-, 2,7- Dihydroxynaphthalin, 6- Dimethylamino-4- hydroxy-2-naphthalinsulfonsäure, 3,6-Dihydroxy-2,7- naphthalinsulfonsäure.Suitable aromatic hydroxy compounds are e.g. 2-, A-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, catechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, - phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, acetophenone, 2-, A-chlororesorcinol, 1-naphthol , 1, 5, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.
Als CH-aktive Verbindungen können beispielhaft genannt werden 1 ,2,3,3- Tetramethyl- 3H- indoliumiodid, 1 ,2,3,3-Tetramethyl-3H-indolium-p-toluoisulfonat, 1 ,2, 3,3-Tetramethyl- 3H-indolium- methansulfonat, Fischersche Base (1 ,3,3-Trimethyl-2- methylenindolin), 2,3- Dimethyl- benzothiazoliumiodid, 2,3-Dimethyl-benzothiazolium-p- toluolsulfonat, Rhodanin, Rhodanin-3- essigsäure, 1 -Ethyl-2-chinaldiniumiodid, 1 -Methyl-2- chinaldiniumiodid Barbitursäure, Thiobarbitursäure, 1 ,3-Dimethylthiobarbitursäure, Diethylthiobarbitursäure, Oxindol, 3-lndoxylacetat, Cumaranon und 1-Methyl-3-phenyl-2-pyrazolinon.As CH-active compounds there can be exemplified 1, 2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium-p-toluoisulfonate, 1,2,3,3-tetramethyl 3H indolium methanesulfonate, Fischer's base (1,3,3-trimethyl-2-methylenindoline), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid , 1-ethyl-2-quinaldinium iodide, 1-methyl-2-quinaldinium iodide barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxylacetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.
Bevorzugt werden die CH-aciden Verbindungen aus den Formeln (II) und/oder (IM) und/oder (IV) ausgewählt The CH-acidic compounds are preferably selected from the formulas (II) and / or (III) and / or (IV)
Figure imgf000040_0001
Figure imgf000040_0001
worinwherein
R8 und R9 stehen unabhängig voneinander für eine lineare oder cyclische d-C6-Alkylgruppe, eine C2-C6-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-C-ι-C6-alkylgruppe, eine C-ι-C6-Hydroxyalkylgruppe, eine C2-C6-Polyhydroxyalkylgruppe, eine C-ι-C6-Alkoxy-C-ι-C6-alkylgruppe, eine Gruppe R'R"N-(CH2)m- , worin R1 und R" stehen unabhängig voneinander für ein Wasserstoffatom, eine C1-C4- Alkylgruppe, eine C-ι-C4-Hydroxyalkylgruppe oder eine Aryl-C-ι-C6-alkylgruppe, wobei R1 und R11 gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,R 8 and R 9 are independently a linear or cyclic dC 6 alkyl group, a C 2 -C 6 alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl C-ι-C6 alkyl group, a C-ι-C 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C-ι-C alkyl 6 -alkoxy-C-ι-C 6, a group R'R "N- (CH 2) m in which R 1 and R "independently of one another represent a hydrogen atom, a C 1 -C 4 -alkyl group, a C 1 -C 4 -hydroxyalkyl group or an aryl-C 1 -C 6 -alkyl group, where R 1 and R 11 together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
R10 und R12 stehen unabhängig voneinander für ein Wasserstoffatom oder eine Ci-C6- Alkylgruppe, wobei mindestens einer der Reste R10 und R12 eine Ci-C6-Alkylgruppe bedeutet, R11 steht für ein Wasserstoffatom, eine d-C6-Alkylgruppe, eine d-C6-Hydroxyalkylgruppe, eine C2-C6-Polyhydroxyalkylgruppe, eine d-C6-Alkoxygruppe, eine d-C6-Hydroxyalkoxygruppe, eine Gruppe RmRlvN-(CH2)q-, worin R1" und Rιv stehen unabhängig voneinander für ein Wasserstoffatom, eine d-C6-Alkylgruppe, eine d-C6-Hydroxyalkylgruppe oder eine Aryl-d-C6- alkylgruppe und q steht für eine Zahl 1 , 2, 3, 4, 5 oder 6, wobei der Rest R11 zusammen mit einem der Reste R10 oder R12 einen 5- oder 6-gliedrigen aromatischen Ring bilden kann, der gegebenenfalls mit einem Halogenatom, einer d-C6-Alkylgruppe, einer Ci-C6- Hydroxyalkylgruppe, einer C2-C6-Polyhydroxyalkylgruppe, einer Ci-C6-Alkoxygruppe, einer d- C6-Hydroxyalkoxygruppe, einer Nitrogruppe, einer Hydroxygruppe, einer Gruppe RVRVIN-(CH2)S-, worin Rv und Rvι stehen unabhängig voneinander für ein Wasserstoffatom, eine Ci-C6- Alkylgruppe, eine Ci-C6-Hydroxyalkylgruppe oder eine Aryl-Ci-C6-alkylgruppe und s steht für eine Zahl 0, 1 , 2, 3, 4, 5 oder 6 substituiert sein kann,R 10 and R 12 independently represent a hydrogen atom, or a Ci-C 6 - alkyl group, wherein at least one of the radicals R 10 and R 12 is a Ci-C 6 alkyl group, R 11 stands for a hydrogen atom, a dC 6 - alkyl group, a dC 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl, a dC 6 alkoxy group, a dC 6 -hydroxyalkoxy group, a group R m R lv N- (CH 2) q - wherein R 1 "and R ιv independently represent a hydrogen atom, a dC 6 alkyl group, a dC 6 hydroxyalkyl group, or an aryl-dC 6 - alkyl group, and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R 11 together with one of R 10 or R 12 may form a 5- or 6-membered aromatic ring optionally substituted with a halogen atom, a dC 6 alkyl group, a Ci-C 6 - hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl , a C 1 -C 6 -alkoxy group, a C 1 -C 6 -hydroxyalkoxy group, a nitro group, a hydroxy group, a Gr R V R VI N- (CH 2 ) S -, in which R v and R vι independently of one another represent a hydrogen atom, a C 1 -C 6 -alkyl group, a C 1 -C 6 -hydroxyalkyl group or an aryl-C 1 -C 6 alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,
R13 und R14 bilden entweder zusammen mit dem Stickstoffatom einen gesättigten oder ungesättigten 5- oder 6-gliedrigen Ring oder stehen unabhängig voneinander für eine (Ci-C6)- Alkylgruppe, eine (C2-C6)-Alkenylgruppe, eine Arylgruppe, eine Aryl-(Ci-C6)-alkylgruppe, eine (C2-C6)-Hydroxyalkylgruppe, eine (C2-C6)-Polyhydroxyalkylgruppe oder eine Gruppe R1R11N- (CH2)m-, worin R1 und R11 stehen unabhängig voneinander für ein Wasserstoffatom, eine (Ci-C6)- Alkylgruppe, eine (C-ι-C6)-Alkenylgruppe oder eine Aryl-C-ι-C6-alkylgruppe, wobei R1 und R11 gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6, undR 13 and R 14 either form together with the nitrogen atom form a saturated or unsaturated 5- or 6-membered ring, or independently represent a (Ci-C 6) - alkyl group, a (C 2 -C 6) alkenyl group, an aryl group , an aryl- (C 1 -C 6 ) -alkyl group, a (C 2 -C 6 ) -hydroxyalkyl group, a (C 2 -C 6 ) -polyhydroxyalkyl group or a group R 1 R 11 N- (CH 2) m - wherein R 1 and R 11 are independently a hydrogen atom, a (Ci-C 6) - alkyl group, a (C-ι-C 6) alkenyl group or an aryl C-ι-C 6 alkyl group, wherein R 1 and R 11 together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, and
• R15 ein Wasserstoffatom, eine (d-C6)-Alkylgruppe, eine (C2-C6)-Alkenylgruppe, eine Arylgruppe, eine Aryl-(d-C6)-alkylgruppe, eine (C2-C6)-Hydroxyalkylgruppe, eine (C2-C6)- Polyhydroxyalkylgruppe oder eine Gruppe RmRlvN-(CH2)n-, worin Rm und Rιv stehen unabhängig voneinander für ein Wasserstoffatom, eine (d-C6)-Alkylgruppe, eine (d-C6)-Alkenylgruppe oder eine Aryl-d-C6-alkylgruppe, wobei Rm und Rιv gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und n steht für eine Zahl 2, 3, 4, 5 oder 6• R 15 represents a hydrogen atom, a (dC 6) alkyl group, a (C 2 -C 6) alkenyl group, an aryl group, an aryl (dC 6) alkyl group, a (C 2 -C 6) hydroxyalkyl group, a (C 2 -C 6 ) - Polyhydroxyalkylgruppe or a group R m R lv N- (CH 2 ) n -, wherein R m and R IV independently represent a hydrogen atom, a (dC 6 ) alkyl group, a (dC 6 ) Alkenyl group or an aryl-dC 6 alkyl group, wherein R m and R ιv together with the nitrogen atom can form a 5-, 6- or 7-membered ring and n is a number 2, 3, 4, 5 or 6
• Y steht für ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe NRV", worin Rv" steht für ein• Y represents an oxygen atom, a sulfur atom or a group NR V ", wherein R v" stands for a
Wasserstoffatom, eine Arylgruppe, eine Heteroarylgruppe, eine Ci-C6-Alkylgruppe oder eine d- C6-Arylalkylgruppe,Hydrogen atom, an aryl group, a heteroaryl group, a C 1 -C 6 -alkyl group or a C 1 -C 6 -arylalkyl group,
• X' steht für ein physiologisch verträgliches Anion,X ' is a physiologically acceptable anion,
• Het steht für einen gegebenenfalls substituierten Heteroaromaten,Het is an optionally substituted heteroaromatic,
• X1 steht für eine direkte Bindung oder eine Carbonylgruppe.• X 1 represents a direct bond or a carbonyl group.
Gleichwirkend zu den Verbindungen der Formel Il sind deren Enaminformen. Es wird hier ausdrücklich auf die Druckschrift W0-A1 -2004/022016 verwiesen, auf die vollinhaltlich Bezug genommen wird.Equivalent to the compounds of formula II are their enamine forms. Reference is hereby made expressly to the document W0-A1-2004 / 022016, to the full contents of which reference is made.
Mindestens eine Gruppe R10 oder R12 gemäß Formel Il steht zwingend für eine d-C6-Alkylgruppe. Diese Alkylgruppe trägt an deren alpha-Kohlenstoffatom bevorzugt mindestens zwei Wasserstoffatome. Besonders bevorzugte Alkylgruppen sind die Methyl-, Ethyl-, Propyl-, n-Butyl-, iso- Butyl, n-Pentyl-, neo-Pentyl-, n-Hexylgruppe. Ganz besonders bevorzugt stehen R10 und R12 unabhängig voneinander für Wasserstoff oder eine Methylgruppe, wobei mindestens eine Gruppe R10 oder R12 eine Methylgruppe bedeutet.At least one group R 10 or R 12 according to formula II necessarily stands for a C 1 -C 6 -alkyl group. This alkyl group preferably carries at least two hydrogen atoms on its alpha carbon atom. Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, neo-pentyl, n-hexyl group. Most preferably, R 10 and R 12 are each independently hydrogen or a methyl group, wherein at least one group R 10 or R 12 is a methyl group.
In einer bevorzugten Ausführungsform steht Y für ein Sauerstoff- oder ein Schwefelatom, besonders bevorzugt für ein Sauerstoffatom.In a preferred embodiment, Y is an oxygen or sulfur atom, more preferably an oxygen atom.
Der Rest R8 wird bevorzugt ausgewählt aus einer (d-C6)-Alkylgruppe (besonders bevorzugt einer Methylgruppe), einer C2-C6-Alkenylgruppe (insbesondere einer Allylgruppe), einer Hydroxy-(C2- bis C6)-alkylgruppe, insbesondere einer 2-Hydroxyethylgruppe, oder einer gegebenenfalls substituierten Benzylgruppe. R11 steht bevorzugt für ein Wasserstoffatom.The radical R 8 is preferably selected from a (C 1 -C 6 ) -alkyl group (particularly preferably a methyl group), a C 2 -C 6 -alkenyl group (in particular an allyl group), a hydroxy (C 2 -C 6 ) -alkyl group, in particular a 2-hydroxyethyl group, or an optionally substituted benzyl group. R 11 is preferably a hydrogen atom.
Besonders bevorzugt stehen die Reste R9, R10 und R12 für eine Methylgruppe, der Rest R11 für ein Wasserstoffatom, Y für ein Sauerstoff- oder ein Schwefelatom und der Rest R8 wird ausgewählt aus einer (C-ι-C6)-Alkylgruppe (besonders bevorzugt einer Methylgruppe), einer C2-C6-Alkenylgruppe (insbesondere einer Allylgruppe), einer Hydroxy-(C2- bis C6)-alkylgruppe, insbesondere einer 2- Hydroxyethylgruppe, oder einer gegebenenfalls substituierten Benzylgruppe.Particularly preferably, the radicals R 9 , R 10 and R 12 are a methyl group, the radical R 11 is a hydrogen atom, Y is an oxygen or sulfur atom and the radical R 8 is selected from a (C-ι-C 6 ) Alkyl group (particularly preferably a methyl group), a C 2 -C 6 alkenyl group (in particular an allyl group), a hydroxy (C 2 to C 6 ) alkyl group, in particular a 2-hydroxyethyl group, or an optionally substituted benzyl group.
Vorzugsweise sind die Verbindungen gemäß Formel Il ausgewählt aus einer oder mehrererPreferably, the compounds according to formula II are selected from one or more
Verbindungen der Gruppe von Salzen mit physiologisch verträglichem Gegenion X' , die gebildet wird aus Salzen desCompounds of the group of salts with physiologically acceptable counterion X ' , which is formed from salts of the
1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diethyl-4,6-dimethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-di(2-hydroxyethyl)-4,6-dimethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3,4-trimethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diethyl-4-methyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-dipropyl-4-methyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-di(2-hydroxyethyl)-4-methyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diphenyl-4-methyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidinium,
1-Allyl-1 ,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium,
1 ,2-Dihydro-1-(2-hydroxyethyl)-3,4,6-trimethyl-2-oxo-pyrimidiniums,1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidiniums,
1 ,2-Dihydro-1 ,3-di(2-hydroxyethyl)-4,6-dimethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3,4-trimethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1, 3,4-trimethyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diethyl-4-methyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-dipropyl-4-methyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-di(2-hydroxyethyl)-4-methyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diphenyl-4-methyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1, 3-diphenyl-4-methyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-3,4-dimethyl-2-oxo-chinazoliniums und1, 2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and
1 ,2-Dihydro-3,4-dimethyl-2-thioxo-chinazoliniums. Ganz besonders bevorzugte erfindungsgemäße Mittel sind dadurch gekennzeichnet, dass sie als CH- acide Verbindung1, 2-dihydro-3,4-dimethyl-2-thioxo-quinazolinium. Very particularly preferred agents according to the invention are characterized in that they are as CH-acidic compound
Salze des 1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-oxopyrimidiniunns,Salts of 1,2-dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinone,
Salze des 1 ,2-Dihydro-1 ,3,4-trimethyl-2-oxopyrimidiniunns,Salts of 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinone,
Salze des 1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-thioxopyrimidiniunns,Salts of 1,2-dihydro-1, 3,4,6-tetramethyl-2-thioxopyrimidinone,
Salze des 1-Allyl-i ,2-dihydro-3,4,6-trimethyl-2-oxopyrinnidiniunns,Salts of 1-allyl-i, 2-dihydro-3,4,6-trimethyl-2-oxopyrinnidine,
Salze des 1 ,2-Dihydro-1-(2-hydroxyethyl)-3,4,6-trimethyl-2-oxopyrimidiniums,Salts of 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium,
2-(Cyanomethyl)benzinnidazol,2- (cyanomethyl) benzinnidazol,
4,5-Dihydro-4-imino-2-(1-piperidinyl)-thiazol und/oder dessen Hydrochlorid,4,5-dihydro-4-imino-2- (1-piperidinyl) thiazole and / or its hydrochloride,
4,5-Dihydro-4-imino-2-(4-morpholinyl)-thiazol und/oder dessen Hydrochlorid,4,5-dihydro-4-imino-2- (4-morpholinyl) thiazole and / or its hydrochloride,
4,5-Dihydro-4-imino-2-(1-pyrrolidinyl)-thiazol und/oder dessen Hydrochlorid enthalten.4,5-dihydro-4-imino-2- (1-pyrrolidinyl) thiazole and / or its hydrochloride.
X' steht in Formel (II) sowie in obigen Listen bevorzugt für Halogenid, Benzolsulfonat, p- Toluolsulfonat, d-C4-Alkansulfonat, Trifluormethansulfonat, Perchlorat, 0.5 Sulfat, Hydrogensulfat, Tetrafluoroborat, Hexafluorophosphat oder Tetrachlorozinkat. Besonders bevorzugt werden die Anionen Chlorid, Bromid, lodid, Hydrogensulfat oder p-Toluolsulfonat als X' eingesetzt.X ' in formula (II) and in the lists above preferably for halide, benzenesulfonate, p-toluenesulfonate, dC 4 alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogen sulfate, tetrafluoroborate, hexafluorophosphate or Tetrachlorozinkat. Particularly preferably, the anions chloride, bromide, iodide, hydrogen sulfate or p-toluenesulfonate are used as X ' .
Der Rest Het gemäß Formel (III) steht bevorzugt für das Molekülfragment mit der Formel (V),The radical Het according to formula (III) preferably represents the molecule fragment of the formula (V),
Figure imgf000043_0001
worin
Figure imgf000043_0001
wherein
R16 und R17 stehen unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, ein Halogenatom, eine Nitrogruppe, eine lineare oder zyklische d-C6-Alkylgruppe, eine C2-C6- Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Cyanmethylgruppe, eine Cyanmethylcarbonylgruppe, eine gegebenenfalls substituierte Heteroarylguppe, eine Aryl-d-C6- alkylgruppe, eine C-ι-C6-Hydroxyalkylgruppe, eine C2-C6-Polyhydroxyalkylgruppe, eine C1-C6- Alkoxygruppe, eine d-C6-Alkoxycarbonylgruppe, eine C-ι-C6-Alkoxy-C2-C6-alkylgruppe, eine C1- C6-Sulfoalkylgruppe, eine C-ι-C6-Carboxyalkylgruppe, eine Gruppe RvmRlxN-(CH2)m-, worin Rvι" und Rιx stehen unabhängig voneinander für ein Wasserstoffatom, eine lineare oder zyklische C1- C6-Alkylgruppe, eine C2-C6-Alkenylgruppe, eine C-ι-C6-Hydroxyalkylgruppe oder eine Aryl-C-ι-C4- alkylgruppe, wobei Rvι" und Rιx gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 0, 1 , 2, 3 oder 4, wobei R16 und/oder R17 einen an den Ring des Restmoleküls ankondensierten, gegebenenfalls substituierten aromatischen oder heteroaromatischen, 5- oder 6-Ring bilden könnenR 16 and R 17 independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic dC 6 alkyl group, a C 2 -C 6 - alkenyl group, an optionally substituted aryl group, a cyanomethyl group, a cyanomethylcarbonyl, an optionally substituted heteroaryl group, an aryl-dC 6 - alkyl group, a C-ι-C 6 hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a C 1 -C 6 - alkoxy group, a dC 6 alkoxycarbonyl group, a C ι-C 6 -alkoxy-C 2 -C 6 alkyl group, a C 1 - C 6 sulfoalkyl, a C-ι-C 6 carboxyalkyl group, a group R vm R lx N- (CH 2) m - wherein R VI "and R ιx independently represent a hydrogen atom, a linear or cyclic C 1 - C 6 alkyl group, a C 2 -C 6 alkenyl group, a C-ι-C6 hydroxyalkyl group or an aryl C-ι C 4 - alkyl group, wherein R vι "and R ιx together with the nitrogen atom, a 5-, 6- or 7-membered Rin g can form and m stands for a number 0, 1, 2, 3 or 4, wherein R 16 and / or R 17 can form a fused to the ring of the remainder of the molecule, optionally substituted aromatic or heteroaromatic, 5- or 6-ring
• X2 und X3 stehen unabhängig voneinander für ein Stickstoffatom oder eine Gruppe CR15, wobei• X 2 and X 3 independently represent a nitrogen atom or a group CR 15 , wherein
R15 steht für ein Wasserstoffatom, eine Hydroxygruppe, ein Halogenatom, eine Nitrogruppe, eine lineare oder zyklische d-C6-Alkylgruppe, eine C2-C6-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Cyanmethylgruppe, eine Cyanmethylcarbonylgruppe, eine gegebenenfalls substituierte Heteroarylguppe, eine Aryl-Ci-C6-alkylgruppe, eine C1-C6- Hydroxyalkylgruppe, eine C2-C6-Polyhydroxyalkylgruppe, eine d-C6-Alkoxygruppe, eine C1-C6- Alkoxycarbonylgruppe, eine C-ι-C6-Alkoxy-C2-C6-alkylgruppe, eine d-C6-Sulfoalkylgruppe, eine d-C6-Carboxyalkylgruppe und eine Gruppe RxRxlN-(CH2)n-, worin Rx und Rxι stehen unabhängig voneinander für ein Wasserstoffatom, eine lineare oder zyklische d-C6-Alkylgruppe, eine C2-C6-Alkenylgruppe, eine d-C6-Hydroxyalkylgruppe oder eine Aryl-d-C4-alkylgruppe, wobei Rx und Rxι gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und n steht für eine Zahl 0, 1 , 2, 3 oder 4, wobei mindestens einer der Substituenten X2 und X3 zusammen mit dem Restmolekül einen ankondensierten gegebenenfalls substituierten aromatischen 5- oder 6-Ring bilden kann,R 15 represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic dC 6 alkyl group, a C 2 -C 6 alkenyl group, an optionally substituted aryl group, a cyanomethyl group, a cyanomethylcarbonyl group, an optionally substituted heteroaryl group, an aryl Ci-C 6 alkyl group, a C 1 -C 6 - hydroxyalkyl group, a C 2 -C 6 polyhydroxyalkyl group, a dC 6 alkoxy group, a C 1 -C 6 - alkoxycarbonyl group, a C-ι-C 6 Alkoxy C 2 -C 6 alkyl group, a dC 6 -Sulfoalkylgruppe, a dC 6 -Carboxyalkylgruppe and a group R x R xl N- (CH 2 ) n -, wherein R x and R xι independently represent a hydrogen atom , a linear or cyclic dC 6 alkyl group, a C 2 -C 6 alkenyl group, a dC 6 -Hydroxyalkylgruppe or an aryl-dC 4 alkyl group, wherein R x and R xι together with the nitrogen atom, a 5-, 6- or Can form a 7-membered ring and n is a number 0, 1, 2, 3 or 4 in which at least one of the substituents X 2 and X 3 together with the remainder of the molecule can form a fused-on optionally substituted aromatic 5- or 6-membered ring,
• X4 steht für ein Sauerstoffatom, ein Schwefelatom, einer Vinylengruppe oder eine Gruppe N-H, wobei die beiden letztgenannten Gruppen unabhängig voneinander gegebenenfalls mit einer linearen oder zyklischen d-C6-Alkylgruppe, einer C2-C6-Alkenylgruppe, einer gegebenenfalls substituierten Arylgruppe, einer gegebenenfalls substituierten Heteroarylguppe, einer Aryl-d-C6- alkylgruppe, einer C2-C6-Hydroxyalkylgruppe, einer C2-C6-Polyhydroxyalkylgruppe, einer C1-C6- Alkoxy-C2-C6-alkylgruppe, einer d-C6-Sulfoalkylgruppe, einer d-C6-Carboxyalkylgruppe, einer Gruppe Rx"RxmN-(CH2)p- steht, worin Rx" und Rxι" stehen unabhängig voneinander für ein Wasserstoffatom, eine lineare oder zyklische d-C6-Alkylgruppe, eine C2-C6-Alkenylgruppe, eine d-C6-Hydroxyalkylgruppe oder eine Aryl-d-C4-alkylgruppe, wobei Rx" und Rxι" gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und p steht für eine Zahl 0, 1 , 2, 3 oder 4, substituiert sein können,• X 4 is an oxygen atom, a sulfur atom, a vinyl group or an NH group, which latter two groups are independently optionally substituted with a linear or cyclic dC 6 alkyl group, a C 2 -C 6 alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-dC 6 -alkyl group, a C 2 -C 6 -hydroxyalkyl group, a C 2 -C 6 -polyhydroxyalkyl group, a C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl group, a dC 6- sulfoalkyl group, a dC 6 -Carboxyalkylgruppe, a group R x "R xm N- (CH 2 ) p -, wherein R x " and R xι "independently represent a hydrogen atom, a linear or cyclic dC 6 alkyl group a C 2 -C 6 alkenyl group, a dC 6 -Hydroxyalkylgruppe or an aryl-dC 4 alkyl group, wherein R x "and R xι " together with the nitrogen atom can form a 5-, 6- or 7-membered ring and p stands for a number 0, 1, 2, 3 or 4, can be substituted
mit der Maßgabe, daß, wenn X4 für eine Vinylengruppe steht, mindestens eine der Gruppen X2 oder X3 ein Stickstoffatom bedeutet.with the proviso that when X 4 is a vinylene group, at least one of X 2 or X 3 represents a nitrogen atom.
Die Bindung des heterozyklischen Rings gemäß Formel (V) zum Molekülfragment -X1-CH2-C≡N unter Erhalt der erfindungsgemäßen Verbindung gemäß Formel (III) erfolgt an den Ring des Heterozyklusses und ersetzt ein an diesen Ring gebundenes Wasserstoffatom. Folglich ist es zwingend notwendig, daß die Substituenten R16, R17, X2, X3 und X4 derart gewählt werden müssen, daß mindestens einer dieser Substituenten eine entsprechende Bindungsbildung ermöglicht. Folglich ist es zwingend, daß mindestens einer der Reste R16 oder R17 die Bindung zum Molekülfragment -X1- CH2-C≡N ausbildet, wenn X4 ein Sauerstoffatom oder ein Schwefelatom ist und X2 und X3 ein Stickstoffatom bedeuten.The bond of the heterocyclic ring according to formula (V) to the molecule fragment -X 1 -CH 2 -C≡N to give the compound according to formula (III) according to the invention takes place at the ring of the heterocycle and replaces a hydrogen atom bound to this ring. Consequently, it is imperative that the substituents R 16 , R 17 , X 2 , X 3 and X 4 must be chosen such that at least one of these substituents allows a corresponding bond formation. consequently it is mandatory that at least one of R 16 or R 17 forms the bond to the molecular fragment -X 1 - CH 2 -C≡N, when X 4 is an oxygen atom or a sulfur atom and X 2 and X 3 denote a nitrogen atom.
Der Rest Het gemäß Formel (IM) wird besonders bevorzugt abgeleitet von den Heteroaromaten Furan, Thiophen, Pyrrol, Isoxazol, Isothiazol, Imidazol, Oxazol, Thiazol, Pyridin, Pyridazin, Pyrimidin, Pyrazin, 1 ,2,3-Triazin, 1 ,2,4-Triazin, 1 ,3,5-Triazin, Benzopyrrol, Benzofuran, Benzothiophen, Benzimidazol, Benzoxazol, Indazol, Benzoisoxazol, Benzoisothiazol, Indol, Chinolin, Isochinolin, Cinnolin, Phthalazin, Chinazolin, Chinoxalin, Acridin, Benzochinolin, Benzoisochinolin, Benzothiazol, Phenazin, Benzocinnolin, Benzochinazolin, Benzochinoxalin, Phenoxazin, Phenothiazin, Nephthyridin, Phenanthrolin, Indolizin, Chinolizin, Carbolin, Purin, Pteridin und Cumarin, wobei die vorgenannten Heteroaromaten mit mindestens einer Gruppe ausgewählt aus einem Halogenatom, einer Nitrogruppe, einer Thiogruppe, einer Thio-(d-C6)-alkylgruppe, einer Heteroarylgruppe, einer Arylgruppe, einer (d-C6)-Alkylgruppe, einer (d-C6)-Alkoxygruppe, einer Hydroxygruppe, einer (C2- C6)-Hydroxyalkylgruppe, einer (C2-C6)-Polyhydroxyalkylgruppe, einer (d-C6)-Alkoxyl-(d-C6)- alkylgruppe, einer Aryl-(d-C6)-alkylgruppe, einer Aminogruppe, einer (d-C6)-Monoalkylaminogruppe, einer (d-C6)-Dialkylaminogruppe, eine Dialkylaminoalkylgruppe -(CH2)n-NR'R", worin n eine ganze Zahl von 2 und 6 ist und R' und R" unabhängig voneinander eine lineare oder verzweigte Alkylgruppe bedeutet, welche gegebenenfalls zusammen einen Ring bilden können, substituiert sein können.The radical Het according to formula (III) is particularly preferably derived from the heteroaromatics furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, pyridine, pyridazine, pyrimidine, pyrazine, 1, 2,3-triazine, 1, 2 , 4-triazine, 1, 3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, indole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, acridine, benzoquinoline, benzoisoquinoline, benzothiazole , Phenazine, benzocinnoline, benzoquinazoline, benzoquinoxaline, phenoxazine, phenothiazine, nephthyridine, phenanthroline, indolizine, quinolizine, carboline, purine, pteridine and coumarin, wherein the aforementioned heteroaromatic compounds having at least one group selected from a halogen atom, a nitro group, a thio group, a thio - (dC 6) alkyl group, a heteroaryl group, an aryl group, a (C 6) alkyl group, a (C 6) alkoxy group, a hydroxy group, a (C 2 - C 6) hydroxyalkyl group, a r (C 2 -C 6 ) polyhydroxyalkyl group, a (dC 6 ) alkoxyl (dC 6 ) alkyl group, an aryl (dC 6 ) alkyl group, an amino group, a (dC 6 ) monoalkylamino group, a (dC 6 ) -dialkylamino group, a dialkylaminoalkyl group - (CH 2 ) n -NR'R ", wherein n is an integer of 2 and 6 and R 'and R" independently represent a linear or branched alkyl group which may optionally together form a ring may be substituted.
Vorzugsweise sind die Verbindungen gemäß Formel (III) ausgewählt aus der Gruppe bestehend aus 2-(2-Furoyl)-acetonitril, 2-(5-Brom-2-furoyl)-acetonitril, 2-(5-Methyl-2-trifluormethyl-3-furoyl)-acetonitril, 3-(2,5-Dimethyl-3-furyl)-3-oxopropanitril, 2-(2-Thenoyl)-acetonitril, 2-(3-Thenoyl)-acetonitril, 2-(5- Fluor-2-thenoyl)-acetonitril, 2-(5-Chlor-2-thenoyl)-acetonitril, 2-(5-Brom-2-thenoyl)-acetonitril, 2-(5- Methyl-2-thenoyl)-acetonitril, 2-(2,5-Dimethylpyrrol-3-oyl)-acetonitril, 2-(1 ,2,5-Trimethylpyrrol-3-oyl)- acetonitril, 1 /-/-Benzimidazol-2-ylacetonitril, 1 /-/-Benzothiazol-2-ylacetonitril, 2-(Pyrid-2-yl)-acetonitril, 2,6-Bis(cyanmethyl)-pyridin, 2-(lndol-3-oyl)-acetonitril, 2-(2-Methyl-indol-3-oyl)-acetonitril, 8- Cyanacetyl-7-methoxy-4-methylcumarin, 2-(2-lsopropyl-5,6-benzochinolin-4-oyl)-acetonitril, 2-(2- Phenyl-5,6-benzochinolin-4-oyl)-acetonitril, 2-(Chinoxalin-2-yl)-acetonitril, 2-(Cumaron-2-yl)- acetonitril, 6,7-Dichlor-5-(cyanoacetyl)-2,3-dihydro-1-benzofuran-2-carbonsäure-tert.-butylester, 2-(6- Hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl)-acetonitril und 2-(1-Phenyl-1 ,4-dihydrothiochromeno[4,3- c]pyrazol-3-oyl)-acetonitril. Besonders bevorzugt ist 1/-/-Benzimidazol-2-ylacetonitril [2- (Cyanomethyl)benzimidazol]. Erfindungsgemäß bevorzugte Mittel sind dadurch gekennzeichnet, dass sie als Haarfärbemittel formuliert sind, die bezogen auf ihr Gewicht 0,01 bis 20 Gew.-%, vorzugsweise 0,05 bis 15 Gew.-%, besonders bevorzugt 0,1 bis 12,5 Gew.-% und insbesondere 0,2 bis 10 Gew.-% einer oder mehrerer CH-acider Verbindung(en) enthalten.Preferably, the compounds according to formula (III) are selected from the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 2- (5-methyl-2-trifluoromethyl- 3-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5- Fluoro-2-thenoyl) -acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) -acetonitrile , 2- (2,5-Dimethylpyrrole-3-oyl) -acetonitrile, 2- (1, 2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1 / - / - benzimidazol-2-ylacetonitrile, 1 / - / Benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indol-3-oyl) -acetonitrile, 2- (2-methyl-indole 3-oyl) -acetonitrile, 8-cyanoacetyl-7-methoxy-4-methylcoumarin, 2- (2-isopropyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (2-phenyl-5,6 -benzoquinolin-4-oyl) -acetonitrile, 2- (quinoxalin-2-yl) -acetonitrile, 2- (cumaron-2-yl) -acetonitrile, 6,7-dichloro-5- (cyanoacetyl) -2,3- dihydro-1-benzofuran-2-carb t-butyl ester, 2- (6-hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile and 2- (1-phenyl-1,4-dihydrothiochromeno [4,3-c] pyrazol-3-oyl) -acetonitrile. Particularly preferred is 1 / - / - benzimidazol-2-ylacetonitrile [2- (cyanomethyl) benzimidazole]. Agents preferred according to the invention are characterized in that they are formulated as hair colorants, based on their weight from 0.01 to 20 wt .-%, preferably 0.05 to 15 wt .-%, particularly preferably 0.1 to 12.5 wt .-% and in particular 0.2 to 10 wt .-% of one or more CH-acidic compound (s) included.
Es hat sich gezeigt, daß der Einsatz von Polyolestern durch den gleichzeitigen Einsatz von Azolen in seiner Wirkung gesteigert werden kann. Insbesondere die Aktivierung von Wasserstoffperoxid und die Verringerung der Gelbfärbung beim Blondieren werden durch den gleichzeitigen Einsatz von Azolen weiter verstärkt.It has been shown that the use of polyol esters can be increased by the simultaneous use of azoles in its action. In particular, the activation of hydrogen peroxide and the reduction of yellowing in bleaching are further enhanced by the simultaneous use of azoles.
Erfindungsgemäß bevorzugte Mittel zum Färben und/oder Aufhellen keratinischer Fasern sind daher dadurch gekennzeichnet, daß sie - bezogen auf ihr Gewicht - 1 bis 20 Gew.-% mindestens eines gegebenenfalls substituierten, insbesondere benzannellierten Azols, vorzugsweise mindestens ein gegebenenfalls substituiertes und/oder benzannelliertes Pyrrol und/oder Pyrazol und/oder Imidazol und/oder 1 ,2,3-Triazol und/oder 1 ,2,4-Triazol und/oder 1 ,2,3,4-Tetrazol, enthalten.Agents preferred according to the invention for dyeing and / or brightening keratinic fibers are therefore characterized in that they contain from 1 to 20% by weight of at least one optionally substituted, in particular benzannellated, azole, preferably at least one optionally substituted and / or benzannellated pyrrole and / or pyrazole and / or imidazole and / or 1, 2,3-triazole and / or 1, 2,4-triazole and / or 1, 2,3,4-tetrazole.
Die Grundkörper der genannten Verbindungen sind nachstehend dargestellt:The basic bodies of the compounds mentioned are shown below:
Figure imgf000046_0001
Figure imgf000046_0001
Die Azole können an den mit einer Bindung gekennzeichneten N-Atomen ein Wasserstoffatom tragen oder substituiert sein. Als Substituenten am jeweiligen N-Atom haben sich Aryl-, Alkyl- oder Alkenylreste bewährt. Zusätzlich können die Azole an dem bzw. den Kohlenstoffatom(en) substituiert oder benzannelliert sein. Bevorzugte erfindungsgemäß einsetzbare benzanenellierte Azole haben folgende Strukturen, wobei die araomatischen Ringe gegebenenfalls weiter substituiert sein können. The azoles may carry or be substituted by a hydrogen atom on the N atoms marked with a bond. Aryl, alkyl or alkenyl radicals have proven useful as substituents on the respective N atom. Additionally, the azoles may be substituted or benzannellated at the carbon atom (s). Preferred benzene-substituted azoles which can be used according to the invention have the following structures, where the araomatic rings may optionally be further substituted.
Figure imgf000047_0001
Figure imgf000047_0001
Besonders bevorzugt ist erfindungsgemäß der Einsatz von Pyrazolen. Hier sind erfindungsgemäß bevorzugte Mittel dadurch gekennzeichnet, daß sie mindestens eine Imidazolverbindung gemäß Formel (VI) und/oder deren physiologisch verträglichen SalzeParticularly preferred according to the invention is the use of pyrazoles. Here, preferred agents according to the invention are characterized in that they contain at least one imidazole compound of the formula (VI) and / or their physiologically tolerated salts
Figure imgf000047_0002
enthalten, worin
Figure imgf000047_0002
contain, in which
R1 steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe oder eine (d-C6)-Alkylgruppe,R 1 represents a hydrogen atom, an optionally substituted aryl group or a (dC 6 ) -alkyl group,
Rz steht für ein Wasserstoffatom, eine Carboxaldehydgruppe, eine (C1-C6)- Alkylgruppe oder eine Nitrogruppe,R z represents a hydrogen atom, a carboxaldehyde group, a (C 1 -C 6 ) -alkyl group or a nitro group,
R3 steht für ein Wasserstoffatom, eine Carboxy-(d-C6)-alkylgruppe, eine Amino-(C-ι-C6)-alkylgruppe, eine Carboxylgruppe, eine Carboxaldehydgruppe, eine (d-C6)-Alkylgruppe, eine Nitrogruppe, eine 2- Amino-3-hydroxypropylgruppe oder eine Gruppe -CH2-CH(NH2)-COOH,R 3 represents a hydrogen atom, a carboxy (dC 6 ) alkyl group, an amino (C 1 -C 6 ) alkyl group, a carboxyl group, a Carboxaldehyde group, a (dC 6 ) alkyl group, a nitro group, a 2-amino-3-hydroxypropyl group or a group -CH 2 -CH (NH 2 ) -COOH,
R4 steht für ein Wasserstoffatom, eine Carboxaldehydgruppe oder eineR 4 represents a hydrogen atom, a carboxaldehyde group or a
Carboxylgruppe.Carboxyl group.
Vorzugsweise wird/werden die Imidazolverbindung(en) der Formel (VI) innerhalb engerer Mengenbereiche eingesetzt. Hier sind erfindungsgemäße Mittel zum Färben und/oder Aufhellen keratinischer Fasern bevorzugt, die mindestens eine Imidazolverbindung gemäß Formel (VI) und/oder deren physiologisch verträgliche Salze in Mengen von 2 bis 15 Gew.-%, vorzugsweise von 2,5 bis 12,5 Gew.-%, besonders bevorzugt von 3 bis 10 Gew.-% und insbesondere von 4 bis 8 Gew.-% enthalten.Preferably, the imidazole compound (s) of formula (VI) is / are used within narrower ranges. Here, agents according to the invention for dyeing and / or lightening keratinic fibers are preferred which contain at least one imidazole compound of the formula (VI) and / or physiologically tolerable salts thereof in amounts of from 2 to 15% by weight, preferably from 2.5 to 12.5 Wt .-%, particularly preferably from 3 to 10 wt .-% and in particular from 4 to 8 wt .-%.
Bevorzugt werden die Imidazolverbindungen gemäß Formel (VI) ausgewählt aus mindestens einem Vertreter aus einer Gruppe, die gebildet wird, aus Histamin, D-Histidin, L-Histidin, DL-Histidin, D- Histidinol, L-Histidinol, DL-Histidinol, Imidazol, lmidazol-4-essigsäure, lmidazol-4-carbonsäure, lmidazol-4,5-dicarbonsäure, lmidazol-2-carboxaldehyd, lmidazol-4-carboxaldehyd, lmidazol-5- carboxaldehyd, 2-Nitroimidazol, 4-Nitroimidazol, 4-Methylimidazol-5-carboxaldehyd, N- Methylimidazol-2-carboxaldehyd, 4-Methylimidazol, 2-Methylimidazol, N-Methylimidazol, N-(4- Aminophenyl)-imidazol, sowie den physiologisch verträglichen Salzen der vorgenannten Verbindungen. Erfindungsgemäß besonders bevorzugt wird Imidazol eingesetzt.Preferably, the imidazole compounds of formula (VI) are selected from at least one member of a group formed from histamine, D-histidine, L-histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, imidazole , imidazole-4-acetic acid, imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazole-2-carboxaldehyde, imidazole-4-carboxaldehyde, imidazole-5-carboxaldehyde, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole 5-carboxaldehyde, N-methylimidazole-2-carboxaldehyde, 4-methylimidazole, 2-methylimidazole, N-methylimidazole, N- (4-aminophenyl) -imidazole, and the physiologically acceptable salts of the aforementioned compounds. Imidazole is particularly preferably used according to the invention.
Zusammenfassend sind erfindungsgemäß bevorzugte Mittel dadurch gekennzeichnet, daß sie mindestens eine Imidazolverbindung gemäß Formel (VI) und/oder deren physiologisch verträgliche Salze in Mengen von 2 bis 15 Gew.-%, vorzugsweise von 2,5 bis 12,5 Gew.-%, besonders bevorzugt von 3 bis 10 Gew.-% und insbesondere von 4 bis 8 Gew.-% enthalten, wobei bevorzugte Imidazolverbindungen gemäß Formel (VI) und/oder deren physiologisch verträgliche Salze ausgewählt ist/sind aus Histamin, D-Histidin, L-Histidin, DL-Histidin, D-Histidinol, L-Histidinol, DL- Histidinol, Imidazol, lmidazol-4-essigsäure, lmidazol-4-carbonsäure, lmidazol-4,5-dicarbonsäure, lmidazol-2-carboxaldehyd, lmidazol-4-carboxaldehyd, lmidazol-5-carboxaldehyd, 2-Nitroimidazol, A- Nitroimidazol, 4-Methylimidazol-5-carboxaldehyd, N-Methylimidazol-2-carboxaldehyd, A- Methylimidazol, 2-Methylimidazol, N-Methylimidazol, N-(4-Aminophenyl)-imidazol, sowie den physiologisch verträglichen Salze der vorgenannten Verbindungen.In summary, preferred agents according to the invention are characterized in that they contain at least one imidazole compound of the formula (VI) and / or their physiologically tolerable salts in amounts of from 2 to 15% by weight, preferably from 2.5 to 12.5% by weight, particularly preferably from 3 to 10% by weight and in particular from 4 to 8% by weight, preferred imidazole compounds according to formula (VI) and / or their physiologically tolerated salts being selected from histamine, D-histidine, Histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, imidazole, imidazole-4-acetic acid, imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazole-2-carboxaldehyde, imidazole-4 carboxaldehyde, imidazole-5-carboxaldehyde, 2-nitroimidazole, A-nitroimidazole, 4-methylimidazole-5-carboxaldehyde, N-methylimidazole-2-carboxaldehyde, A-methylimidazole, 2-methylimidazole, N-methylimidazole, N- (4-aminophenyl ) -imidazole, as well as the physiologically acceptable salts of the aforementioned compounds.
Auch der zusätzliche Einsatz von Carbonaten bzw. so genannten Carbonatanaloga hat sich als bevorzugt erwiesen, da die Aktivierung von Wasserstoffperoxid weiter verstärkt wird. Bevorzugte erfindungsgemäße Mittel zum Färben und/oder Aufhellen keratinischer Fasern sind dabei dadurch gekennzeichnet, daß sie zusätzlich 0,1 bis 25 Gew.%, vorzugsweise 0,5 bis 20 Gew.%, besonders bevorzugt 1 bis 15 Gew.% und insbesondere 1 ,5 bis 10 Gew.% mindestens eines Stoffes aus den Gruppen der ii. Carbonate und/oder iii. Monoalkylcarbonate (Kohlensäuremonoester) und/oder iv. Kohlensäuremonoamide und/oder v. Silylcarbonate und/oder vi. Silylcarbamate enthalten.The additional use of carbonates or so-called carbonate analogues has proved to be preferred because the activation of hydrogen peroxide is further enhanced. Preferred agents according to the invention for dyeing and / or lightening keratinic fibers are characterized in that they additionally contain 0.1 to 25% by weight, preferably 0.5 to 20% by weight, especially preferably 1 to 15 wt.% And in particular 1, 5 to 10 wt.% Of at least one substance from the groups of ii. Carbonates and / or iii. Monoalkyl carbonates (carbonic acid monoesters) and / or iv. Carbonic acid monoamides and / or v. Silyl carbonates and / or vi. Silylcarbamate included.
Als Carbonate bieten sich insbesondere Ammonium-, Alkalimetall- und Erdalkalimetallcarbonate und -hydrogencarbonate an. Besonders bevorzugt sind beispielsweise Natriumhydrogencarbonat, Ammoniumhydrogencarbonat, Natriumcarbonat, Ammoniumcarbonat und Ammoniumcarbannat.Particularly suitable carbonates are ammonium, alkali metal and alkaline earth metal carbonates and bicarbonates. For example, sodium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate and ammonium carbananate are particularly preferred.
Zusätzlich zu Carbonaten oder an deren Stelle können die erfindungsgemäßen Mittel vorzugsweise auch mindestens einen Kohlensäuremonoester und/oder mindestens ein Kohlensäuremonoamid enthalten. Diese Substanzen werden nachfolgend detailliert beschrieben.In addition to or in place of carbonates, the compositions according to the invention may preferably also contain at least one carbonic acid monoester and / or at least one carbonic acid monoamide. These substances are described in detail below.
Erfindungsgemäß bevorzugte Mittel sind dadurch gekennzeichnet, daß sie mindestens einen Kohlensäuremonoester der Formel (C-I)Agents preferred according to the invention are characterized in that they contain at least one carbonic acid monoester of the formula (C-I)
R-O-C(O)-O-H (C-I)R-O-C (O) -O-H (C-I)
enthalten, in der R für einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest, oder eine substituierte oder unsubstiuierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus steht.in which R represents a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.
In Formel (C-I) steht R vorzugsweise für einen substituierten oder unsubstituierten, geradkettigen oder verzweigten Alkyl-, Alkenyl- oder Alkinylrest, wobei als Substituenten bevorzugt Hydroxy-, Amino-, Nitro-, Sulfonsäuregruppen oder Halogene in Frage kommen. Weitere Bevorzugte Reste R sind Phenyl- und Benzylreste sowie weiter substituierte Vertreter. Besonders bevorzugt steht R für eine C-|.6-Alkylgruppe. Beispiele für erfindungsgemäße d-C6-Alkylgruppen sind die Gruppen Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sec-Butyl, iso-Butyl, tert-Butyl, Pentyl, iso-Pentyl und Hexyl.In formula (CI), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably R is a C-. 6- alkyl group. Examples of C 1 -C 6 -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.
Erfindungsgemäß besonders bevorzugte Mittel sind dadurch gekennzeichnet, daß der Rest R in Formel (C-I) ausgewählt ist aus Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, terf-Butyl- sowie Hydroxymethyl- und Hydroxyethyl-Resten. Alternativ zum Kohlensäuremonoester oder in Verbindung mit ihm können die erfindungsgemäßen Mittel Kohlensäuremonoamide enthalten. Hier sind erfindungsgemäß bevorzugte Mittel dadurch gekennzeichnet, daß sie mindestens ein Kohlensäuremonoamid der Formel (C-Il)Particularly preferred agents according to the invention are characterized in that the radical R in formula (CI) is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl as well as hydroxymethyl and hydroxyethyl radicals. As an alternative to the carbonic acid monoester or in conjunction with it, the compositions according to the invention may contain carbonic acid monoamides. Here, preferred agents according to the invention are characterized in that they contain at least one carbonic acid monoamide of the formula (C-II)
R-NH-C(O)-O-H (C-Il)R-NH-C (O) -O-H (C-II)
enthält, in der R für einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest, oder eine substituierte oder unsubstiuierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus steht.in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.
In Formel (C-Il) steht R vorzugsweise für einen substituierten oder unsubstituierten, geradkettigen oder verzweigten Alkyl-, Alkenyl- oder Alkinylrest, wobei als Substituenten bevorzugt Hydroxy-, Amino-, Nitro-, Sulfonsäuregruppen oder Halogene in Frage kommen. Weitere Bevorzugte Reste R sind Phenyl- und Benzylreste sowie weiter substituierte Vertreter. Besonders bevorzugt steht R für eine Ci_6-Alkylgruppe. Beispiele für erfindungsgemäße d-C6-Alkylgruppen sind die Gruppen Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sec-Butyl, iso-Butyl, tert-Butyl, Pentyl, iso-Pentyl und Hexyl.In formula (C-II), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably, R is a Ci_ 6 alkyl group. Examples of C 1 -C 6 -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.
Erfindungsgemäß besonders bevorzugte Mittel sind dadurch gekennzeichnet, daß der Rest R in Formel (C-I) ausgewählt ist aus Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, terf-Butyl- sowie Hydroxymethyl- und Hydroxyethyl-Resten.Particularly preferred agents according to the invention are characterized in that the radical R in formula (CI) is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl as well as hydroxymethyl and hydroxyethyl radicals.
Das acide H-Atom des Kohlensäuremonoesters bzw. -monoamids kann auch in neutralisierter Form vorliegen, d.h. es können erfindungsgemäß auch Salze von Kohlensäuremonoestern bzw. Kohlensäuremonoamiden eingesetzt werden. Hier sind erfindungsgemäße Mittel bevorzugt, die den Kohlensäuremonoester bzw. das Kohlensäuremonoamid in ganz oder teilweise neutralisierter Form, vorzugsweise in Form seines Alkalimetall-, Ammonium-, Erdalkalimetall- oder Aluminiumsalzes und insbesondere in Form seines Natriumsalzes, enthalten.The acidic H atom of the carbonic acid monoester or monoamide may also be in neutralized form, i. salts of carbonic acid monoesters or carbonic acid monoamides can also be used according to the invention. Here, agents according to the invention are preferred which contain the carbonic acid monoester or the carbonic acid monoamide in completely or partially neutralized form, preferably in the form of its alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt.
Unabhängig davon, ob die erfindungsgemäßen Mittel einen oder mehrere Kohlensäuremonoester und/oder ein oder mehrere Kohlensäuremonoamide enthalten, sind erfindungsgemäße Mittel bevorzugt, die den bzw. die Kohlensäuremonoester und/oder Kohlensäuremonoamide in Mengen von 0,1 bis 20 Gew.%, vorzugsweise von 0,5 bis 18 Gew.%, besonders bevorzugt von 2 bis 15 Gew.% und insbesondere von 5 bis 12 Gew.%, jeweils bezogen auf das gesamte Mittel, enthalten. Zusätzlich zu Carbonaten und/oder Kohlensäuremonoestern und/oder Kohlensäuremonoamiden oder an deren Stelle können die erfindungsgemäßen Mittel vorzugsweise auch mindestens ein Silylcarbonat und/oder mindestens ein Silylcarbamat enthalten. Diese Substanzen werden nachfolgend detailliert beschrieben.Regardless of whether the compositions according to the invention comprise one or more carbonic acid monoesters and / or one or more carbonic acid monoamides, agents according to the invention are preferred which contain the carbonic acid monoester and / or carbonic acid monoamides in amounts of from 0.1 to 20% by weight, preferably from 0 , 5 to 18 wt.%, Particularly preferably from 2 to 15 wt.% And in particular from 5 to 12 wt.%, Each based on the total agent. In addition to or in place of carbonates and / or carbonic acid monoesters and / or carbonic acid monoamides, the compositions according to the invention may preferably also contain at least one silyl carbonate and / or at least one silyl carbamate. These substances are described in detail below.
Erfindungsgemäß bevorzugte Mittel sind dadurch gekennzeichnet, daß sie mindestens ein Silylcarbonat der Formel (C-III)Agents preferred according to the invention are characterized in that they contain at least one silyl carbonate of the formula (C-III)
R2 R 2
R1-Si-O-C(O)-O-R4 (C-III)R 1 -Si-OC (O) -OR 4 (C-III)
R3 R 3
enthalten, in der die Reste R1, R2 und R3 unabhängig voneinander für ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine Trialkylsilylgruppe, vorzugsweise eine Trimethylsilylgruppe oder für eine substituierte oder unsubstiuierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus oder für ein Halogen, eine substituierte oder unsubstituierte Hydroxy-, Oxo-, Amino-, Iminogruppen stehen und der Rest R4 für eine chemische Bindung zum Si-Atom oder zu einem der Reste R1, R2 oder R3, ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine substituierte oder unsubstituierte SiIyI- oder Aluminylgruppe oder für eine substituierte oder unsubstituierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus steht.in which the radicals R 1 , R 2 and R 3 independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted Aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino, imino groups and the radical R 4 is a chemical bond to the Si atom or to one of the radicals R 1 , R 2 or R 3 , a hydrogen atom, a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical or for a substituted or unsubstituted SiIyI or alumino group or for a substituted or unsubstituted aryl group or a substituted or unsubstituted Het rocyclus stands.
Bevorzugte Reste R1, R2 und R3 in der oben genannten Formel (C-III) sind substituierte oder unsubstituierte, geradkettige oder verzweigte Alkylreste. Unter diesen sind die Alkylreste mit 1 bis 5 Kohlenstoffatomen sowie die Hydroxyalkylreste bevorzugt, so daß bevorzugte erfindungsgemäße Mittel dadurch gekennzeichnet sind, daß die Reste R1, R2 und R3 in Formel (C-III) ausgewählt sind aus Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, terf-Butyl- sowie Hydroxymethyl- und Hyd roxyethyl-Resten .Preferred radicals R 1 , R 2 and R 3 in the abovementioned formula (C-III) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among these, the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred agents according to the invention are characterized in that the radicals R 1 , R 2 and R 3 in formula (C-III) are selected from methyl, ethyl , n-propyl, iso-propyl, n-butyl, iso-butyl, terf-butyl and hydroxymethyl and hydroxyethyl radicals.
Bevorzugte Reste R4 in der oben genannten Formel (C-III) sind Wasserstoff, substituierte oder unsubstituierte, geradkettige oder verzweigte Alkylreste sowie Trialkylsilylreste. Unter diesen sind Wasserstoff, Methyl-, Ethyl-, tert.-Butyl- und Trimethylsilylreste bevorzugt. Das acide H-Atom des Silylcarbonats (R4 = -H in Formel C-III) kann auch in neutralisierter Form vorliegen, d.h. es können erfindungsgemäß auch Salze von Silylcarbonaten eingesetzt werden. Hier sind erfindungsgemäße Mittel bevorzugt, die mindestens ein Silylcarbonat in ganz oder teilweise neutralisierter Form, vorzugsweise in Form seines Alkalimetall-, Ammonium-, Erdalkalimetall- oder Aluminiumsalzes und insbesondere in Form seines Natriumsalzes, enthalten.Preferred radicals R 4 in the abovementioned formula (C-III) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals. The acidic H atom of the silyl carbonate (R 4 = -H in formula C-III) may also be present in neutralized form, ie it is also possible according to the invention to use salts of silyl carbonates. Here, agents according to the invention are preferred which comprise at least one silyl carbonate in completely or partially neutralized form, preferably in the form of its alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt.
Zusätzlich zu den Siliylcarbonaten oder an ihrer Stelle können die erfindungsgemäßen Mittel Silylcarbamate enthalten.In addition to the silylcarbonates or in their place, the compositions of the invention may contain silyl carbamates.
Erfindungsgemäß bevorzugte Mittel sind dadurch gekennzeichnet, daß sie ein Silylcarbamat der Formel C-IV)Agents preferred according to the invention are characterized in that they contain a silyl carbamate of the formula C-IV)
R2 R 2
R1-Si-O-C(O)-NR4R5 (C-IV)R 1 -Si-OC (O) -NR 4 R 5 (C-IV)
R3 R 3
enthalten, in der enthält, in der die Reste R1, R2 und R3 unabhängig voneinander für ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine Trialkylsilylgruppe, vorzugsweise eine Trimethylsilylgruppe oder für eine substituierte oder unsubstituierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus oder für ein Halogen, eine substituierte oder unsubstituierte Hydroxy-, Oxo-, Aminogruppen stehen und die Rest R4 und R5 unabhängig voneinander für eine chemische Bindung zum Si-Atom oder zu einem der Reste R1, R2 oder R3, ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine substituierte oder unsubstituierte SiIyI- oder Aluminylgruppe oder für eine substituierte oder unsubstituierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus stehen.containing, in which the radicals R 1 , R 2 and R 3 independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or for a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino groups and the radicals R 4 and R 5 independently of one another for a chemical bond to the Si atom or to a the radicals R 1 , R 2 or R 3 , a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted SiIyI or alumino group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.
Bevorzugte Reste R1, R2 und R3 in der oben genannten Formel (C-IV) sind substituierte oder unsubstituierte, geradkettige oder verzweigte Alkylreste. Unter diesen sind die Alkylreste mit 1 bis 5 Kohlenstoffatomen sowie die Hydroxyalkylreste bevorzugt, so daß bevorzugte erfindungsgemäße Mittel dadurch gekennzeichnet sind, daß die Reste R1, R2 und R3 in Formel (VII) ausgewählt sind aus Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, terf-Butyl- sowie Hydroxymethyl- und Hyd roxyethyl-Resten . Bevorzugte Reste R4 und R5 in der oben genannten Formel (C-IV) sind Wasserstoff, substituierte oder unsubstituierte, geradkettige oder verzweigte Alkylreste sowie Trialkylsilylreste. Unter diesen sind Wasserstoff, Methyl-, Ethyl-, tert.-Butyl- und Trimethylsilylreste bevorzugt.Preferred radicals R 1 , R 2 and R 3 in the abovementioned formula (C-IV) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among these, the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred agents according to the invention are characterized in that the radicals R 1 , R 2 and R 3 in formula (VII) are selected from methyl, ethyl, n Propyl, iso-propyl, n-butyl, iso-butyl, terf-butyl and hydroxymethyl and hydroxyethyl radicals. Preferred radicals R 4 and R 5 in the abovementioned formula (C-IV) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.
Unabhängig davon, ob die erfindungsgemäßen Mittel ein oder mehrere Silylcarbonate und/oder ein oder mehrere Silylcarbamate enthalten, sind erfindungsgemäße Mittel bevorzugt, die das bzw. die Silylcarbonat(e) und/oder Silylcarbamat(e) in Mengen von 0,1 bis 25 Gew.%, vorzugsweise von 0,5 bis 20 Gew.%, besonders bevorzugt von 1 bis 15 Gew.% und insbesondere von 1 ,5 bis 10 Gew.%, jeweils bezogen auf das gesamte Mittel, enthalten.Regardless of whether the compositions according to the invention contain one or more silyl carbonates and / or one or more silyl carbamates, agents according to the invention are preferred which contain the silyl carbonate (s) and / or silyl carbamate (s) in amounts of from 0.1 to 25% by weight .%, Preferably from 0.5 to 20 wt.%, Particularly preferably from 1 to 15 wt.% And in particular from 1, 5 to 10 wt.%, Each based on the total agent.
Eine weitere Steigerung der Aufhelleistung läßt sich durch den Zusatz von Cyanaten bzw. „Cyanatanaloga" erreichen, die in Kombination mit dem erfindungsgemäßen Einsatz der Polyolester eine Wirkungssteigerung ermöglichen. Bevorzugte erfindungsgemäße Mittel können daher 0,05 bis 5 Gew.-% mindestens eines Cyanats der FormelA further increase in the whitening power can be achieved by the addition of cyanates or "cyanate analogues" which, in combination with the use according to the invention of the polyol esters, make it possible to increase the activity formula
M+ [OCN]" in der M+ für K+, Na+, Li+ oder NH4 + oder 1/2 Ca2+, 1/2 Mg2+ oder 1/2 Zn2+ steht und/oderM + [OCN] "in which M + is K +, Na +, Li + or NH 4 +, or 1/2 Ca 2+, 1/2 Mg 2+ or 1/2 Zn 2+ and / or
0,05 bis 5 Gew.-% mindestens einer Verbindung der Formel H2N-C(O)-L in der L für eine durch das Anion "C1C1H verdrängbare Gruppe steht, enthalten0.05 to 5 wt .-% of at least one compound of the formula H 2 NC (O) -L in the L is a displaceable by the anion " C 1 C 1 H group
Als Cyanate können erfindungsgemäß Kaliumcyanat, KOCN, und/oder Natriumcyanat, NaOCN, und/oder Lithiumcyanat, LiOCN, und/oder Ammoniumcyanat, NH4OCN, und/oder Calciumcyanat, Ca(OCN)2, und/oder Magnesiumcyanat, Mg(OCN)2, und/oder Zinkcyanat, Zn(OCN)2, eingesetzt werden.As cyanates according to the invention potassium cyanate, KOCN, and / or sodium cyanate, NaOCN, and / or lithium cyanate, LiOCN, and / or ammonium cyanate, NH 4 OCN, and / or calcium cyanate, Ca (OCN) 2 , and / or magnesium cyanate, Mg (OCN ) 2 , and / or zinc cyanate, Zn (OCN) 2 .
Erfindungsgemäß bevorzugte Mittel sind dadurch gekennzeichnet, daß sie 0,075 bis 4 Gew.-%, vorzugsweise 0,1 bis 2,5 Gew.-% und insbesondere 0,2 bis 1 Gew.-% Natriumcyanat und/oder Kaliumcyanat und/oder Ammoniumcyanat enthalten, wobei Natriumcyanat besonders bevorzugt ist.Agents preferred according to the invention are characterized in that they contain 0.075 to 4% by weight, preferably 0.1 to 2.5% by weight and in particular 0.2 to 1% by weight of sodium cyanate and / or potassium cyanate and / or ammonium cyanate with sodium cyanate being particularly preferred.
Anstelle von Cyanaten oder in Kombination mit ihnen können auch Verbindungen der Formel H2N- C(O)-L, in der L für eine durch das Anion ~OOH verdrängbare Gruppe steht, in den erfindungsgemäßen Mitteln enthalten sein. Hier sind erfindungsgemäß bevorzugte Mittel dadurch gekennzeichnet, daß sie 0,075 bis 4 Gew.-%, vorzugsweise 0,1 bis 3,5 Gew.-% und insbesondere 0,2 bis 3 Gew.-% mindestens einer Verbindung der FormelInstead of cyanates or in combination with them, compounds of the formula H 2 N-C (O) -L in which L is a group displaceable by the anion ~ OOH can also be present in the agents according to the invention. Here are preferred agents according to the invention characterized in that they are 0.075 to 4 wt .-%, preferably 0.1 to 3.5 wt .-% and in particular 0.2 to 3 wt .-% of at least one compound of the formula
H2N-C(O)-L enthalten, in der L ausgewählt ist aus -S-CH2-COOH, -S-(CH2)3SO3H, -S-(CH2)2-NH2, -OCH3, -O-(C6H4)-SO3M, -Q+, -NH-OH, -0-C(O)-R1, -0-C(O)-H, -0-CH(OH)2, -SO3M, -PH(O)OH, -P(O)(OH)2, -(NH-Glucosamin)n, -NH-C(O)-NH2, -NH-NH2, -NH-CN, -P(OH)(O)-C(O)NH2, -SCN, -OCN, -S-C(NH)NH2, OONa
Figure imgf000054_0002
H 2 NC (O) -L in which L is selected from -S-CH 2 -COOH, -S- (CH 2 ) 3 SO 3 H, -S- (CH 2 ) 2 -NH 2 , -OCH 3 , -O- (C 6 H 4 ) -SO 3 M, -Q + , -NH-OH, -O-C (O) -R 1 , -O-C (O) -H, -O-CH (OH) 2 , -SO 3 M, -PH (O) OH, -P (O) (OH) 2 , - (NH-glucosamine) n , -NH-C (O) -NH 2 , -NH-NH 2 , -NH-CN, - P (OH) (O) -C (O) NH 2 , -SCN, -OCN, -SC (NH) NH 2 , OONa
Figure imgf000054_0002
Figure imgf000054_0001
und M für -H, Na, K, NH4 steht, Q ausgewählt ist aus den aus tertiären Aminen gebildeten quartären Ammoniumresten, Heteroarylresten oder nicht-aromatischen Heterocyclen und R1 für -H, -CH3, - CH2CH3, -(CH2)2CH3, -CH(CH3)2 oder eine andere Alkylgruppe steht.
Figure imgf000054_0001
and M is -H, Na, K, NH4, Q is selected from quaternary ammonium radicals, heteroaryl radicals or nonaromatic heterocycles formed from tertiary amines, and R 1 is -H, -CH 3 , -CH 2 CH 3 , - ( CH 2 ) 2 CH 3 , -CH (CH 3 ) 2 or another alkyl group.
Erfindungsgemäß besonders bevorzugte Mittel enthalten 0,075 bis 4 Gew.-%, vorzugsweise 0,1 bis 3,5 Gew.-% und insbesondere 0,2 bis 3 Gew.-% mindestens einer der nachstehend aufgeführten Verbindungen:Particularly preferred agents according to the invention contain from 0.075 to 4% by weight, preferably from 0.1 to 3.5% by weight and in particular from 0.2 to 3% by weight of at least one of the compounds listed below:
- H2N-C(O)-S-CH2-COOH _ H2N-C(O)-S-(CH2)2-NH2 - H 2 NC (O) -S-CH 2 -COOH _H 2 NC (O) -S- (CH 2 ) 2 -NH 2
- H2N-C(O)-S-(CH2)3SO3Na- H 2 NC (O) -S- (CH 2 ) 3 SO 3 Na
- H2N-C(O)-S-(CH2)3SO3K- H 2 NC (O) -S- (CH 2 ) 3 SO 3 K
- H2N-C(O)-S-(CH2)3SO3NH4 - H 2 NC (O) -S- (CH 2 ) 3 SO 3 NH 4
- H2N-C(O)-SO3H- H 2 NC (O) -SO 3 H
- H2N-C(O)-SO3Na- H 2 NC (O) -SO 3 Na
- H2N-C(O)-SO3K- H 2 NC (O) -SO 3 K
- H2N-C(O)-SO3NH4 - H 2 NC (O) -SO 3 NH 4
- H2N-C(O)-O-(C6H4)-SO3H- H 2 NC (O) -O- (C 6 H 4 ) -SO 3 H
- H2N-C(O)-O-(C6H4)-SO3Na- H 2 NC (O) -O- (C 6 H 4 ) -SO 3 Na
- H2N-C(O)-O-(C6H4)-SO3K- H 2 NC (O) -O- (C 6 H 4 ) -SO 3 K
- H2N-C(O)-O-(C6H4)-SO3NH4 - H 2 NC (O) -O- (C 6 H 4 ) -SO 3 NH 4
- H2N-C(O)-O-C(O)-H- H 2 NC (O) -OC (O) -H
■ H2N-C(O)-O-C(O)-CH3 ■ H 2 NC (O) -OC (O) -CH 3
■ H2N-C(O)-O-C(O)-CH2CH3 ■ H 2 NC (O) -OC (O) -CH 2 CH 3
■ H2N-C(O)-O-C(O)-(CH2)2CH3 ■ H 2 NC (O) -OC (O) - (CH 2 ) 2 CH 3
■ H2N-C(O)-O-C(O)-CH(CH3)2 - H2N-C(O)-OCH3 ■ H 2 NC (O) -OC (O) -CH (CH 3 ) 2 - H 2 NC (O) -OCH 3
- H2N-C(O)-NH-OH- H 2 NC (O) -NH-OH
- H2N-C(O)-O-CH(OH)2 - H 2 NC (O) -O-CH (OH) 2
- H2N-C(O)-PH(O)OH- H 2 NC (O) -PH (O) OH
- H2N-C(O)-P(O)(OH)2 - H 2 NC (O) -P (O) (OH) 2
- H2N-C(O)-NH-C(O)-NH2 - H 2 NC (O) -NH-C (O) -NH 2
- H2N-C(O)-NH-NH2 - H 2 NC (O) -NH-NH 2
- H2N-C(O)-NH-CN- H 2 NC (O) -NH-CN
- H2N-C(O)-P(OH)(O)-C(O)NH2 - H 2 NC (O) -P (OH) (O) -C (O) NH 2
- H2N-C(O)-SCN- H 2 NC (O) -SCN
- H2N-C(O)-OCN- H 2 NC (O) -OCN
- H2N-C(O)-S-C(NH)NH2 - H 2 NC (O) -SC (NH) NH 2
- H2N-C(O)-N(CHs)3 + Cr- H 2 NC (O) -N (CH 3 ) 3 + Cr
- H2N-C(O)-N(CH2CHs)3 + Cl" H 2 NC (O) -N (CH 2 CHs) 3 + Cl "
- H2N-C(O)-N((CH2)2CH3)3 + Cl" - H 2 NC (O) -N ((CH 2 ) 2 CH 3 ) 3 + Cl "
- H2N-C(O)-N(CH(CH3)2)3 + Cl" - H 2 NC (O) -N (CH (CH 3 ) 2 ) 3 + Cl "
- H2N-C(O)-N(C6Hs)3 + Cl" H 2 NC (O) -N (C 6 Hs) 3 + Cl "
- H2N-C(O)-N(CH2-Ph)3 + Cl" H 2 NC (O) -N (CH 2 -Ph) 3 + Cl "
- H2N-C(O)-N(CH3)3 + Br" - H 2 NC (O) -N (CH 3 ) 3 + Br "
- H2N-C(O)-N(CH2CH3)3 + Br" H 2 NC (O) -N (CH 2 CH 3 ) 3 + Br "
- H2N-C(O)-N((CH2)2CH3)3 + Br" - H 2 NC (O) -N ((CH 2 ) 2 CH 3 ) 3 + Br "
- H2N-C(O)-N(CH(CH3)2)3 + Br" - H 2 NC (O) -N (CH (CH 3 ) 2 ) 3 + Br "
- H2N-C(O)-N(C6Hs)3 + Br" - H 2 NC (O) -N (C 6 Hs) 3 + Br "
- H2N-C(O)-N(CH2-Ph)3 + Br" H 2 NC (O) -N (CH 2 -Ph) 3 + Br "
- H2N-C(O)-N(CH3)3 + H3C-OSO3 " H 2 NC (O) -N (CH 3 ) 3 + H 3 C-OSO 3 "
- H2N-C(O)-N(CH2CH3)3 + H3C-OSO3 " H 2 NC (O) -N (CH 2 CH 3 ) 3 + H 3 C-OSO 3 "
- H2N-C(O)-N((CH2)2CH3)3 + H3C-OSO3 " H 2 NC (O) -N ((CH 2 ) 2 CH 3 ) 3 + H 3 C-OSO 3 "
- H2N-C(O)-N(CH(CH3)2)3 + H3C-OSO3 " H 2 NC (O) -N (CH (CH 3 ) 2 ) 3 + H 3 C-OSO 3 "
- H2N-C(O)-N(C6Hs)3 + H3C-OSO3 " H 2 NC (O) -N (C 6 Hs) 3 + H 3 C-OSO 3 "
- H2N-C(O)-N(CH2-Ph)3 + H3C-OSO3 " H 2 NC (O) -N (CH 2 -Ph) 3 + H 3 C-OSO 3 "
- H2N-C(O)-N(CH3)3 + H3C-CH2-OSO3 " H 2 NC (O) -N (CH 3 ) 3 + H 3 C-CH 2 -OSO 3 "
- H2N-C(O)-N(CH2CH3)3 + H3C-CH2-OSO3 " H 2 NC (O) -N (CH 2 CH 3 ) 3 + H 3 C-CH 2 -OSO 3 "
- H2N-C(O)-N((CH2)2CH3)3 + H3C-CH2-OSO3 " H 2 NC (O) -N ((CH 2 ) 2 CH 3 ) 3 + H 3 C-CH 2 -OSO 3 "
- H2N-C(O)-N(CH(CH3)2)3 + H3C-CH2-OSO3 " H 2 NC (O) -N (CH (CH 3 ) 2 ) 3 + H 3 C-CH 2 -OSO 3 "
- H2N-C(O)-N(C6Hs)3 + H3C-CH2-OSO3 " H 2 NC (O) -N (C 6 Hs) 3 + H 3 C-CH 2 -OSO 3 "
- H2N-C(O)-N(CH2-Ph)3 + H3C-CH2-OSO3 " Auch Piperidone bzw. ihre Derivate können die Effekte der Polyolester verstärken, so daß ein Einsatz von 0,1 bis 20 Gew.-% mindestens eines Piperidons und/oder Piperidonderivats in den erfindungsgemäßen Mitteln bevorzugt ist. Vorzugsweise enthalten die erfindungsgemäßen Mittel 0,5 bis 15 Gew.-%, besonders bevorzugt 1 bis 12,5 Gew.-% und insbesondere 2,5 bis 10 Gew.-% mindestens einer Verbindung aus der GruppeH 2 NC (O) -N (CH 2 -Ph) 3 + H 3 C-CH 2 -OSO 3 " Piperidones or their derivatives can also enhance the effects of the polyol esters, so that use of from 0.1 to 20% by weight of at least one piperidone and / or piperidone derivative in the agents according to the invention is preferred. The agents according to the invention preferably contain from 0.5 to 15% by weight, more preferably from 1 to 12.5% by weight and in particular from 2.5 to 10% by weight, of at least one compound from the group
- 2-Piperidon und/oder2-piperidone and / or
- der Derivate von 2-Piperidon, insbesondere der 2-Piperidiniumsalze und/oderthe derivatives of 2-piperidone, especially the 2-piperidinium salts and / or
- 3-Piperidon und/oder3-piperidone and / or
- der Derivate von 3-Piperidon, insbesondere der 3-Piperidiniumsalze und/oderthe derivatives of 3-piperidone, especially the 3-piperidinium salts and / or
- 4-Piperidon und/oder4-piperidone and / or
- der Derivate von 4-Piperidon, insbesondere der 4-Piperidiniumsalze- The derivatives of 4-piperidone, in particular the 4-piperidinium salts
Piperidone sind Verbindungen, die eine Ketofunktion an einem Sechsring aufweisen, der aus fünf Kohlenstoffatomen und einem Stickstoffatom gebildet wird. Je nach Stellung des Stickstoffatom es zur Ketogruppe bezeichnet man den unsubstituierten Grundkörper als 2-Piperidon (Piperidin-2-on, δ- Valerolactam, alpha-Piperidon), 3-Piperidon (Piperidin-3-on, beta-Piperidon) oder 4-Piperidon (Piperidin-4-on, gamma-Piperidon).Piperidones are compounds having a keto function on a six-membered ring formed of five carbon atoms and one nitrogen atom. Depending on the position of the nitrogen atom it is called the keto group, the unsubstituted base body as 2-piperidone (piperidine-2-one, δ-valerolactam, alpha-piperidone), 3-piperidone (piperidin-3-one, beta-piperidone) or 4- Piperidone (piperidin-4-one, gamma-piperidone).
Diese drei Piperidone sind erfindungsgemäß bevorzugt einsetzbar. Als zusätzlich zu den Piperidonen oder an ihrer Stelle erfindungsgemäß einsetzbare Piperidonderivate kommen sowohl am C-Gerüst, als auch am Stickstoffatom substituierte Piperidone in Frage, wobei die N-substituierten Piperidonderviate eine große Bedeutung haben, da sich das H-Atom am Stickstoff leicht austauschen läßt. Unter diesen Piperidonderviaten haben sich erfindungsgemäß folgende als besonders bevorzugt erwiesen:These three piperidones are preferably used according to the invention. In addition to the piperidones or piperidone derivatives which can be used according to the invention, substituted piperidones are suitable both on the C-skeleton and on the nitrogen atom, the N-substituted piperidone derivatives being of great importance, since the nitrogen can be easily exchanged for nitrogen , Among these piperidone derivatives, the following have been found to be particularly preferred according to the invention:
1-Methyl-Piperidin-4-on (N-Methyl-4-piperidon)1-methyl-piperidin-4-one (N-methyl-4-piperidone)
1-Methyl-Piperidin-3-on (N-Methyl-3-piperidon)1-methyl-piperidin-3-one (N-methyl-3-piperidone)
1-Methyl-Piperidin-2-on (N-Methyl-2-piperidon)1-methyl-piperidin-2-one (N-methyl-2-piperidone)
1-Ethyl-Piperidin-4-on (N-Ethyl-4-piperidon)1-ethyl-piperidin-4-one (N-ethyl-4-piperidone)
1-Ethyl-Piperidin-3-on (N-Ethyl-3-piperidon)1-ethyl-piperidin-3-one (N-ethyl-3-piperidone)
1-Ethyl-Piperidin-2-on (N-Ethyl-2-piperidon)1-ethyl-piperidin-2-one (N-ethyl-2-piperidone)
1-Propyl-Piperidin-4-on (N-Propyl-4-piperidon)1-Propyl-piperidin-4-one (N-propyl-4-piperidone)
1-Propyl-Piperidin-3-on (N-Propyl-3-piperidon)1-Propyl-piperidin-3-one (N-propyl-3-piperidone)
1-Propyl-Piperidin-2-on (N-Propyl-2-piperidon) 1-lsopropyl-Piperidin-4-on (N-lsopropyl-4-piperidon) 1-lsopropyl-Piperidin-3-on (N-lsopropyl-3-piperidon) 1-lsopropyl-Piperidin-2-on (N-lsopropyl-2-piperidon) 1-Butyl-Piperidin-4-on (N-Butyl-4-piperidon) 1-Butyl-Piperidin-3-on (N-Butyl-3-piperidon) 1-Butyl-Piperidin-2-on (N-Butyl-2-piperidon) 1-Pentyl-Piperidin-4-on (N-Pentyl-4-piperidon) 1-Pentyl-Piperidin-3-on (N-Pentyl-3-piperidon) 1-Pentyl-Piperidin-2-on (N-Pentyl-2-piperidon) 1-Hexyl-Piperidin-4-on (N-Hexyl-4-piperidon) 1-Hexyl-Piperidin-3-on (N-Hexyl-3-piperidon) 1-Hexyl-Piperidin-2-on (N-Hexyl-2-piperidon) 1-Heptyl-Piperidin-4-on (N-Heptyl-4-piperidon) 1-Heptyl-Piperidin-3-on (N-Heptyl-3-piperidon) 1-Heptyl-Piperidin-2-on (N-Heptyl-2-piperidon) 1-Octyl-Piperidin-4-on (N-Octyl-4-piperidon) 1-Octyl-Piperidin-3-on (N-Octyl-3-piperidon) 1-Octyl-Piperidin-2-on (N-Octyl-2-piperidon) 1-Nonyl-Piperidin-4-on (N-Nonyl-4-piperidon) 1-Nonyl-Piperidin-3-on (N-Nonyl-3-piperidon) 1-Nonyl-Piperidin-2-on (N-Nonyl-2-piperidon) 1-Decyl-Piperidin-4-on (N-Decyl-4-piperidon) 1-Decyl-Piperidin-3-on (N-Decyl-3-piperidon) 1-Decyl-Piperidin-2-on (N-Decyl-2-piperidon)1-Propyl-piperidin-2-one (N-propyl-2-piperidone) 1-isopropyl-piperidin-4-one (N-isopropyl-4-piperidone) 1-isopropyl-piperidin-3-one (N-isopropyl-3-piperidone) 1-isopropyl-piperidin-2-one (N-isopropyl- 2-piperidone) 1-Butyl-piperidin-4-one (N-butyl-4-piperidone) 1-butyl-piperidin-3-one (N-butyl-3-piperidone) 1-butyl-piperidin-2-one ( N-butyl-2-piperidone) 1-Pentyl-piperidin-4-one (N-pentyl-4-piperidone) 1-pentyl-piperidin-3-one (N-pentyl-3-piperidone) 1-pentyl-piperidine 2-one (N-pentyl-2-piperidone) 1-hexyl-piperidin-4-one (N-hexyl-4-piperidone) 1-hexyl-piperidin-3-one (N-hexyl-3-piperidone) 1- Hexyl-piperidin-2-one (N-hexyl-2-piperidone) 1-heptyl-piperidin-4-one (N-heptyl-4-piperidone) 1-heptyl-piperidin-3-one (N-heptyl-3-one piperidone) 1-heptyl-piperidin-2-one (N-heptyl-2-piperidone) 1-octyl-piperidin-4-one (N-octyl-4-piperidone) 1-octyl-piperidin-3-one (N- Octyl-3-piperidone) 1-octyl-piperidin-2-one (N-octyl-2-piperidone) 1-nonyl-piperidin-4-one (N-nonyl-4-piperidone) 1-nonyl-piperidine-3 on (N-nonyl-3-piperidone) 1-nonyl-piperidin-2-one (N-nonyl-2-piperidone) 1-decyl-piperidine-4 -on (N-decyl-4-piperidone) 1-decyl-piperidin-3-one (N-decyl-3-piperidone) 1-decyl-piperidin-2-one (N-decyl-2-piperidone)
Das N-Atom in den erfindungsgemäß vorzugsweise eingesetzten Piperidonen kann auch quaterniert vorliegen, so daß erfindungsgemäß bevorzugt auch Piperidiniumsalze eingesetzt werden können. Hier sind erfindungsgemäß besonders bevorzugte Mittel, dadurch gekennzeichnet, daß sie 3- Piperidiniumsalze der Formel (VII) und/oder 4-Piperidiniumsalze der Formel (VIII) enthaltenThe N atom in the piperidones preferably used according to the invention may also be present in quaternized form, so that it is also possible according to the invention to use piperidinium salts. Here are particularly preferred agents according to the invention, characterized in that they contain 3-piperidinium salts of the formula (VII) and / or 4-piperidinium salts of the formula (VIII)
Figure imgf000057_0001
Figure imgf000057_0001
(VIl) (VlIl) in denen die Reste R1 bzw. R2 bzw. R3 bzw. R4 bzw. R5 bzw. R6 unabhängig voneinander ausgewählt sind aus -H, -CH3, -CH2CH3, -(CH2)2CH2, -CH(CH3)2, -(CH2)3CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)2, oder anderen Alkylresten, Alkenylresten, gegebenenfalls substituierten Arylresten und bei denen das Gegenion vorzugsweise ausgewählt ist aus Chlorid, Bromid, Methosulfat, Toluolsulfonat.(VIl) (VIl) in which the radicals R 1 or R 2 or R 3 or R 4 or R 5 or R 6 are independently selected from -H, -CH 3 , -CH 2 CH 3 , - (CH 2 ) 2 CH 2 , -CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH (CH 3 ) CH 2 CH 3 , -CH 2 CH (CH 3 ) 2 , or other alkyl, alkenyl, optionally substituted aryl radicals and wherein the counterion is preferably selected from chloride, bromide, methosulfate, toluenesulfonate.
Vorzugsweise können die Reste bzw. R3 bzw. R4 bzw. R5 bzw. R6 ein Wasserstoffatom sein. Unter diesen Piperidiniumsalzen haben sich erfindungsgemäß folgende als besonders bevorzugt erwiesen:Preferably, the radicals or R 3 or R 4 or R 5 or R 6 may be a hydrogen atom. Among these piperidinium salts, the following have been found to be particularly preferred according to the invention:
- 3-oxo-Piperidinium-Chlorid (R1 = R2 = H in Formel VII)3-oxo-piperidinium chloride (R 1 = R 2 = H in formula VII)
- 4-oxo-Piperidinium-Chlorid (R1 = R2 = H in Formel VIII)4-oxo-piperidinium chloride (R 1 = R 2 = H in formula VIII)
- 3-oxo-Piperidinium-Bromid (R1 = R2 = H in Formel VII)3-oxo-piperidinium bromide (R 1 = R 2 = H in formula VII)
- 4-oxo-Piperidinium-Bromid (R1 = R2 = H in Formel VIII)4-oxo-piperidinium bromide (R 1 = R 2 = H in formula VIII)
- 3-oxo-Piperidinium-Methosulfat (R1 = R2 = H in Formel VII)3-oxo-piperidinium methosulfate (R 1 = R 2 = H in formula VII)
- 4-oxo-Piperidinium-Methosulfat (R1 = R2 = H in Formel VIII)4-oxo-piperidinium methosulfate (R 1 = R 2 = H in formula VIII)
- 3-oxo-Piperidinium-Tosylat (R1 = R2 = H in Formel VII)3-oxo-piperidinium tosylate (R 1 = R 2 = H in formula VII)
- 4-oxo-Piperidinium-Tosylat (R1 = R2 = H in Formel VIII)4-oxo-piperidinium tosylate (R 1 = R 2 = H in formula VIII)
- N-Methyl-3-oxo-piperidinium-Chlorid (R1 = -CH3, R2 = H in Formel VII)N-methyl-3-oxopiperidinium chloride (R 1 = -CH 3 , R 2 = H in formula VII)
- N-Methyl-4-oxo-piperidinium-Chlorid (R1 = -CH3, R2 = H in Formel VIII)N-methyl-4-oxopiperidinium chloride (R 1 = -CH 3 , R 2 = H in formula VIII)
- N-Methyl-3-oxo-piperidinium-Bromid (R1 = -CH3, R2 = H in Formel VII)N-methyl-3-oxopiperidinium bromide (R 1 = -CH 3 , R 2 = H in formula VII)
- N-Methyl-4-oxo-piperidinium-Bromid (R1 = -CH3, R2 = H in Formel VIII)N-methyl-4-oxopiperidinium bromide (R 1 = -CH 3 , R 2 = H in formula VIII)
- N-Methyl-3-oxo-piperidinium-Methosulfat (R1 = -CH3, R2 = H in Formel VII)N-methyl-3-oxopiperidinium methosulfate (R 1 = -CH 3 , R 2 = H in formula VII)
- N-Methyl-4-oxo-piperidinium-Methosulfat (R1 = -CH3, R2 = H in Formel VIII)N-methyl-4-oxopiperidinium methosulfate (R 1 = -CH 3 , R 2 = H in formula VIII)
- N-Methyl-3-oxo-piperidinium-Tosylat (R1 = -CH3, R2 = H in Formel VII)N-methyl-3-oxopiperidinium tosylate (R 1 = -CH 3 , R 2 = H in formula VII)
- N-Methyl-4-oxo-piperidinium-Tosylat (R1 = -CH3, R2 = H in Formel VIII)N-methyl-4-oxopiperidinium tosylate (R 1 = -CH 3 , R 2 = H in formula VIII)
- N-Ethyl-3-oxo-piperidinium-Chlorid (R1 = -CH2CH3, R2 = H in Formel VII)N-ethyl-3-oxopiperidinium chloride (R 1 = -CH 2 CH 3 , R 2 = H in formula VII)
- N-Ethyl-4-oxo-piperidinium-Chlorid (R1 = -CH2CH3, R2 = H in Formel VIII)N-ethyl-4-oxopiperidinium chloride (R 1 = -CH 2 CH 3 , R 2 = H in formula VIII)
- N-Ethyl-3-oxo-piperidinium-Bromid (R1 = -CH2CH3, R2 = H in Formel VII)N-ethyl-3-oxopiperidinium bromide (R 1 = -CH 2 CH 3 , R 2 = H in formula VII)
- N-Ethyl-4-oxo-piperidinium-Bromid (R1 = -CH2CH3, R2 = H in Formel VIII)N-ethyl-4-oxopiperidinium bromide (R 1 = -CH 2 CH 3 , R 2 = H in formula VIII)
- N-Ethyl-3-oxo-piperidinium-Methosulfat (R1 = -CH2CH3, R2 = H in Formel VII)N-ethyl-3-oxopiperidinium methosulfate (R 1 = -CH 2 CH 3 , R 2 = H in formula VII)
- N-Ethyl-4-oxo-piperidinium-Methosulfat (R1 = -CH2CH3, R2 = H in Formel VIII)N-ethyl-4-oxopiperidinium methosulfate (R 1 = -CH 2 CH 3 , R 2 = H in formula VIII)
- N-Ethyl-3-oxo-piperidinium-Tosylat (R1 = -CH2CH3, R2 = H in Formel VII)N-ethyl-3-oxopiperidinium tosylate (R 1 = -CH 2 CH 3 , R 2 = H in formula VII)
- N-Ethyl-4-oxo-piperidinium-Tosylat (R1 = -CH2CH3, R2 = H in Formel VIII)N-ethyl-4-oxopiperidinium tosylate (R 1 = -CH 2 CH 3 , R 2 = H in formula VIII)
- N-Propyl-3-oxo-piperidinium-Chlorid (R1 = -CH2CH2CH3, R2 = H in Formel VII)N-propyl-3-oxopiperidinium chloride (R 1 = -CH 2 CH 2 CH 3 , R 2 = H in formula VII)
- N-Propyl-4-oxo-piperidinium-Chlorid (R1 = -CH2CH2CH3, R2 = H in Formel VIII)N-propyl 4-oxopiperidinium chloride (R 1 = -CH 2 CH 2 CH 3 , R 2 = H in formula VIII)
- N-Propyl-3-oxo-piperidinium-Bromid (R1 = -CH2CH2CH3, R2 = H in Formel VII)N-propyl-3-oxopiperidinium bromide (R 1 = -CH 2 CH 2 CH 3 , R 2 = H in formula VII)
- N-Propyl-4-oxo-piperidinium-Bromid (R1 = -CH2CH2CH3, R2 = H in Formel VIII)N-propyl 4-oxopiperidinium bromide (R 1 = -CH 2 CH 2 CH 3 , R 2 = H in formula VIII)
- N-Propyl-3-oxo-piperidinium-Methosulfat (R1 = -CH2CH2CH3, R2 = H in Formel VII) - N-Propyl-4-oxo-piperidinium-Methosulfat (R1 = -CH2CH2CH3, R2 = H in Formel VIII)N-propyl-3-oxopiperidinium methosulfate (R 1 = -CH 2 CH 2 CH 3 , R 2 = H in formula VII) N-propyl-4-oxopiperidinium methosulfate (R 1 = -CH 2 CH 2 CH 3 , R 2 = H in formula VIII)
- N-Propyl-3-oxo-piperidinium-Tosylat (R1 = -CH2CH2CH3, R2 = H in Formel VII)N-propyl-3-oxopiperidinium tosylate (R 1 = -CH 2 CH 2 CH 3 , R 2 = H in formula VII)
- N-Propyl-4-oxo-piperidinium-Tosylat (R1 = -CH2CH2CH3, R2 = H in Formel VIII)N-propyl 4-oxopiperidinium tosylate (R 1 = -CH 2 CH 2 CH 3 , R 2 = H in formula VIII)
- N-lsopropyl-3-oxo-piperidinium-Chlorid (R1 = -CH(CH3)2, R2 = H in Formel VII)N-isopropyl-3-oxopiperidinium chloride (R 1 = -CH (CH 3 ) 2 , R 2 = H in formula VII)
- N-lsopropyl-4-oxo-piperidinium-Chlorid (R1 = -CH(CH3)2, R2 = H in Formel VIII)N-isopropyl-4-oxopiperidinium chloride (R 1 = -CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N-lsopropyl-3-oxo-piperidinium-Bromid (R1 = -CH(CH3)2R2 = H in Formel VII)N-isopropyl-3-oxopiperidinium bromide (R 1 = -CH (CH 3 ) 2 R 2 = H in formula VII)
- N-lsopropyl-4-oxo-piperidinium-Bromid (R1 = -CH(CH3)2, R2 = H in Formel VIII)N-isopropyl-4-oxopiperidinium bromide (R 1 = -CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N-lsopropyl-3-oxo-piperidinium-Methosulfat (R1 = -CH(CH3)2, R2 = H in Formel VII)N-isopropyl-3-oxopiperidinium methosulfate (R 1 = -CH (CH 3 ) 2 , R 2 = H in formula VII)
- N-lsopropyl-4-oxo-piperidinium-Methosulfat (R1 = -CH(CH3)2, R2 = H in Formel VIII)N-isopropyl-4-oxopiperidinium methosulfate (R 1 = -CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N-lsopropyl-3-oxo-piperidinium-Tosylat (R1 = -CH(CH3)2, R2 = H in Formel VII)N-isopropyl-3-oxopiperidinium tosylate (R 1 = -CH (CH 3 ) 2 , R 2 = H in formula VII)
- N-lsopropyl-4-oxo-piperidinium-Tosylat (R1 = -CH(CH3)2, R2 = H in Formel VIII)N-isopropyl-4-oxopiperidinium tosylate (R 1 = -CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N-Butyl-3-oxo-piperidinium-Chlorid (R1 = -(CH2)3CH3, R2 = H in Formel VII)N-butyl-3-oxopiperidinium chloride (R 1 = - (CH 2 ) 3 CH 3 , R 2 = H in formula VII)
- N-Butyl-4-oxo-piperidinium-Chlorid (R1 = -(CH2)3CH3, R2 = H in Formel VIII)N-butyl-4-oxopiperidinium chloride (R 1 = - (CH 2 ) 3 CH 3 , R 2 = H in formula VIII)
- N-Butyl-3-oxo-piperidinium-Bromid (R1 = -(CH2)3CH3, R2 = H in Formel VII)N-butyl-3-oxopiperidinium bromide (R 1 = - (CH 2 ) 3 CH 3 , R 2 = H in formula VII)
- N-Butyl-4-oxo-piperidinium-Bromid (R1 = -(CH2)3CH3, R2 = H in Formel VIII)N-butyl-4-oxopiperidinium bromide (R 1 = - (CH 2 ) 3 CH 3 , R 2 = H in formula VIII)
- N-Butyl-3-oxo-piperidinium-Methosulfat (R1 = -(CH2)3CH3, R2 = H in Formel VII)N-butyl-3-oxopiperidinium methosulfate (R 1 = - (CH 2 ) 3 CH 3 , R 2 = H in formula VII)
- N-Butyl-4-oxo-piperidinium-Methosulfat (R1 = -(CH2)3CH3, R2 = H in Formel VIII)N-butyl-4-oxopiperidinium methosulfate (R 1 = - (CH 2 ) 3 CH 3 , R 2 = H in formula VIII)
- N-Butyl-3-oxo-piperidinium-Tosylat (R1 = -(CH2)3CH3, R2 = H in Formel VII)N-butyl-3-oxopiperidinium tosylate (R 1 = - (CH 2 ) 3 CH 3 , R 2 = H in formula VII)
- N-Butyl-4-oxo-piperidinium-Tosylat (R1 = -(CH2)3CH3, R2 = H in Formel VIII)N-butyl 4-oxopiperidinium tosylate (R 1 = - (CH 2 ) 3 CH 3 , R 2 = H in formula VIII)
- N-lsobutyl-3-oxo-piperidinium-Chlorid (R1 = -CH2CH(CH3)2, R2 = H in Formel VII)N-isobutyl-3-oxopiperidinium chloride (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N-lsobutyl-4-oxo-piperidinium-Chlorid (R1 = -CH2CH(CH3)2, R2 = H in Formel VIII)N-isobutyl-4-oxopiperidinium chloride (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N-lsobutyl-3-oxo-piperidinium-Bromid (R1 = -CH2CH(CH3)2, R2 = H in Formel VII)N-isobutyl-3-oxopiperidinium bromide (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N-lsobutyl-4-oxo-piperidinium-Bromid (R1 = -CH2CH(CH3)2, R2 = H in Formel VIII)N-isobutyl-4-oxopiperidinium bromide (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N-lsobutyl-3-oxo-piperidinium-Methosulfat (R1 = -CH2CH(CH3)2, R2 = H in Formel VII)N-isobutyl-3-oxopiperidinium methosulfate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N-lsobutyl-4-oxo-piperidinium-Methosulfat (R1 = -CH2CH(CH3)2, R2 = H in Formel VIII)N-isobutyl-4-oxopiperidinium methosulfate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N-lsobutyl-3-oxo-piperidinium-Tosylat (R1 = -CH2CH(CH3)2, R2 = H in Formel VII)N-isobutyl-3-oxopiperidinium tosylate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N-lsobutyl-4-oxo-piperidinium-Tosylat (R1 = -CH2CH(CH3)2, R2 = H in Formel VIII)N-isobutyl-4-oxopiperidinium tosylate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N-sec-Butyl-3-oxo-piperidinium-Chlorid (R1 = -CH2CH(CH3)2, R2 = H in Formel VII)N-sec-butyl-3-oxopiperidinium chloride (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N-sec-Butyl-4-oxo-piperidinium-Chlorid (R1 = -CH2CH(CH3)2, R2 = H in Formel VIII)N-sec-butyl-4-oxopiperidinium chloride (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N-sec-Butyl-3-oxo-piperidinium-Bromid (R1 = -CH2CH(CH3)2, R2 = H in Formel VII)N-sec-butyl-3-oxopiperidinium bromide (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N-sec-Butyl-4-oxo-piperidinium-Bromid (R1 = -CH2CH(CH3)2, R2 = H in Formel VIII)N-sec-butyl-4-oxopiperidinium bromide (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N-sec-Butyl-3-oxo-piperidinium-Methosulfat (R1 = -CH2CH(CH3)2, R2 = H in Formel VII)N-sec-butyl-3-oxopiperidinium methosulfate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N-sec-Butyl-4-oxo-piperidinium-Methosulfat (R1 = -CH2CH(CH3)2, R2 = H in Formel VIII)N-sec-butyl-4-oxopiperidinium methosulfate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N-sec-Butyl-3-oxo-piperidinium-Tosylat (R1 = -CH2CH(CH3)2, R2 = H in Formel VII)N-sec-butyl-3-oxopiperidinium tosylate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N-sec-Butyl-4-oxo-piperidinium-Tosylat (R1 = -CH2CH(CH3)2, R2 = H in Formel VIII)N-sec-butyl-4-oxopiperidinium tosylate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N,N-Dimethyl-3-oxo-piperidinium-Chlorid (R1 = R2 = -CH3 in Formel VII) - N,N-Dimethyl-4-oxo-piperidinium-Chlorid (R1 = R2 = -CH3 in Formel VIII)N, N-dimethyl-3-oxopiperidinium chloride (R 1 = R 2 = -CH 3 in formula VII) N, N-dimethyl-4-oxopiperidinium chloride (R 1 = R 2 = -CH 3 in formula VIII)
- N,N-Dimethyl-3-oxo-piperidinium-Bromid (R1 = R2 = -CH3 in Formel VII)N, N-dimethyl-3-oxopiperidinium bromide (R 1 = R 2 = -CH 3 in formula VII)
- N,N-Dimethyl-4-oxo-piperidinium-Bromid (R1 = R2 = -CH3 in Formel VIII)N, N-dimethyl-4-oxopiperidinium bromide (R 1 = R 2 = -CH 3 in formula VIII)
- N,N-Dimethyl-3-oxo-piperidinium-Methosulfat (R1 = R2 = -CH3 in Formel VII)N, N-dimethyl-3-oxopiperidinium methosulfate (R 1 = R 2 = -CH 3 in formula VII)
- N,N-Dimethyl-4-oxo-piperidinium-Methosalufat (R1 = R2 = -CH3 in Formel VIII)N, N-dimethyl-4-oxopiperidinium methosalufate (R 1 = R 2 = -CH 3 in formula VIII)
- N,N-Dimethyl-3-oxo-piperidinium-Tosylat (R1 = R2 = -CH3 in Formel VII)N, N-dimethyl-3-oxopiperidinium tosylate (R 1 = R 2 = -CH 3 in formula VII)
- N,N-Dimethyl-4-oxo-piperidinium-Tosylat (R1 = R2 = -CH3 in Formel VIII)N, N-dimethyl-4-oxopiperidinium tosylate (R 1 = R 2 = -CH 3 in formula VIII)
- N,N-Diethyl-3-oxo-piperidinium-Chlorid (R1 = -CH2CH3, R2 = H in Formel VII)N, N-diethyl-3-oxopiperidinium chloride (R 1 = -CH 2 CH 3 , R 2 = H in formula VII)
- N,N-Diethyl-4-oxo-piperidinium-Chlorid (R1 = -CH2CH3, R2 = H in Formel VIII)N, N-diethyl-4-oxopiperidinium chloride (R 1 = -CH 2 CH 3 , R 2 = H in formula VIII)
- N,N-Diethyl-3-oxo-piperidinium-Bromid (R1 = -CH2CH3, R2 = H in Formel VII)N, N-diethyl-3-oxopiperidinium bromide (R 1 = -CH 2 CH 3 , R 2 = H in formula VII)
- N,N-Diethyl-4-oxo-piperidinium-Bromid (R1 = -CH2CH3, R2 = H in Formel VIII)N, N-diethyl-4-oxopiperidinium bromide (R 1 = -CH 2 CH 3 , R 2 = H in formula VIII)
- N,N-Diethyl-3-oxo-piperidinium-Methosulfat (R1 = -CH2CH3, R2 = H in Formel VII)N, N-diethyl-3-oxopiperidinium methosulfate (R 1 = -CH 2 CH 3 , R 2 = H in formula VII)
- N,N-Diethyl-4-oxo-piperidinium-Methosulfat (R1 = -CH2CH3, R2 = H in Formel VIII)N, N-diethyl-4-oxopiperidinium methosulfate (R 1 = -CH 2 CH 3 , R 2 = H in formula VIII)
- N,N-Diethyl-3-oxo-piperidinium-Tosylat (R1 = -CH2CH3, R2 = H in Formel VII)N, N-diethyl-3-oxopiperidinium tosylate (R 1 = -CH 2 CH 3 , R 2 = H in formula VII)
- N,N-Diethyl-4-oxo-piperidinium-Tosylat (R1 = -CH2CH3, R2 = H in Formel VIII)N, N-diethyl-4-oxopiperidinium tosylate (R 1 = -CH 2 CH 3 , R 2 = H in formula VIII)
- N.N-Dipropyl-S-oxo-piperidinium-Chlorid (R1 = R2 = -CH2CH2CH3 in Formel VII)N, N-dipropyl-S-oxopiperidinium chloride (R 1 = R 2 = -CH 2 CH 2 CH 3 in formula VII)
- N,N-Dipropyl-4-oxo-piperidinium-Chlorid (R1 = R2 = -CH2CH2CH3 in Formel VIII)N, N-dipropyl-4-oxopiperidinium chloride (R 1 = R 2 = -CH 2 CH 2 CH 3 in formula VIII)
- N,N-Dipropyl-3-oxo-piperidinium-Bromid (R1 = R2 = -CH2CH2CH3 in Formel VII)N, N-dipropyl-3-oxopiperidinium bromide (R 1 = R 2 = -CH 2 CH 2 CH 3 in formula VII)
- N,N-Dipropyl-4-oxo-piperidinium-Bromid (R1 = R2 = -CH2CH2CH3 in Formel VIII)N, N-dipropyl-4-oxopiperidinium bromide (R 1 = R 2 = -CH 2 CH 2 CH 3 in formula VIII)
- N,N-Dipropyl-3-oxo-piperidinium-Methosulfat (R1 = R2 = -CH2CH2CH3 in Formel VII)N, N-dipropyl-3-oxopiperidinium methosulfate (R 1 = R 2 = -CH 2 CH 2 CH 3 in formula VII)
- N,N-Dipropyl-4-oxo-piperidinium-Methosulfat (R1 = R2 = -CH2CH2CH3 in Formel VIII)N, N-dipropyl-4-oxopiperidinium methosulfate (R 1 = R 2 = -CH 2 CH 2 CH 3 in formula VIII)
- N,N-Dipropyl-3-oxo-piperidinium-Tosylat (R1 = R2 = -CH2CH2CH3 in Formel VII)N, N-dipropyl-3-oxopiperidinium tosylate (R 1 = R 2 = -CH 2 CH 2 CH 3 in formula VII)
- N,N-Dipropyl-4-oxo-piperidinium-Tosylat (R1 = R2 = -CH2CH2CH3 in Formel VIII)N, N-dipropyl-4-oxopiperidinium tosylate (R 1 = R 2 = -CH 2 CH 2 CH 3 in formula VIII)
- N.N-Diisopropyl-S-oxo-piperidinium-Chlorid (R1 = R2 = -CH(CH3)2 in Formel VII)N, N-diisopropyl-S-oxopiperidinium chloride (R 1 = R 2 = -CH (CH 3 ) 2 in formula VII)
- N,N-Diisopropyl-4-oxo-piperidinium-Chlorid (R1 = R2 = -CH(CH3)2 in Formel VIII)N, N-diisopropyl-4-oxopiperidinium chloride (R 1 = R 2 = -CH (CH 3 ) 2 in formula VIII)
- N,N-Diisopropyl-3-oxo-piperidinium-Bromid (R1 = R2 = -CH(CH3)2 in Formel VII)N, N-diisopropyl-3-oxopiperidinium bromide (R 1 = R 2 = -CH (CH 3 ) 2 in formula VII)
- N,N-Diisopropyl-4-oxo-piperidinium-Bromid (R1 = R2 = -CH(CH3)2 in Formel VIII)N, N-diisopropyl-4-oxopiperidinium bromide (R 1 = R 2 = -CH (CH 3 ) 2 in formula VIII)
- N,N-Diisopropyl-3-oxo-piperidinium-Methosulfat (R1 = R2 = -CH(CH3)2 in Formel VII)N, N-diisopropyl-3-oxopiperidinium methosulfate (R 1 = R 2 = -CH (CH 3 ) 2 in formula VII)
- N,N-Diisopropyl-4-oxo-piperidinium-Methosulfat (R1 = R2 = -CH(CH3)2 in Formel VIII)N, N-diisopropyl-4-oxopiperidinium methosulfate (R 1 = R 2 = -CH (CH 3 ) 2 in formula VIII)
- N,N-Diisopropyl-3-oxo-piperidinium-Tosylat (R1 = R2 = -CH(CH3)2 in Formel VII)N, N-diisopropyl-3-oxopiperidinium tosylate (R 1 = R 2 = -CH (CH 3 ) 2 in formula VII)
- N,N-Diisopropyl-4-oxo-piperidinium-Tosylat (R1 = R2 = -CH(CH3)2 in Formel VIII)N, N-diisopropyl-4-oxopiperidinium tosylate (R 1 = R 2 = -CH (CH 3 ) 2 in formula VIII)
- N,N-Dibutyl-3-oxo-piperidinium-Chlorid (R1 = R2 = -(CH2)3CH3 in Formel VII)N, N-dibutyl-3-oxopiperidinium chloride (R 1 = R 2 = - (CH 2 ) 3 CH 3 in formula VII)
- N,N-Dibutyl-4-oxo-piperidinium-Chlorid (R1 = R2 = -(CH2)3CH3 in Formel VIII)N, N-dibutyl-4-oxopiperidinium chloride (R 1 = R 2 = - (CH 2 ) 3 CH 3 in formula VIII)
- N,N-Dibutyl-3-oxo-piperidinium-Bromid (R1 = R2 = -(CH2)3CH3 in Formel VII)N, N-dibutyl-3-oxopiperidinium bromide (R 1 = R 2 = - (CH 2 ) 3 CH 3 in formula VII)
- N,N-Dibutyl-4-oxo-piperidinium-Bromid (R1 = R2 = -(CH2)3CH3 in Formel VIII)N, N-dibutyl-4-oxopiperidinium bromide (R 1 = R 2 = - (CH 2 ) 3 CH 3 in formula VIII)
- N,N-Dibutyl-3-oxo-piperidinium-Methosulfat (R1 = R2 = -(CH2)3CH3 in Formel VII) - N,N-Dibutyl-4-oxo-piperidinium-Methosulfat (R1 = R2 = -(CH2)SCH3 in Formel VIII)N, N-dibutyl-3-oxopiperidinium methosulfate (R 1 = R 2 = - (CH 2 ) 3 CH 3 in formula VII) N, N-dibutyl-4-oxopiperidinium methosulfate (R 1 = R 2 = - (CH 2 ) S CH 3 in formula VIII)
- N,N-Dibutyl-3-oxo-piperidinium-Tosylat (R1 = R2 = -(CH2)3CH3 in Formel VII)N, N-dibutyl-3-oxopiperidinium tosylate (R 1 = R 2 = - (CH 2 ) 3 CH 3 in formula VII)
- N,N-Dibutyl-4-oxo-piperidinium-Tosylat (R1 = R2 = -(CH2)3CH3 in Formel VIII)N, N-dibutyl-4-oxopiperidinium tosylate (R 1 = R 2 = - (CH 2 ) 3 CH 3 in formula VIII)
- N,N-Diisobutyl-3-oxo-piperidinium-Chlorid (R1 = -CH2CH (CH3)2, R2 = H in Formel VII)N, N-diisobutyl-3-oxopiperidinium chloride (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N,N-Diisobutyl-4-oxo-piperidinium-Chlorid (R1 = -CH2CH (CH3)2, R2 = H in Formel VIII)N, N-diisobutyl-4-oxopiperidinium chloride (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N,N-Diisobutyl-3-oxo-piperidinium-Bromid (R1 = -CH2CH (CH3)2, R2 = H in Formel VII)N, N-diisobutyl-3-oxopiperidinium bromide (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N,N-Diisobutyl-4-oxo-piperidinium-Bromid (R1 = -CH2CH (CH3)2, R2 = H in Formel VIII)N, N-diisobutyl-4-oxopiperidinium bromide (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N,N-Diisobutyl-3-oxo-piperidinium-Methosulfat (R1 = -CH2CH (CH3)2, R2 = H in Formel VII)N, N-diisobutyl-3-oxopiperidinium methosulfate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N,N-Diisobutyl-4-oxo-piperidinium-Methosulfat (R1 = -CH2CH (CH3)2, R2 = H in Formel VIII)N, N-diisobutyl-4-oxopiperidinium methosulfate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N,N-Diisobutyl-3-oxo-piperidinium-Tosylat (R1 = -CH2CH (CH3)2, R2 = H in Formel VII)N, N-diisobutyl-3-oxopiperidinium tosylate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VII)
- N,N-Diisobutyl-4-oxo-piperidinium-Tosylat (R1 = -CH2CH (CH3)2, R2 = H in Formel VIII)N, N-diisobutyl-4-oxopiperidinium tosylate (R 1 = -CH 2 CH (CH 3 ) 2 , R 2 = H in formula VIII)
- N,N-Di(sec-Butyl)-3-oxo-piperidinium-Chlorid (R1 = R2 = -CH2CH(CH3)2 in Formel VII)N, N-di (sec-butyl) -3-oxopiperidinium chloride (R 1 = R 2 = -CH 2 CH (CH 3 ) 2 in formula VII)
- N,N-Di(sec-Butyl)-4-oxo-piperidinium-Chlorid (R1 = R2 = -CH2CH(CH3)2 in Formel VIII)N, N-di (sec-butyl) -4-oxopiperidinium chloride (R 1 = R 2 = -CH 2 CH (CH 3 ) 2 in formula VIII)
- N,N-Di(sec-Butyl)-3-oxo-piperidinium-Bromid (R1 = R2 = -CH2CH(CH3)2 in Formel VII)N, N-di (sec-butyl) -3-oxopiperidinium bromide (R 1 = R 2 = -CH 2 CH (CH 3 ) 2 in formula VII)
- N,N-Di(sec-Butyl)-4-oxo-piperidinium-Bromid (R1 = R2 = -CH2CH(CH3)2 in Formel VIII))N, N-di (sec-butyl) -4-oxopiperidinium bromide (R 1 = R 2 = -CH 2 CH (CH 3 ) 2 in formula VIII))
- N,N-Di(sec-Butyl)-3-oxo-piperidinium-Methosulfat (R1 = R2 = -CH2CH(CH3)2 in Formel VII)N, N-di (sec-butyl) -3-oxopiperidinium methosulfate (R 1 = R 2 = -CH 2 CH (CH 3 ) 2 in formula VII)
- N,N-Di(sec-Butyl)-4-oxo-piperidinium-Methosulfat (R1 = R2 = -CH2CH(CH3)2 in Formel VIII)N, N-di (sec-butyl) -4-oxopiperidinium methosulfate (R 1 = R 2 = -CH 2 CH (CH 3 ) 2 in formula VIII)
- N,N-Di(sec-Butyl)-3-oxo-piperidinium-Tosylat (R1 = R2 = -CH2CH(CH3)2 in Formel VII))N, N-di (sec-butyl) -3-oxopiperidinium tosylate (R 1 = R 2 = -CH 2 CH (CH 3 ) 2 in formula VII))
- N,N-Di(sec-Butyl)-4-oxo-piperidinium-Tosylat (R1 = R2 = -CH2CH(CH3)2 in Formel VIII)N, N-di (sec-butyl) -4-oxopiperidinium tosylate (R 1 = R 2 = -CH 2 CH (CH 3 ) 2 in formula VIII)
- N,N-3,5-Tetramethyl-4-oxo-piperidinium-lodid (R1 = R2 = R3 = R4 = -CH3 in Formel VIII)N, N-3,5-tetramethyl-4-oxopiperidinium iodide (R 1 = R 2 = R 3 = R 4 = -CH 3 in formula VIII)
- N,N-2,6-Tetramethyl-4-oxo-piperidinium-lodid (R1 = R2 = R5 = R6 = -CH3 in Formel VIII)N, N-2,6-tetramethyl-4-oxopiperidinium iodide (R 1 = R 2 = R 5 = R 6 = -CH 3 in formula VIII)
Als zusätzliches Alkalisierungsmittel können die erfindungsgemäßen Mittel mindestens eine Verbindung aus Aminosäuren und/oder Oligopeptiden enthalten, wobei diese jeweils mindestens zwei Aminogruppen und mindestens eine -COOH- oder -SO H-Gruppe aufweisen und deren 2,5-%igeAs an additional alkalizing agent, the compositions according to the invention may comprise at least one compound of amino acids and / or oligopeptides, these each having at least two amino groups and at least one -COOH or -SO H group and their 2.5% strength
Lösung in Wasser jeweils einen pH-Wert von größer 9,0 aufweist.Solution in water in each case has a pH greater than 9.0.
Bevorzugte Alkalisierungsmittel sind Aminocarbonsäuren, insbesondere α-Aminocarbonsäuren und omega-Aminocarbonsäuren. Unter den α-Aminocarbonsäuren sind wiederum Lysin und insbesondere Arginin besonders bevorzugt.Preferred alkalizing agents are aminocarboxylic acids, in particular α-aminocarboxylic acids and omega-aminocarboxylic acids. Among the α-aminocarboxylic acids lysine and especially arginine are again particularly preferred.
Besagte Aminosäuren können den erfindungsgemäßen Mitteln bevorzugt in freier Form zugegeben werden. In einer Reihe von Fällen ist es jedoch auch möglich, die Aminosäuren in Salzform einzusetzen. Bevorzugte Salze sind dann die Verbindungen mit Halogenwasserstoffsäuren, insbesondere die Hydrochloride und die Hydrobromide. Weiterhin können die Aminosäuren auch in Form von Oligopeptiden und Proteinhydrolysaten eingesetzt werden, wenn sichergestellt ist, dass die erforderlichen Mengen der erfindungsgemäß eingesetzten Aminosäuren darin enthalten sind.Said amino acids can preferably be added to the agents according to the invention in free form. In a number of cases, however, it is also possible to use the amino acids in salt form. Preferred salts are then the compounds with hydrohalic acids, in particular the hydrochlorides and hydrobromides. Furthermore, the amino acids can also be used in the form of oligopeptides and protein hydrolysates, if it is ensured that the required amounts of the amino acids used according to the invention are contained therein.
Ein besonders bevorzugtes Alkalisierungsmittel ist Arginin.A particularly preferred alkalizing agent is arginine.
Erfindungsgemäß bevorzugte Mittel sind dadurch gekennzeichnet, dass sie zusätzlich - 0,05 bis 5 Gew.-%, vorzugsweise 0,1 bis 2,5 Gew.-%, besonders bevorzugt 0,15 bis 1 Gew.-% und insbesondere 0,2 bis 0,5 Gew.-% Aminosäure(n), vorzugsweise (eine) Aminosäure(n) aus der Gruppe Glycin und/oder Alanin und/oder Valin und/oder Lysin und/oder Leucin und/oder Threonin und/oder Serin enthalten.Agents preferred according to the invention are characterized in that they additionally contain from 0.05 to 5% by weight, preferably from 0.1 to 2.5% by weight, particularly preferably from 0.15 to 1% by weight and in particular 0.2 to 0.5 wt .-% amino acid (s), preferably (one) amino acid (s) from the group glycine and / or alanine and / or valine and / or lysine and / or leucine and / or threonine and / or serine ,
Wie bereits erwähnt, können erfindungsgemäße Mittel auch direkt vor der Anwendung aus zwei oder mehreren getrennt verpackten Zubereitungen hergestellt werden. Dies bietet sich insbesondere zur Trennung inkompatibler Inhaltsstoffe an, um eine vorzeitige Reaktion zu vermeiden.As already mentioned, agents according to the invention can also be prepared directly before use from two or more separately packaged preparations. This is particularly useful for the separation of incompatible ingredients to avoid premature reaction.
Ein üblicher Weg besteht daher darin, ein erfindungsgemäßes Mittel A direkt vor der Anwendung mit einer Oxidationsmittelzubereitung B zu einer Anwendungsmischung zu vermischen.A common way is therefore to mix an agent A according to the invention with an oxidizing agent preparation B directly before use to form an application mixture.
Ein weiterer Gegenstand der vorliegenden Erfindung ist daher ein Mittel zum Färben und/oder Aufhellen keratinischer Fasern, insbesondere menschlicher Haare, welches unmittelbar vor dem Aufbringen auf das Haar aus einer fließfähigen Zubereitung A, einer Oxidationsmittelzubereitung B, enthaltend mindestens ein Oxidationsmittel, ausgewählt aus Wasserstoffperoxid und dessen Anlagerungsverbindungen an feste Träger und einer Zubereitung C, die miteinander zu einem Färbe- und/oder Aufhellansatz vermischt werden, erhalten wird, wobei die Zusammensetzung A und/oder C eine erfindungsgemäße Zusammensetzung ist.Another object of the present invention is therefore an agent for dyeing and / or whitening keratinic fibers, in particular human hair, which immediately before application to the hair from a flowable preparation A, an oxidizing agent preparation B containing at least one oxidizing agent selected from hydrogen peroxide and whose addition compounds to solid carriers and a preparation C, which are mixed together to a dyeing and / or Aufhellansatz, is obtained, wherein the composition A and / or C is a composition according to the invention.
Eine Oxidationsmittelzubereitung B enthält mindestens ein Oxidationsmittel, ausgewählt aus Wasserstoffperoxid und dessen Anlagerungsverbindungen an feste Träger. Als erfindungsgemäßes Oxidationsmittel wird bevorzugt Wasserstoffperoxid selbst verwendet. Das Wasserstoffperoxid wird als Lösung oder in Form einer festen Anlagerungsverbindung von Wasserstoffperoxid an anorganische oder organische Verbindungen, wie beispielsweise Natriumperborat, Natriumpercarbonat, Magnesiumpercarbonat, Natriumpercarbamid, Polyvinylpyrrolidon n H2O2 (n ist eine positive ganze Zahl größer 0), Harnstoffperoxid und Melaminperoxid, eingesetzt. Erfindungsgemäß ganz besonders bevorzugt sind wässrige Wasserstoffperoxid-Lösungen. Die Konzentration einer Wasserstoffperoxid-Lösung wird einerseits von den gesetzlichen Vorgaben und andererseits von dem gewünschten Effekt bestimmt; vorzugsweise werden 6- bis 12-prozentige Lösungen in Wasser verwendet. Erfindungsgemäß bevorzugte Mittel zum Färben und/oder Aufhellen keratinischer Fasern sind dadurch gekennzeichnet, daß die Oxidationsmittelzubereitung B - bezogen auf ihr Gewicht - 0,5 bis 10 Gew.-%, vorzugsweise 0,75 bis 9,0 Gew.-%, besonders bevorzugt 1 bis 8,0 Gew.-%, weiter bevorzugt 1 ,25 bis 7,0 Gew.-% und insbesondere 1 ,5 bis 6,0 Gew.-% Wasserstoffperoxid (berechnet als 100 %iges H2O2) enthält.An oxidizer formulation B contains at least one oxidizer selected from hydrogen peroxide and its attachment compounds to solid supports. As the oxidant of the present invention, hydrogen peroxide itself is preferably used. The hydrogen peroxide is used as a solution or in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H 2 O 2 (n is a positive integer greater than 0), urea peroxide and melamine peroxide, used. Very particularly preferred according to the invention are aqueous hydrogen peroxide solutions. The concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6-12% solutions in water are used. According to preferred means for dyeing and / or lightening keratinischer fibers are characterized in that the oxidizing agent preparation B - based on their weight - 0.5 to 10 wt .-%, preferably 0.75 to 9.0 wt .-%, particularly preferably 1 to 8.0 wt .-%, more preferably 1, 25 to 7.0 wt .-% and in particular 1, 5 to 6.0 wt .-% hydrogen peroxide (calculated as 100% H 2 O 2 ) contains.
Die Oxidationsmittelzubereitung B ist vorzugsweise eine wäßrige, fließfähige Oxidationsmittelzubereitung. Demnach sind bevorzugte erfindungsgemäße Mittel zum Färben und/oder Aufhellen keratinischer Fasern dadurch gekennzeichnet, dass die fließfähige Oxidationsmittelzubereitung B - bezogen auf ihr Gewicht - 40 bis 90 Gew.-%, vorzugsweise 50 bis 85 Gew.-%, besonders bevorzugt 55 bis 80 Gew.-%, weiter bevorzugt 60 bis 77,5 Gew.-% und insbesondere 65 bis 75 Gew.-% Wasser enthält.The oxidizer formulation B is preferably an aqueous, flowable oxidizer formulation. Accordingly, preferred agents for dyeing and / or lightening keratinic fibers according to the invention are characterized in that the flowable oxidizing agent preparation B - based on its weight - 40 to 90 wt .-%, preferably 50 to 85 wt .-%, particularly preferably 55 to 80 wt .-%, more preferably 60 to 77.5 wt .-% and in particular 65 to 75 wt .-% water.
Bezogen auf die Anwendungsmischung sind erfindungsgemäße Mittel zum Färben und/oder Aufhellen keratinischer Fasern bevorzugt, die 0,5 bis 15 Gew.-%, vorzugsweise 1 bis 12,5 Gew.-%, besonders bevorzugt 2,5 bis 10 Gew.-% und insbesondere 3 bis 6 Gew.-% Wasserstoffperoxid (berechnet als 100%iges H2O2) enthalten.Based on the application mixture, agents according to the invention for dyeing and / or lightening keratinic fibers are preferred, which contain 0.5 to 15% by weight, preferably 1 to 12.5% by weight, particularly preferably 2.5 to 10% by weight. and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H 2 O 2 ) included.
Vorzugsweise wird der fließfähigen Oxidationsmittelzubereitung B ein Emulgator bzw. ein Tensid zugesetzt, wobei oberflächenaktive Substanzen je nach Anwendungsgebiet als Tenside oder als Emulgatoren bezeichnet werden und aus anionischen, kationischen, zwitterionischen, ampholytischen und nichtionischen Tensiden und Emulgatoren ausgewählt sind. Diese Stoffe werden weiter unten ausführlich beschrieben.Preferably, an emulsifier or a surfactant is added to the flowable oxidizing agent preparation B, surfactants depending on the field of use being referred to as surfactants or as emulsifiers and being selected from anionic, cationic, zwitterionic, ampholytic and nonionic surfactants and emulsifiers. These substances are described in detail below.
Die Oxidationsmittelzubereitung kann weitere Oxidationsmittel enthalten, die auch als „Booster" bezeichnet werden. Die Auswahl dieser weiteren Peroxoverbindung unterliegt prinzipiell keinen Beschränkungen; übliche, dem Fachmann bekannte Peroxoverbindungen sind beispielsweise Ammoniumperoxidisulfat, Kaliumperoxidisulfat, Natriumperoxidisulfat, Ammoniumpersulfat, Kaliumpersulfat, Natriumpersulfat, Percarbonate wie Magnesiumpercarbonat, Peroxide wie Bariumperoxid sowie Perborate, Harnstoffperoxid und Melaminperoxid. Unter diesen Peroxoverbindungen, die auch in Kombination eingesetzt werden können, sind erfindungsgemäß die anorganischen Verbindungen bevorzugt. Besonders bevorzugt sind die Peroxidisulfate, insbesondere Kombinationen aus mindestens zwei Peroxidisulfaten. Hier sind erfindungsgemäße Mittel zum Färben und/oder Aufhellen keratinischer Fasern bevorzugt, die zusätzlich 0,01 bis 2 Gew.-% mindestens einer festen Peroxoverbindung, die ausgewählt ist aus Ammonium-, Alkalimetall- und Erdalkalimetallpersulfaten, -peroxomonosulfaten und -peroxidisulfaten enthalten, wobei bevorzugte Mittel Peroxidisulfate enthalten, die vorzugsweise ausgewählt sind aus Natriumperoxidisulfat und/oder Kaliumperoxidisulfat und/oder Ammoniumperoxidisulfat und wobei besonders bevorzugte Mittel mindestens zwei verschiedene Peroxid islfate enthalten.The choice of this further peroxo compound is subject in principle to no restrictions, and conventional peroxo compounds known to the person skilled in the art are, for example, ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, ammonium persulfate, potassium persulfate, sodium persulfate, percarbonates, such as magnesium percarbonate. Peroxides such as barium peroxide and also perborates, urea peroxide and melamine peroxide are among these peroxo compounds which can also be used in combination.Partoxysulfates are particularly preferred according to the invention, in particular combinations of at least two peroxydisulfates and / or lightening keratinic fibers which additionally contain from 0.01 to 2% by weight of at least one solid peroxy compound selected from ammonium, alkali metal and alkaline earth metal persulfates, peroxomonosulfates and peroxydisulfates, preferred agents containing peroxydisulfates are preferably selected from sodium peroxydisulfate and / or potassium peroxydisulfate and / or ammonium peroxydisulfate and particularly preferred agents containing at least two different peroxide islfate.
Weiterhin besonders bevorzugt sind Persulfate, insbesondere das als Carosche Salz bezeichnete Gemisch aus Kaliumperoxosulfat, Kaliumhydrogensulfat und Kaliumsulfat.Particular preference is furthermore given to persulfates, in particular the mixture of potassium peroxosulfate, potassium hydrogen sulfate and potassium sulfate, referred to as Caro's salt.
Da die „Booster" hydrolytisch leicht zersetzt werden, ist es bevorzugt, diese der Oxidationsmittelzubereitung bzw. der Anwendungsmischung erst unmittelbar vor der Anwendung zuzugeben.Since the "boosters" are easily decomposed hydrolytically, it is preferred to add them to the oxidizing agent preparation or the application mixture only immediately before use.
Die erfindungsgemäßen wasserfreien Zusammensetzungen können zusätzlich mindestens einen weiteren Bleichverstärker, der von den anorganischen Persalzen verschieden ist, enthalten.The anhydrous compositions of the present invention may additionally contain at least one other bleaching enhancer other than the inorganic persalts.
Als Bleichverstärker können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1 ,5-Diacetyl- 2,4-dioxohexahydro-1 ,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran.As bleach amplifiers, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
Zur weiteren Steigerung der Aufhellleistung können erfindungsgemäße wasserfreie Mittel zusätzlich als Bleichverstärker mindestens eine gegebenenfalls hydratisierte SiO2-Verbindung enthalten. Obwohl bereits geringe Mengen der gegebenenfalls hydratisierten SiO2-Verbindungen die Aufhellleistung erhöhen, kann es erfindungsgemäß bevorzugt sein, die gegebenenfalls hydratisierten SiO2-Verbindungen in Mengen von 0,05 Gew.-% bis 15 Gew.-%, besonders bevorzugt in Mengen von 0,15 Gew.-% bis 10 Gew.-% und ganz besonders bevorzugt in Mengen von 0,2 Gew.-% bis 5 Gew.- %, jeweils bezogen auf die erfindungsgemäße wasserfreie Zusammensetzung, einzusetzen. Die Mengenangaben geben dabei jeweils den Gehalt der SiO2-Verbindungen (ohne deren Wasseranteil) in den Mitteln wieder.In order to further increase the lightening power, anhydrous compositions according to the invention may additionally contain as bleaching boosters at least one optionally hydrated SiO 2 compound. Although even small amounts of the optionally hydrated SiO 2 compounds increase the lightening power, it may be preferred according to the invention, the optionally hydrated SiO 2 compounds in amounts of 0.05 wt .-% to 15 wt .-%, particularly preferably in amounts of 0.15% by weight to 10% by weight and very particularly preferably in amounts of from 0.2% by weight to 5% by weight, based in each case on the anhydrous composition according to the invention. The amounts given in each case the content of the SiO 2 compounds (without their water content) in the funds again.
Hinsichtlich der gegebenenfalls hydratisierten SiO2-Verbindungen unterliegt die vorliegende Erfindung prinzipiell keinen Beschränkungen. Bevorzugt sind Kieselsäuren, deren Oligomeren und Polymeren sowie deren Salze. Bevorzugte Salze sind die Alkalisalze, insbesondere die Kalium und Natriumsalze. Die Natriumsalze sind ganz besonders bevorzugt.With regard to the optionally hydrated SiO 2 compounds, the present invention is in principle subject to no restrictions. Preference is given to silicic acids, their oligomers and polymers and their salts. Preferred salts are the alkali salts, especially the potassium and sodium salts. The sodium salts are very particularly preferred.
Die gegebenenfalls hydratisierten SiO2-Verbindungen können in verschiedenen Formen vorliegen. Erfindungsgemäß bevorzugt werden die SiO2-Verbindungen in Form von Kieselgelen (Silicagel) oder besonders bevorzugt als Wasserglas eingesetzt. Diese SiO2-Verbindungen können teilweise in wäßriger Lösung vorliegen.The optionally hydrated SiO 2 compounds can be present in various forms. According to the invention, the SiO 2 compounds are preferably used in the form of silica gels (silica gel) or particularly preferably as water glass. These SiO 2 compounds may be partially present in aqueous solution.
Erfindungsgemäß ganz besonders bevorzugt sind Wassergläser, die aus einem Silikat der Formel (SiO2)n(Na2O)m(K2O)p gebildet werden, wobei n steht für eine positive rationale Zahl und m und p stehen unabhängig voneinander für eine positive rationale Zahl oder für 0, mit den Maßgaben, daß mindestens einer der Parameter m oder p von 0 verschieden ist und das Verhältnis zwischen n und der Summe aus m und p zwischen 1 :4 und 4:1 liegt.Very particularly preferred according to the invention are water glasses which are formed from a silicate of the formula (SiO 2 ) n (Na 2 O) m (K 2 O) p , where n is a positive rational number and m and p are each independently one positive rational number or 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1.
Neben den durch die Summenformel beschriebenen Komponenten können die Wassergläser in geringen Mengen noch weitere Zusatzstoffe, wie beispielsweise Phosphate oder Magnesiumsalze, enthalten.In addition to the components described by the empirical formula, the water glasses in small amounts may contain other additives, such as phosphates or magnesium salts.
Erfindungsgemäß besonders bevorzugte Wassergläser werden unter anderem von der Firma Henkel unter den Bezeichnungen Ferrosil® 119, Natronwasserglas 40/42, Portil® A, Portil® AW und Portil® W und von der Firma Akzo unter der Bezeichnung Britesil® C20 vertrieben.According to the invention particularly preferred water glasses are sold among others by Henkel under the names Ferrosil® ® 119, soda water glass 40/42, Portil ® A, Portil ® AW and Portil ® W and by Akzo under the name Britesil® ® C20.
Erfindungsgemäß bevorzugte Mittel sind dadurch gekennzeichnet, dass sie zusätzlich 0,05 bis 15 Gew.-%, besonders bevorzugt 0,15 bis 10 Gew.-% und insbesondere 0,2 bis 5 Gew.-% mindestens einer gegebenenfalls hydratisierte SiO2-Verbindung enthalten, wobei bevorzugte Mittel Wassergläser enthalten, die aus einem Silikat der Formel (SiO2)n(Na2O)m(K2O)p gebildet werden, worin n steht für eine positive rationale Zahl und m und p unabhängig voneinander für eine positive rationale Zahl oder für 0 stehen, mit den Maßgaben, dass mindestens einer der Parameter m oder p von 0 verschieden ist und das Verhältnis zwischen n und der Summe aus m und p zwischen 1 :4 und 4:1 liegt. Weiterhin hat es sich als vorteilhaft erwiesen, wenn die erfindungsgemäßen Färbe- und/oder Aufhellmittel nichtionogene grenzflächenaktive Stoffe enthalten. Dabei sind solche grenzflächenaktive Stoffe, die einen HLB-Wert von 5,0 und größer aufweisen, bevorzugt. Für die Definition des HLB- Wertes wird ausdrücklich auf die Ausführungen in Hugo Janistyn, Handbuch der Kosmetika und Riechstoffe, III. Band: Die Körperpflegemittel, 2. Auflage, Dr. Alfred Hüthig Verlag Heidelberg, 1973, Seiten 68-78 und Hugo Janistyn, Taschenbuch der modernen Parfümerie und Kosmetik, 4. Auflage, Wissenschaftliche Verlagsgesellschaft m.b.H. Stuttgart, 1974, Seiten 466-474, sowie die darin zitierten Originalarbeiten Bezug genommen.Agents preferred according to the invention are characterized in that they additionally contain 0.05 to 15% by weight, particularly preferably 0.15 to 10% by weight and in particular 0.2 to 5% by weight of at least one optionally hydrated SiO 2 compound Preferred agents include water glasses formed from a silicate of the formula (SiO 2 ) n (Na 2 O) m (K 2 O) p , where n is a positive rational number and m and p are independently one positive rational number or 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1. Furthermore, it has proved to be advantageous if the dyeing and / or brightening agents according to the invention contain nonionic surfactants. Such surfactants having an HLB of 5.0 and greater are preferred. For the definition of the HLB value, reference is explicitly made to the statements in Hugo Janistyn, Handbuch der Kosmetika und Riechstoffe, III. Volume: The personal care products, 2nd edition, Dr. med. Alfred Hüthig Verlag Heidelberg, 1973, pages 68-78 and Hugo Janistyn, Paperback of modern perfumery and cosmetics, 4th edition, Scientific Verlagsgesellschaft mbH Stuttgart, 1974, pages 466-474, as well as the original works cited therein reference.
Besonders bevorzugte nichtionogene oberflächenaktive Substanzen sind dabei wegen der einfachen Verarbeitbarkeit Substanzen, die kommerziell als Feststoffe oder Flüssigkeiten in reiner Form erhältlich sind. Die Definition für Reinheit bezieht sich in diesem Zusammenhang nicht auf chemisch reine Verbindungen. Vielmehr können, insbesondere wenn es sich um Produkte auf natürlicher Basis handelt, Mischungen verschiedener Homologen eingesetzt werden, beispielsweise mit verschiedenen Alkylkettenlängen, wie sie bei Produkten auf Basis natürlicher Fette und Öle erhalten werden. Auch bei alkoxylierten Produkten liegen üblicherweise Mischungen unterschiedlicher Alkoxylierungsgrade vor. Der Begriff Reinheit bezieht sich in diesem Zusammenhang vielmehr auf die Tatsache, dass die gewählten Substanzen bevorzugt frei von Lösungsmitteln, Stellmitteln und anderen Begleitstoffen sein sollen.Particularly preferred non-ionic surface-active substances are substances that are commercially available as solids or liquids in pure form because of their ease of processing. The definition of purity in this context does not refer to chemically pure compounds. Rather, especially when it comes to natural-based products, mixtures of different homologs can be used, for example, with different alkyl chain lengths, such as those obtained with products based on natural fats and oils. Even with alkoxylated products, mixtures of different degrees of alkoxylation are usually present. The term purity in this context refers rather to the fact that the selected substances should preferably be free from solvents, adjuvants and other impurities.
Bevorzugte nichtionogene grenzflächenaktive Stoffe sindPreferred nonionic surfactants are
- alkoxylierte Fettalkohole mit 8 bis 22, insbesondere 10 bis 16, Kohlenstoffatomen in der Fettalkylgruppe und 1 bis 30, insbesondere 1 bis 15, Ethylenoxid- und/oder- alkoxylated fatty alcohols having 8 to 22, in particular 10 to 16, carbon atoms in the fatty alkyl group and 1 to 30, in particular 1 to 15, ethylene oxide and / or
Propylenoxid-Einheiten. Bevorzugte Fettalkylgruppen sind beispielsweise Lauryl-, Myristyl-, Cetyl-, aber auch Stearyl-, Isostearyl- und Oleylgruppen. Besonders bevorzugte Verbindungen dieser Klasse sind beispielsweise Laurylalkohol mit 2 bis 4 Ethylenoxid-Einheiten, Oleyl- und Cetylalkohol mit jeweils 5 bis 10 Ethylenoxideinheiten, Cetyl- und Stearylalkohol sowie deren Mischungen mit 10 bis 30 Ethylenoxideinheiten sowie das Handelsprodukt Aethoxal®B (Henkel), ein Laurylalkohol mit jeweils 5 Ethylenoxid- und Propylenoxideinheiten. Neben den üblichen alkoxylierten Fettalkoholen können auch sogenannte „endgruppenverschlossene" Verbindungen erfindungsgemäß eingesetzt werden. Bei diesen Verbindungen weist die Alkoxygruppe am Ende keine OH-Gruppe auf, sondern ist in Form eines Ethers, insbesondere eines C1-C4-Alkyl-Ethers, „verschlossen". Ein Beispiel für eine solche Verbindung ist das Handelsprodukt Dehypon®LT 054, ein Ci2-18-Fettalkoholol + 4,5 Ethylenoxid-butylether. - alkoxylierte Fettsäuren mit 8 bis 22, insbesondere 10 bis 16, Kohlenstoffatomen in der Fettsäuregruppe und 1 bis 30, insbesondere 1 bis 15, Ethylenoxid- und/oder Propylenoxid- Einheiten. Bevorzugte Fettsäuren sind beispielsweise Laurin-, Myristin-, Palmitin-, Stearin-, Isostearin- und Ölsäure.Propylene oxide units. Preferred fatty alkyl groups are, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl groups. Particularly preferred compounds of this class are, for example, lauryl alcohol with 2 to 4 ethylene oxide units, oleyl and cetyl alcohol with 5 to 10 ethylene oxide, cetyl alcohol and stearyl alcohol and mixtures thereof with 10 to 30 ethylene oxide units and the commercial product Aethoxal ® B (Henkel), Lauryl alcohol with 5 ethylene oxide and 3 propylene oxide units. In addition to the usual alkoxylated fatty alcohols, it is also possible to use so-called "end-capped" compounds according to the invention In these compounds, the alkoxy group has no OH group at the end but is "closed" in the form of an ether, in particular a C 1 -C 4 -alkyl ether. , An example of such a compound is the commercially available product ® Dehypon LT 054, a C 2-18 -Fettalkoholol + 4.5 ethylene oxide-butyl ether. - alkoxylated fatty acids having 8 to 22, in particular 10 to 16, carbon atoms in the fatty acid group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty acids are, for example, lauric, myristic, palmitic, stearic, isostearic and oleic acids.
- alkoxylierte, bevorzugt propoxylierte und insbesondere ethoxylierte, Mono-, Di- und Triglyceride. Beispiele für bevorzugte Verbindungen sind Glycerinmonolaurat + 20 Ethylenoxid und Glycerinmonostearat + 20 Ethylenoxid.- alkoxylated, preferably propoxylated and especially ethoxylated, mono-, di- and triglycerides. Examples of preferred compounds are glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide.
- Polyglycerinester und alkoxylierte Polyglycerinester. Bevorzugte Verbindungen dieser Klasse sind beispielsweise Poly(3)glycerindiisostearat (Handelsprodukt: Lamefornn®TGI (Henkel)) und Poly(2)glycerinpolyhydroxy-stearat (Handelsprodukt:- Dehymuls®PGPH (Henkel)).Polyglycerol esters and alkoxylated polyglycerol esters. Preferred compounds of this class are for example poly (3) glycerol diisostearate (commercial product: Lamefornn ® TGI (Henkel)) and poly (2) glycerinpolyhydroxy stearate (commercial product: - Dehymuls ® PGPH (Henkel)).
- Sorbitan-Fettsäureester und alkoxylierte Sorbitan- Fettsäureester wie beispielsweise Sorbitanmonolaurat und Sorbitanmonolaurat + 20 Ethylenoxid (EO).Sorbitan fatty acid esters and alkoxylated sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monolaurate + 20 ethylene oxide (EO).
- Alkylphenole und Alkylphenolalkoxylate mit 6 bis 21 , insbesondere 6 bis 15, Kohlenstoffatomen in der Alkylkette und 0 bis 30 Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Vertreter dieser Klasse sind beispielsweise Nonylphenol + 4 EO, Nonylphenol + 9 EO, Octylphenol + 3 EO und Octylphenol + 8 EO.- Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15, carbon atoms in the alkyl chain and 0 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 4 EO, nonylphenol + 9 EO, octylphenol + 3 EO and octylphenol + 8 EO.
Besonders bevorzugte Klassen an nichtionogenen grenzflächenaktiven Stoffen stellen die alkoxylierten Fettalkohole, die alkoxylierten Fettsäuren sowie die Alkylphenole und Alkylphenolalkoxylate dar.Particularly preferred classes of nonionic surfactants are the alkoxylated fatty alcohols, the alkoxylated fatty acids and the alkylphenols and alkylphenol alkoxylates.
Als besonders vorteilhaft haben sich erfindungsgemäße Mittel erwiesen, die nichtionogene grenzflächenaktive Substanzen in Mengen von 1 - 5 Gew.-% enthalten.Agents according to the invention which contain non-ionic surface-active substances in amounts of 1 to 5% by weight have proved to be particularly advantageous.
Weiterhin können die erfindungsgemäßen Färbe- und/oder Aufhellmittel alle in solchen Zubereitungen bekannten Wirk-, Zusatz- und Hilfsstoffe enthalten. In vielen Fällen enthalten die Mittel mindestens ein Tensid, wobei prinzipiell sowohl anionische als auch zwitterionische, ampholytische, nichtionische und kationische Tenside geeignet sind. In vielen Fällen hat es sich aber als vorteilhaft erwiesen, die Tenside aus anionischen, kationischen oder nichtionischen Tensiden auszuwählen. Anionische Tenside können dabei ganz besonders bevorzugt sein. Bevorzugte anionische Tenside sind Alkylsulfate, Ethercarbonsäuresalze mit 10 bis 18 C-Atomen in der Alkylgruppe und bis zu 12 Glykolethergruppen im Molekül wie C12H25-(C2H4O)6-CH2-COONa sowie insbesondere Salze von gesättigten und speziell ungesättigten C8-C22-Carbonsäuren wie Ölsäure, Stearinsäure, Isostearinsäure und Palmitinsäure.Furthermore, the dyeing and / or brightening agents according to the invention may contain all known in such preparations active ingredients, additives and excipients. In many cases, the agents contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, cationic or nonionic surfactants. Anionic surfactants may be very particularly preferred. Preferred anionic surfactants are alkyl sulfates, ether carboxylic acid salts having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule such as C 12 H 25 - (C 2 H 4 O) 6 -CH 2 -COONa and in particular salts of saturated and especially unsaturated C8-C22 carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.
Diese anionischen Tenside sollten bevorzugt in fester, insbesondere Pulverform vorliegen. Ganz besonders bevorzugt sind dabei bei Raumtemperatur feste Seifen, insbesondere Natriumstearat. Diese liegen bevorzugt in Mengen von 5 bis 20 Gew.-%, insbesondere 10 bis 15 Gew.-.%, vor.These anionic surfactants should preferably be present in solid, in particular powder form. Very particular preference is given to solid soaps, especially sodium stearate, at room temperature. These are preferably present in amounts of from 5 to 20% by weight, in particular from 10 to 15% by weight.
Als nichtionische Tenside eignen sich insbesondere C8-C22-Alkylmono- und oligoglycoside und deren ethoxylierte Analoga. Insbesondere die nichtethoxylierten Verbindungen haben sich als besonders geeignet erwiesen.Suitable nonionic surfactants are in particular C 8 -C 22 -alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated compounds have been found to be particularly suitable.
Beispiele für die in den erfindungsgemäßen Haarbehandlungsmitteln verwendbaren kationischen Tenside sind insbesondere quartäre Ammoniumverbindungen. Bevorzugt sind Ammoniumhalogenide wie Alkyltrimethylammoniumchloride, Dialkyldimethylammoniumchloride undExamples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and
Trialkylmethylammoniumchloride, z. B. Cetyltrimethylammoniumchlorid, Stearyltrimethyl- ammoniumchlorid, Distearyldimethylammoniumchlorid, Lauryldimethylammoniumchlorid,Trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride,
Lauryldimethylbenzylammoniumchlorid und Tricetylmethylammoniumchlorid. Weitere erfindungsgemäß verwendbare kationische Tenside stellen die quaternisierten Proteinhydrolysate dar.Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.
Alkylamidoamine, insbesondere Fettsäureamidoamine wie das unter der Bezeichnung Tego Amid®S 18 erhältliche Stearylamidopropyldimethylamin, zeichnen sich neben einer guten konditionierenden Wirkung speziell durch ihre gute biologische Abbaubarkeit aus.Alkylamidoamines, in particular fatty acid amidoamines, such as the stearylamidopropyldimethylamine obtainable under the name Tego Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.
Ebenfalls sehr gut biologisch abbaubar sind quaternäre Esterverbindungen, sogenannte "Esterquats", wie das unter der Bezeichnung Dehyquart®F 75 in Abmischung mit Cetearylalkohle erhältliche Distearoylethylhydroxyethylammoniummethosulfat.Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as the Distearoylethylhydroxyethylammoniummethosulfat available in a blend with Cetearylalkohle under the name Dehyquart® ® F 75 miles.
Bei den als Tenside eingesetzten Verbindungen mit Alkylgruppen kann es sich jeweils um einheitliche Substanzen handeln. Es ist jedoch in der Regel bevorzugt, bei der Herstellung dieser Stoffe von nativen pflanzlichen oder tierischen Rohstoffen auszugehen, so dass man Substanzgemische mit unterschiedlichen, vom jeweiligen Rohstoff abhängigen Alkylkettenlängen erhält. Weitere Wirk-, Hilfs- und Zusatzstoffe sind beispielsweiseThe compounds containing alkyl groups used as surfactants may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained. Other active ingredients, auxiliaries and additives are, for example
nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere,nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers,
Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane, kationische Polymere wie quaternisierte Celluloseether und andere, als Feststoff stabile bzw. imPolyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers and others, stable as solid or im
Handel erhältliche Verbindungen, zwitterionische und amphotere Polymere, die als Feststoffe stabil bzw. bevorzugt alsCommercially available compounds, zwitterionic and amphoteric polymers which are stable or preferred as solids
Handelsprodukte erhältlich sind, anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren undCommercial products are available, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids and
Vinylacetat/Crotonsäure-Copolymere, sofern diese als Feststoffe stabil bzw. bevorzugt imVinyl acetate / crotonic acid copolymers, provided that they are stable as solids or preferably in
Handel erhältlich sind,Trade are available,
Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum,Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic,
Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B.Karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B.
Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen undMethylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and
Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetischeDerivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic
Hydrokolloide wie z.B. Polyvinylalkohol,Hydrocolloids such as e.g. polyvinyl alcohol,
Strukturanten wie Glucose, Maleinsäure und Milchsäure, haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline, sowie SilikonöleStructurants such as glucose, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example, soybean lecithin, egg lecithin and cephalins, and silicone oils
Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- undProtein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and
Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierteWheat protein hydrolysates, their condensation products with fatty acids and quaternized
Proteinhydrolysate,protein,
Parfümöle, Dimethylisosorbid und Cyclodextrine,Perfume oils, dimethylisosorbide and cyclodextrins,
Farbstoffe zum Einfärben der Zubereitungen,Dyes for coloring the preparations,
Wirkstoffe wie Panthenol, Pantothensäure, Allantoin, Pyrrolidoncarbonsäuren und derenActive ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their
Salze,salts
Cholesterin,Cholesterol,
Fette und Wachse wie Walrat, Bienenwachs, Montanwachs, Paraffine,Fats and waxes such as spermaceti, beeswax, montan wax, paraffins,
Fettalkohole und Fettsäureester,Fatty alcohols and fatty acid esters,
Fettsäurealkanolamide,fatty acid,
Komplexbildner wie EDTA, NTA und Phosphonsäuren, Quell- und Penetrationsstoffe wie Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,Complexing agents such as EDTA, NTA and phosphonic acids, Swelling and penetration substances such as carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
Die Auswahl dieser weiteren Stoffe wird der Fachmann gemäß der gewünschten Eigenschaften der Mittel treffen.The choice of these other substances will be made by those skilled in the art according to the desired properties of the agents.
Als weiteren Bestandteil können die erfindungsgemäßen Zusammensetzungen mindestens eine Ammoniumverbindung aus der Gruppe Ammoniumchlorid, Ammoniumcarbonat, Ammoniumbicarbonat, Ammoniumsulfat und/oder Ammoniumcarbamat in einer Menge von 0,5 bis 10, vorzugsweise 1 bis 5 Gew.-%, bezogen auf die Gesamtzusammensetzung des Mittels enthalten.As a further constituent, the compositions according to the invention may contain at least one ammonium compound from the group consisting of ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate in an amount of from 0.5 to 10, preferably from 1 to 5,% by weight, based on the total composition of the composition ,
Ferner können die erfindungsgemäßen Färbe- und/oder Aufhellmittel weitere Wirk-, Hilfs- undFurthermore, the dyeing and / or brightening agents according to the invention may contain further active ingredients, auxiliaries and
Zusatzstoffe, wie beispielsweise nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere,Additives such as nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers,
Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane, kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen,Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups,
Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl-ammoniumchlorid-Dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride
Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidon-Copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone
Copolymere, Vinylpyrrolidon-lmidazolinium-methochlorid-Copolymere und quaternierter Polyvinyl- alkohol, zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-tri- methylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.
Butylaminoethylmethacrylat^-Hydroxypropylmethacrylat-Copolymere, anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren,Butylaminoethyl methacrylate ^ -hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids,
Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere,Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers,
Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Malein-säureanhydrid-Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride
Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,Copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,
Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya
Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methyl- cellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wieGum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. As methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as
Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z.B. Polyvinylalkohol,Amylose, amylopectin and dextrins, clays such as Bentonite or fully synthetic hydrocolloids such as e.g. polyvinyl alcohol,
Strukturanten wie Maleinsäure und Milchsäure, haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin undStructural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, such as soybean lecithin, egg lecithin and
Kephaline, Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- undcephalins, Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and
Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierteWheat protein hydrolysates, their condensation products with fatty acids and quaternized
Proteinhydrolysate,protein,
Parfümöle, Dimethylisosorbid und Cyclodextrine,Perfume oils, dimethylisosorbide and cyclodextrins,
Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol, faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose, quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfatSolvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2 -alkylimidazolinium methosulfate
Entschäumer wie Silikone,Defoamers like silicones,
Farbstoffe zum Anfärben des Mittels,Dyes for staining the agent,
Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondereSubstances for adjusting the pH, such as conventional acids, in particular
Genußsäuren und Basen,Pleasure acids and bases,
Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B3, B5, B6, C,Vitamins, provitamins and vitamin precursors, in particular those of groups A, B 3 , B 5 , B 6 , C,
E, F und H,E, F and H,
Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis,Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel,
Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera,Hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera,
Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone,Spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime,
Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut,Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam,
Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng undQuenelles, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and
Ingwerwurzel,.Ginger root ,.
Cholesterin,Cholesterol,
Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
Fettsäurealkanolamide,fatty acid,
Komplexbildner wie EDTA, NTA, ß-Alanindiessigsäure und Phosphonsäuren,Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate,Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates,
Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,Hydrogencarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-CopolymereOpacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
Pigmente,pigments
Stabilisierungsmittel für Wasserstoffperoxid und andere Oxidationsmittel,Stabilizing agent for hydrogen peroxide and other oxidizing agents,
Treibmittel wie Propan-Butan-Gemische, N2O, Dimethylether, CO2 und Luft, Antioxidantien, enthaltenPropellants such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air, Antioxidants, included
Bezüglich weiterer fakultativer Komponenten sowie die eingesetzten Mengen dieser Komponenten wird ausdrücklich auf die dem Fachmann bekannten einschlägigen Handbücher, z. B. Kh. Schrader, Grundlagen und Rezepturen der Kosmetika, 2. Auflage, Hüthig Buch Verlag, Heidelberg, 1989, verwiesen.With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.
Die erfindungsgemäßen Mittel können die Inhaltsstoffe in einem geeigneten wäßrigen, alkoholischen oder wäßrig-alkoholischen Träger enthalten. Zum Zwecke der Haarfärbung sind solche Träger beispielsweise Cremes, Emulsionen, Gele oder auch tensidhaltige schäumende Lösungen, wie beispielsweise Shampoos, Schaumaerosole oder andere Zubereitungen, die für die Anwendung auf dem Haar geeignet sind. Es ist aber auch möglich, eine pulverförmige oder auch Tabletten-förmige Formulierung bereitzustellen, was für Färbe- und/oder Aufhellmittel bevorzugt ist.The compositions according to the invention may contain the ingredients in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. But it is also possible to provide a powdered or tablet-shaped formulation, which is preferred for dyeing and / or brightening agents.
Unter wäßrig-alkoholischen Lösungen sind im Sinne der vorliegenden Erfindung wäßrige Lösungen enthaltend 3 bis 70 Gew.-% eines C1-C4-AIkOhOIs, insbesondere Ethanol bzw. Isopropanol, zu verstehen. Die erfindungsgemäßen Mittel können zusätzlich weitere organische Lösemittel, wie beispielsweise Methoxybutanol, Benzylalkohol, Ethyldiglykol oder 1 ,2-Propylenglykol, enthalten. Bevorzugt sind dabei alle wasserlöslichen organischen Lösemittel.For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C 1 -C 4 -alkoxyethane, in particular ethanol or isopropanol. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.
Bevorzugte erfindungsgemäße Mittel sind dadurch gekennzeichnet, daß sie zusätzlich ein nichtwässriges Lösungsmittel enthalten, wobei besonders bevorzugte erfindungsgemäße Mittel das Lösungsmittel in einer Konzentration von 0,1 - 30 Gewichtsprozent, bevorzugt in einer Konzentration von 1 - 20 Gewichtsprozent, ganz besonders bevorzugt in einer Konzentration von 2 - 10 Gewichtsprozent, jeweils bezogen auf das Mittel, enthalten.Preferred agents according to the invention are characterized in that they additionally contain a nonaqueous solvent, particularly preferred compositions according to the invention the solvent in a concentration of 0.1 to 30 weight percent, preferably in a concentration of 1 to 20 weight percent, most preferably in a concentration of 2 - 10 weight percent, each based on the agent included.
In weiter bevorzugten erfindungsgemäßen Mitteln ist das Lösungsmittel ausgewählt aus Ethanol, n- Propanol, Isoropanol, n-Butanol, Propylenglykol, n- Butylenglykol, Glycerin, Diethylenglykolmonoethylether, Diethylenglykolmono-n- butylether , Phenoxyethanol und Benzylalkohol sowie ihren Mischungen.In further preferred agents according to the invention, the solvent is selected from ethanol, n-propanol, isoropanol, n-butanol, propylene glycol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, phenoxyethanol and benzyl alcohol and mixtures thereof.
Der pH-Wert der erfindungsgemäßen Mittel kann durch geeignete Inhaltstoffe wie Acidifizierungsmittel oder Alkalisierungsmittel in einem weiten Bereich eingestellt werden. Eine oxidative Färbung der Fasern kann in Gegenwart von Oxidationsfarbstoffvorprodukten grundsätzlich mit Luftsauerstoff erfolgen. Bevorzugt wird jedoch ein chemisches Oxidationsmittel eingesetzt, besonders dann, wenn neben der Färbung ein Aufhelleffekt an menschlichem Haar gewünscht ist. Dieser Aufhelleffekt kann unabhängig von der Färbemethode gewünscht sein. Die Gegenwart von Oxidationsfarbstoffvorprodukten ist demnach keine zwingende Voraussetzung für einen Einsatz von Oxidationsmitteln in den erfindungsgemäßen Mitteln. Als Oxidationsmittel kommen Persulfate, Chlorite und insbesondere Wasserstoffperoxid oder dessen Anlagerungsprodukte an Harnstoff, Melamin sowie Natriumborat in Frage.The pH of the compositions according to the invention can be adjusted within a wide range by suitable ingredients such as acidifying agent or alkalizing agent. Oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen in the presence of oxidation dye precursors. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. This lightening effect may be desired regardless of the staining method. The presence of oxidation dye precursors is therefore not a mandatory requirement for the use of oxidizing agents in the compositions of the invention. Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate.
Erfindungsgemäß kann aber das Oxidationsfärbemittel auch zusammen mit einem Katalysator auf das Haar aufgebracht werden, der die Oxidation der Farbstoffvorprodukte, z.B. durch Luftsauerstoff, aktiviert. Solche Katalysatoren sind z.B. Metallionen, lodide, Chinone oder bestimmte Enzyme.However, according to the invention, the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.
Geeignete Metallionen sind beispielsweise Zn2+, Cu2+, Fe2+, Fe3+, Mn2+, Mn4+, Li+, Mg2+, Ca2+ und Al3+. Besonders geeignet sind dabei Zn2+, Cu2+ und Mn2+. Die Metallionen können prinzipiell in der Form eines beliebigen, physiologisch verträglichen Salzes oder in Form einer Komplexverbindung eingesetzt werden. Bevorzugte Salze sind die Acetate, Sulfate, Halogenide, Lactate und Tartrate. Durch Verwendung dieser Metallsalze kann sowohl die Ausbildung der Färbung beschleunigt als auch die Farbnuance gezielt beeinflusst werden.Suitable metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Mn 4+ , Li + , Mg 2+ , Ca 2+ and Al 3+ . Particularly suitable are Zn 2+ , Cu 2+ and Mn 2+ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.
Geeignete Enzyme sind z.B. Peroxidasen, die die Wirkung geringer Mengen an Wasserstoffperoxid deutlich verstärken können. Weiterhin sind solche Enzyme erfindungsgemäß geeignet, die mit Hilfe von Luftsauerstoff die Oxidationsfarbstoffvorprodukte direkt oxidieren, wie beispielsweise die Laccasen, oder in situ geringe Mengen Wasserstoffperoxid erzeugen und auf diese Weise die Oxidation der Farbstoffvorprodukte biokatalytisch aktivieren. Besonders geeignete Katalysatoren für die Oxidation der Farbstoffvorläufer sind die sogenannten 2-Elektronen-Oxidoreduktasen in Kombination mit den dafür spezifischen Substraten, z.B.Suitable enzymes are e.g. Peroxidases that can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g.
Pyranose-Oxidase und z.B. D-Glucose oder Galactose,Pyranose oxidase and e.g. D-glucose or galactose,
Glucose-Oxidase und D-Glucose, Glycerin-Oxidase und Glycerin,Glucose oxidase and D-glucose, glycerol oxidase and glycerin,
Pyruvat-Oxidase und Benztraubensäure oder deren Salze, - Alkohol-Oxidase und Alkohol (MeOH, EtOH), Lactat-Oxidase und Milchsäure und deren Salze, Tyrosinase-Oxidase und Tyrosin, Uricase und Harnsäure oder deren Salze, Cholinoxidase und Cholin, Aminosäure-Oxidase und Aminosäuren.Pyruvate oxidase and pyruvic acid or its salts, - alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and their salts, tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, Choline oxidase and choline, amino acid oxidase and amino acids.
Bei einer Anwendung von Oxidationsmitteln wird das eigentliche Färbemittel zweckmäßigerweise unmittelbar vor der Anwendung durch Mischung der Zubereitung des Oxidationsmittels mit der Zubereitung, enthaltend die Verbindungen der Formel I und gegebenenfalls Farbstoffvorprodukte, hergestellt. Das dabei entstehende gebrauchsfertige Haarfärbepräparat sollte bevorzugt einen pH- Wert im Bereich von 6 bis 12 aufweisen. Besonders bevorzugt ist die Anwendung der Haarfärbemittel in einem schwach alkalischen Milieu. Die Anwendungstemperaturen können in einem Bereich zwischen 15 und 40 0C liegen. Nach einer Einwirkungszeit von 5 bis 45 Minuten wird das Haarfärbemittel durch Ausspülen von dem zu färbenden Haar entfernt. Das Nachwaschen mit einem Shampoo entfällt, wenn ein stark tensidhaltiger Träger, z.B. ein Färbeshampoo, verwendet wurde.In an application of oxidants, the actual colorant is conveniently prepared immediately prior to use by mixing the preparation of the oxidizing agent with the preparation containing the compounds of formula I and optionally dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures can be in a range between 15 and 40 0 C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.
Insbesondere bei schwer färbbarem Haar kann ein erfindungsgemäßes Mittel gegebenenfalls mit zusätzlichen Farbstoffvorprodukten aber auch ohne vorherige Vermischung mit der Oxidationskomponente auf das Haar aufgebracht werden. Nach einer Einwirkdauer von 20 bis 30 Minuten wird dann - gegebenenfalls nach einer Zwischenspülung - die Oxidationskomponente aufgebracht. Nach einer weiteren Einwirkdauer von 10 bis 20 Minuten wird dann gespült und ge- wünschtenfalls nachshampooniert. Bei dieser Ausführungsform wird gemäß einer ersten Variante, bei der das vorherige Aufbringen der Farbstoffvorprodukte eine bessere Penetration in das Haar bewirken soll, das entsprechende Mittel auf einen pH-Wert von etwa 4 bis 7 eingestellt. Gemäß einer zweiten Variante wird zunächst eine Luftoxidation angestrebt, wobei das aufgebrachte Mittel bevorzugt einen pH-Wert von 7 bis 10 aufweist. Bei der anschließenden beschleunigten Nachoxidation kann die Verwendung von sauer eingestellten Peroxidisulfat-Lösungen als Oxidationsmittel bevorzugt sein.In particular, in the case of hair that is difficult to dye, an agent according to the invention may optionally be applied to the hair with additional dye precursors but also without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After a further exposure time of 10 to 20 minutes, the product is then rinsed and, if desired, shampooed again. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to effect a better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent.
Für die Anwendung der erfindungsgemäßen Mittel auf dem Haar werden die Färbe- und/oder Aufhellmittel unmittelbar vor dem Auftragen mit einer Wasserstoffperoxid-Lösung vermischt. Die Konzentration dieser Wasserstoffperoxid-Lösung wird einerseits von den gesetzlichen Vorgaben und andererseits von dem gewünschten Effekt bestimmt; in der Regel werden 6- bis 12prozentige Lösungen in Wasser verwendet. Die Mengenverhältnisse von Färbe- und/oder Aufhellmittel und Wasserstoffperoxid-Lösung liegen dabei üblicherweise im Bereich 1 :1 bis 1 :2, wobei ein Überschuß an Wasserstoffperoxid-Lösung insbesondere dann gewählt wird, wenn keine zu ausgeprägte Blondierwirkung erwünscht ist. Zusätzlich können die erfindungsgemäßen Mittel weitere Inhaltsstoffe enthalten. Ein Einsatz bestimmter Metallionen oder -komplexe kann beispielsweise bevorzugt sein, um intensive Färbungen zu erhalten. Hier sind erfindungsgemäße Mittel bevorzugt, die zusätzlich Cu-, Fe-, Mn-, Ru-Ionen oder Komplexe dieser Ionen enthalten.For the application of the compositions of the invention on the hair dyeing and / or brightening agents are mixed immediately before application with a hydrogen peroxide solution. The concentration of this hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; As a rule, 6-12% solutions in water are used. The proportions of dyeing and / or lightening agent and hydrogen peroxide solution are usually in the range 1: 1 to 1: 2, with an excess of hydrogen peroxide solution is particularly selected when no too pronounced Blondierwirkung is desired. In addition, the compositions according to the invention may contain further ingredients. For example, use of certain metal ions or complexes may be preferred to obtain intense colorations. Agents according to the invention which additionally contain Cu, Fe, Mn, Ru ions or complexes of these ions are preferred here.
Bevorzugte erfindungsgemäße Mittel zum Färben und/oder Aufhellen keratinischer Fasern enthalten zusätzlich Cu-, Fe-, Mn-, Co-, Ce-, V-, Ru-Ionen oder Komplexe dieser Ionen, wobei bevorzugte Mittel 0,0001 bis 2,5 Gew.-%, vorzugsweise 0,001 bis 1 Gew.-% mindestens einer Verbindung aus der Gruppe Kupferchlorid (CuCI2), Kupfersulfat (CuSO4), Eisen(ll)sulfat, Mangan(ll)sulfat, Mangan(ll)chlorid, Kobalt(ll)chlorid, Cersulfat, Cerchlorid, Vanadiumsulfat, Mangandioxid (MnO2) enthalten.Preferred agents according to the invention for dyeing and / or lightening keratinic fibers additionally contain Cu, Fe, Mn, Co, Ce, V, Ru ions or complexes of these ions, preferred agents being from 0.0001 to 2.5% by weight .-%, preferably 0.001 to 1 wt .-% of at least one compound from the group copper chloride (CuCl 2 ), copper sulfate (CuSO 4 ), iron (II) sulfate, manganese (II) sulfate, manganese (II) chloride, cobalt ( ll) chloride, cerium sulfate, cerium chloride, vanadium sulfate, manganese dioxide (MnO 2 ).
Erfindungsgemäß bevorzugt ist auch der Einsatz von sogenannten Komplexbildnern. Komplexbilder sind Stoffe, die Metallionen komplexieren können. Bevorzugte Komplexbildner sind sogenannte Chelatkomplexbildner, also Stoffe, die mit Metallionen cyclische Verbindungen bilden, wobei ein einzelner Ligand mehr als eine Koordinationsstelle an einem Zentralatom besetzt, d. h. mind. "zweizähnig" ist. In diesem Falle werden also normalerweise gestreckte Verbindungen durch Komplexbildung über ein Ion zu Ringen geschlossen. Die Zahl der gebundenen Liganden hängt von der Koordinationszahl des zentralen Ions ab.Also preferred according to the invention is the use of so-called complexing agents. Complex images are substances that can complex metal ions. Preferred complexing agents are so-called chelate complexing agents, ie substances which form cyclic compounds with metal ions, a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.
Gebräuchliche und im Rahmen der vorliegenden Erfindung bevorzugte Chelatkomplexbilder sind beispielsweise Polyoxycarbonsäuren, Polyamine, Ethylendiamintetraessigsäure (EDTA), Nitrilotriessigsäure (NTA) und Hydroxyethandiphosphonsäuren bzw. deren Alkalisalze. Auch komplexbildende Polymere, also Polymere, die entweder in der Hauptkette selbst oder seitenständig zu dieser funktionelle Gruppen tragen, die als Liganden wirken können und mit geeigneten Metall- Atomen in der Regel unter Bildung von Chelat-Komplexen reagieren, sind erfindungsgemäß einsetzbar. Die Polymer-gebundenen Liganden der entstehenden Metall-Komplexe können dabei aus nur einem Makromolekül stammen oder aber zu verschiedenen Polymerketten gehören. Letzteres führt zur Vernetzung des Materials, sofern die komplexbildenden Polymere nicht bereits zuvor über kovalente Bindungen vernetzt waren.Customary and preferred chelate complex images in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and hydroxyethanediphosphonic acids or their alkali metal salts. Complex-forming polymers, ie polymers which carry functional groups either in the main chain themselves or in the side thereof, which can act as ligands and generally react with suitable metal atoms to form chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
Komplexierende Gruppen (Liganden) üblicher komplexbildender Polymere sind Iminodi-essigsäure-, Hydroxychinolin-, Thioharnstoff-, Guanidin-, Dithiocarbamat-, Hydroxamsäure-, Amidoxim-, Aminophosphorsäure-, (cycl.) Polyamino-, Mercapto-, 1 ,3-Dicarbonyl- und Kronenether-Reste mit z. T. sehr spezif. Aktivitäten gegenüber Ionen unterschiedlicher Metalle. Basispolymere vieler auch kommerziell bedeutender komplexbildender Polymere sind Polystyrol, Polyacrylate, Polyacrylnitrile, Polyvinylalkohole, Polyvinylpyridine und Polyethylenimine. Auch natürliche Polymere wie Cellulose, Stärke od. Chitin sind komplexbildende Polymere. Darüber hinaus können diese durch polymeranaloge Umwandlungen mit weiteren Ligand-Funktionalitäten versehen werden.Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1, 3-dicarbonyl - And crown ether residues with z. T. very specific. Activities towards ions of different metals. Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, Polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.
Besonders bevorzugt ist im Rahmen der vorliegenden Erfindung der Einsatz eines oder mehrerer Chelatkomplexbildner aus den Gruppen derIn the context of the present invention, it is particularly preferable to use one or more chelating agents from the groups of
(i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,(i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
(ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,(ii) nitrogen-containing mono- or polycarboxylic acids,
(iii) geminalen Diphosphonsäuren,(iii) geminal diphosphonic acids,
(iv) Aminophosphonsäuren,(iv) aminophosphonic acids,
(v) Phosphonopolycarbonsäuren,(v) phosphonopolycarboxylic acids,
(vi) Cyclodextrine.(vi) cyclodextrins.
Im Rahmen der vorliegenden Erfindung können alle Komplexbildner des Standes der Technik eingesetzt werden. Diese können unterschiedlichen chemischen Gruppen angehören. Vorzugsweise werden einzeln oder im Gemisch miteinander eingesetzt:In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:
a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure, b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N- Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N, N- Di-(ß-hydroxyethyl)glycin, N-(1 ,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1 ,2-Dicarboxy-2- hydroxyethyl)asparaginsäure oder Nitrilotriessigsäure (NTA), c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1 ,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1 ,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon, d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylen- triaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure), e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1 ,2,4-tricarbonsäure sowie f) Cyclodextrine. Als Polycarbonsäuren a) werden im Rahmen dieser Patentanmeldung Carbonsäuren -auch Monocarbonsäuren- verstanden, bei denen die Summe aus Carboxyl- und den im Molekül enthaltenen Hydroxylgruppen mindestens 5 beträgt. Komplexbildner aus der Gruppe der stickstoffhaltigen Polycarbonsäuren, insbesondere EDTA, sind bevorzugt. Bei den erfindungsgemäß erforderlichen alkalischen pH-Werten der Behandlungslösungen liegen diese Komplexbildner zumindest teilweise als Anionen vor. Es ist unwesentlich, ob sie in Form der Säuren oder in Form von Salzen eingebracht werden. Im Falle des Einsatzes als Salze sind Alkali-, Ammonium- oder Alkylammoniumsalze, insbesondere Natriumsalze, bevorzugt.a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid, b) nitrogen-containing mono- or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N , N-di (β-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA), c) geminal diphosphonic acids such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1, 1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof, d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methyl enphosphonic acid) or nitrilotri (methylenephosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and f) cyclodextrins. For the purposes of this patent application, polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. In the case of the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.
Ebenso sind als weitere bevorzugte Komplexbildner polymere Aminodicarbonsäuren, deren Salze oder deren Vorläufersubstanzen zu nennen. Besonders bevorzugt sind Polyasparaginsäuren bzw. deren Salze und Derivate, die neben Cobuilder-Eigenschaften auch eine bleichstabilisierende Wirkung aufweisen.Also to be mentioned as further preferred complexing polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
Weitere geeignete Komplexbildner sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Further suitable complexing agents are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
Eine weitere Substanzklasse mit komplexbildenden Eigenschaften stellen die Phosphonate dar. Dabei handelt es sich insbesondere um Hydroxyalkan- bzw. Aminoalkanphosphonate. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1 ,1-diphosphonat (HEDP) von besonderer Bedeutung. Es wird vorzugsweise als Natriumsalz eingesetzt, wobei das Dinatriumsalz neutral und das Tetranatriumsalz alkalisch (pH 9) reagiert. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Sie werden vorzugsweise in Form der neutral reagierenden Natriumsalze, z. B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octa- Natriumsalz der DTPMP, eingesetzt. Als Komplexbildner wird dabei aus der Klasse der Phosphonate bevorzugt HEDP verwendet. Die Aminoalkanphosphonate besitzen zudem ein ausgeprägtes Schwermetallbindevermögen. Dementsprechend kann es, insbesondere wenn die Mittel auch Bleiche enthalten, bevorzugt sein, Aminoalkanphosphonate, insbesondere DTPMP, einzusetzen, oder Mischungen aus den genannten Phosphonaten zu verwenden. Diese Stoffe werden nachstehend beschrieben. Erfindungsgemäß bevorzugte Komplexbildner sind Phosphonate, vorzugsweise Hydroxyalkan- bzw. Aminoalkanphosphonate und insbesondere 1-Hydroxyethan-1 ,1-diphosphonat (HEDP) bzw. dessen Di- oder Tetranatriumsalz und/oder Ethylendiamintetramethylenphosphonat (EDTMP) bzw. dessen Hexanatriumsalz und/oder Diethylentriaminpentamethylenphosphonat (DTPMP) bzw. dessen Hepta- oder Octanatriumsalz.Another class of substances with complex-forming properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as hexasodium salt of EDTMP or as hepta- and octa sodium salt of DTPMP used. The complexing agent used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. These substances will be described below. Compounds which are preferred according to the invention are phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its hexasodium salt and / or diethylenetriaminepentamethylenephosphonate (DTPMP ) or its hepta- or octasodium salt.
Aus den vorstehend genannten Stoffgruppen sind einige Vertreter im Rahmen der vorliegenden Erfindung besonders bevorzugt. Erfindungsgemäß besonders bevorzugte Mittel enthalten einen oder mehrere Stoffe aus der GruppeFrom the above-mentioned groups of substances, some representatives are particularly preferred in the context of the present invention. Particularly preferred agents according to the invention contain one or more substances from the group
(a) Nitrilotriessigsäure (NTA),(a) nitrilotriacetic acid (NTA),
(b) Diethylenetriaminpentaesigsäure (DTPA),(b) diethylenetriaminepentaacetic acid (DTPA),
(c) Ethylendiamindibernsteinsäure (EDDS),(c) ethylenediamine disuccinic acid (EDDS),
(d) Ethylenediamindiglutarsäure (EDGA),(d) ethylenediamine-diglutaric acid (EDGA),
(e) 2- Hydroxypropylendiamindibernsteinsäure (HPDS),(e) 2-hydroxypropylenediamine disuccinic acid (HPDS),
(f) Glycinamid-N,N'- dibernsteinsäure (GADS),(f) glycinamide-N, N'-disuccinic acid (GADS),
(g) Ethylendiamin-N-N'-diglutarsäure (EDDG),(g) ethylenediamine-N-N'-diglutaric acid (EDDG),
(h) 2-Hydroxypropylendiamin-N-N'-dibernsteinsäure (HPDDS),(h) 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS),
(i) Ethylendiamintetraessigsäure (EDTA),(i) ethylenediaminetetraacetic acid (EDTA),
(j) Ethylendicysteinsäure (EDC),(j) ethylene dicysteic acid (EDC),
(k) Diaminoalkyldi(sulfobernsteinsäure) (DDS),(k) diaminoalkyldi (sulfosuccinic acid) (DDS),
(I) Ethylendiamine-N-N'-bis(ortho-hydroxyphenylesigsäure (EDDHA),(I) ethylenediamine-N-N'-bis (ortho-hydroxyphenylacetic acid (EDDHA),
(m) N-2-hydroxyethyl-N,N-diessigsäure,(m) N-2-hydroxyethyl-N, N-diacetic acid,
(n) Glyceryliminodiessigsäure,(n) glyceryliminodiacetic acid,
(o) lminodiessigsäure-N-2-hydroxypropylsulfonsäure,(o) lminodiacetic acid N-2-hydroxypropylsulfonic acid,
(p) Asparaginsäure-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonsäure,(p) aspartic acid-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonic acid,
(q) 8-Alanin-N,N'-diessigsäure,(q) 8-alanine-N, N'-diacetic acid,
(r) Asparaginsäure-N,N'-diessigsäure,(r) aspartic acid-N, N'-diacetic acid,
(s) Asparaginsäure-N-monoessigsäure,(s) aspartic acid N-monoacetic acid,
(t) Dipicolinsäure,(t) dipicolinic acid,
(u) sowie deren Salze und/oder Derivate(u) and their salts and / or derivatives
Erfindungsgemäß bevorzugte Mittel sind dadurch gekennzeichnet, dass sie zusätzlich einen oder mehrere Chelatkomplexbildner aus den Gruppen derAgents preferred according to the invention are characterized in that they additionally comprise one or more chelate complexing agents from the groups of
(i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt, (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,(i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, (ii) nitrogen-containing mono- or polycarboxylic acids,
(iii) geminalen Diphosphonsäuren,(iii) geminal diphosphonic acids,
(iv) Aminophosphonsäuren,(iv) aminophosphonic acids,
(v) Phosphonopolycarbonsäuren,(v) phosphonopolycarboxylic acids,
(vi) Cyclodextrine enthalten, wobei bevorzugte Mittel Phosphonate, vorzugsweise Hydroxyalkan- bzw. Aminoalkanphosphonate und insbesondere 1-Hydroxyethan-1 ,1-diphosphonat (HEDP) bzw. dessen Di- oder Tetranatriumsalz und/oder Ethylendiamintetramethylenphosphonat (EDTMP) bzw. dessen Hexanatriumsalz und/oder Diethylentriaminpentamethylenphosphonat (DTPMP) bzw. dessen Hepta- oder Octanatriumsalz, enthalten.(vi) cyclodextrins, preferred agents being phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and especially 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its hexasodium salt and or diethylenetriaminepentamethylenephosphonate (DTPMP) or its hepta- or octasodium salt.
Bevorzugte erfindungsgemäße Mittel werden wasserarm bzw. wasserfrei formuliert. Erfindungsgemäß besonders bevorzugte Mittel sind dadurch gekennzeichnet, dass sie weniger als 5 Gew.-%, vorzugsweise weniger als 2 Gew.-%, besonders bevorzugt weniger als 1 Gew.-% und insbesondere weniger als 0,5 Gew.-% Wasser enthalten, wobei bevorzugte Mittel wasserfrei sind. Der Wassergehalt der Mittel läßt sich beispielsweise mittels Titration nach Karl Fischer bestimmen.Preferred agents according to the invention are formulated with little or no water. Particularly preferred agents according to the invention are characterized in that they contain less than 5% by weight, preferably less than 2% by weight, more preferably less than 1% by weight and in particular less than 0.5% by weight of water, preferred agents being anhydrous. The water content of the agent can be determined, for example, by means of titration according to Karl Fischer.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Aufhellen von Keratinfasern, insbesondere menschlichen Haaren, dadurch gekennzeichnet, daß gewünschtenfalls ein Vorbehandlungsmittel M1 auf die Faser aufgebracht wird, dann ein Mittel M2 auf der Faser zur Anwendung kommt, wobei gewünschtenfalls dem Mittel M2 vor der Anwendung ein weiteres Mittel M3 zugegeben wird, dieses Mittel M2 nach einer Zeit von 5-30 Minuten von der Faser abgespült wird und nach der Behandlung gegebenenfalls ein Nachbehandlungsmittel M4 auf die Faser aufgetragen und nach einer Einwirkzeit von einigen Minuten wieder abgespült wird, wobei mindestens eines der Mittel M1 , M2 oder M3 ein erfindungsgemäßes Mittel ist.Another object of the present invention is a method for whitening keratin fibers, in particular human hair, characterized in that, if desired, a pretreatment agent M1 is applied to the fiber, then a means M2 on the fiber is used, wherein, if desired, the means M2 before the Application of a further agent M3 is added, this agent M2 is rinsed from the fiber after a time of 5-30 minutes and after treatment optionally a post-treatment agent M4 applied to the fiber and rinsed after a contact time of a few minutes, wherein at least one the agent M1, M2 or M3 is an agent according to the invention.
Die erfindungsgemäßen Mittel können demnach als Einkomponentenmittel (Färbe- und Aufhellmittel M2 bzw. Nachbehandlungsmittel M4), als Zweikomponenten Mittel (M2 + M3) oder als Dreikomponentenmittel (M2 + M3 + M4) formuliert und entsprechend angewendet werden. Eine Auftrennung in Mehrkomponentensysteme bietet sich insbesondere dort an, wo Inkompatibilitäten der Inhaltsstoffe zu erwarten oder zu befürchten sind; das einzusetzende Mittel wird bei solchen Systemen vom Verbraucher direkt vor der Anwendung durch Vermischen der Komponente hergestellt. Ein Färbe- und Aufhellungsverfahren, bei dem die Aufhellcreme und das Oxidationsmittel zunächst getrennt vorliegen, ist dabei bevorzugt. Ein weiterer Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zum Färben und Aufhellen von menschlichen Haaren, bei dem eine Zusammensetzung auf wäßriger Grundlage, enthaltend Wasserstoffperoxid, mit einem erfindungsgemäßen Mittel zu einer homogenen Zusammensetzung vermischt, und diese auf das Haar aufgebracht wird.The agents according to the invention can accordingly be formulated as single-component agents (dyeing and whitening agents M2 or aftertreatment agents M4), as two-component agents (M2 + M3) or as three-component agents (M2 + M3 + M4) and used accordingly. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or feared; the agent to be used in such systems is manufactured by the consumer just prior to use by mixing the component. A dyeing and whitening process in which the whitening cream and the oxidizing agent are initially separate is preferred. A further subject of the present invention is therefore a process for dyeing and lightening human hair, in which an aqueous-based composition containing hydrogen peroxide is mixed with an agent according to the invention to form a homogeneous composition and applied to the hair.
In bevorzugten erfindungsgemäßen Verfahren dieser Art enthält die Zusammensetzung auf wäßriger Grundlage bezogen auf ihr Gewicht 1 bis 20 Gew.%, vorzugsweise 2 bis 10 Gew.% und insbesondere 3 bis 6 Gew.% Wasserstoffperoxid, berechnet als 100%iges H2O2.In preferred processes of this type according to the invention, the aqueous composition contains from 1 to 20% by weight, preferably from 2 to 10% by weight and in particular from 3 to 6% by weight of hydrogen peroxide, calculated as 100% H 2 O 2 .
Weiter bevorzugte erfindungsgemäße Verfahren dieser Art sind dadurch gekennzeichnet, daß die Zusammensetzung auf wäßriger Grundlage, enthaltend Wasserstoffperoxid, mit einem erfindungsgemäßen Mittel im Gewichtsverhältnis 1 :5 bis 10:1 , vorzugsweise 1 :2 bis 5:1 und insbesondere 1 :2 bis 2:1 zu einer homogenen Zusammensetzung vermischt, und diese auf das Haar aufgebracht wird.Further preferred processes of this kind according to the invention are characterized in that the aqueous-based composition comprising hydrogen peroxide is mixed with an agent according to the invention in a weight ratio of 1: 5 to 10: 1, preferably 1: 2 to 5: 1 and in particular 1: 2 to 2: 1 is mixed to a homogeneous composition, and this is applied to the hair.
Alternativ kann - wie vorstehend erwähnt - auch ein Dreikomponentensystem zur Anwendung gelangen. Ein weiterer Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zum Färben und Aufhellen von menschlichen Haaren, bei dem eine Zusammensetzung auf wäßriger Grundlage, enthaltend Wasserstoffperoxid, mit einem weiteren Mittel enthaltend vorzugsweise mindestens einen Alkalitätsgeber und/oder direktziehenden Haarfarbstoff und/oder mindestens ein Oxidationsfarbstoffvorprodukt, und einem erfindungsgemäßen Mittel zu einer homogenen Zusammensetzung vermischt, und diese auf das Haar aufgebracht wird.Alternatively, as mentioned above, a three-component system may also be used. A further subject of the present invention is therefore a process for dyeing and lightening human hair, comprising an aqueous-based composition containing hydrogen peroxide with a further agent containing preferably at least one alkalinity donor and / or substantive hair dye and / or at least one oxidation dye precursor, and a composition according to the invention mixed to a homogeneous composition, and this is applied to the hair.
Bezüglich weiterer bevorzugter Ausführungsformen der erfindungsgemäßen Verfahren gilt mutatis mutandis das zur erfindungsgemäßen Verwendung Gesagte.With regard to further preferred embodiments of the method according to the invention, the statements made on the use according to the invention apply mutatis mutandis.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von Polyolestern der Formel (I) A further subject of the present invention is the use of polyol esters of the formula (I)
Figure imgf000081_0001
worin
Figure imgf000081_0001
wherein
R1 und R2 stehen unabhängig voneinander für -H oder einen einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C-ι-24-Alkyl- oder -Alkenylrest, vorzugsweise für -H, -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 R 1 and R 2 independently of one another are -H or a straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 24 -alkyl or -alkenyl radical, preferably -H, -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
R3 und R4 stehen unabhängig voneinander für -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 n steht für Werte von 1 bis 12, vorzugsweise für 2, 3, 4, 5, 6. in Mitteln zum Färben und/oder Aufhellen keratinischer Fasern.R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3 n is from 1 to 12, preferably from 2, 3, 4, 5, 6 in agents for dyeing and / or lightening keratinischer fibers.
Besonders bevorzugt dient der Einsatz der Verbindungen der Erzielung bestimmter vorteilhafterParticularly preferably, the use of the compounds is the achievement of certain advantageous
Effekte. Erfindungsgemäß bevorzugt sind Verwendungen zur i. Steigerung der Aufhell- bzw. Blondierleistung und/oder ii. Steigerung der Hautverträglichkeit von Aufhell- bzw. Blondiermitteln und/oder iii. Erzielung neutraler Farbergebnisse beim Blondieren und/oder iv. Verringerung von gelben Farbtönen beim Blondieren und/oder v. Verringerung von Vergilbungen auf keratinischen Fasern.Effects. Preferred according to the invention are uses for i. Increase in the whitening or bleaching performance and / or ii. Increasing the skin compatibility of brightening or bleaching agents and / or iii. Achieving neutral color results when bleaching and / or iv. Reduction of yellow shades when bleaching and / or v. Reduction of yellowing on keratin fibers.
Bezüglich bevorzugter erfindungsgemäßer Verwendungen gilt mutatis mutandis das zu den bevorzugten Mitteln Ausgeführte. Beispiele:With regard to preferred uses according to the invention, the mutated mutandis applies to the preferred agents. Examples:
Die Untersuchungen wurden in wässrigen Lösungen durchgeführt. Strähnen aus dunkelblonden Haaren (Code: Kerling 7/0) von ca.0,5 g Gewicht wurden in Bechergläsern mit der 15 fachen Menge an Wirkstofflösung Übergossen und 30 Minuten bei 320C blondiert. Der pH-Wert wurde auf ca.10,0 bzw.8,0 eingestellt.The investigations were carried out in aqueous solutions. Strands of dark blond hair (code: Kerling 7/0) of ca.0.5 g weight were in beakers with the 15-fold amount of active ingredient solution and bleached 30 minutes at 32 0 C bleached. The pH was adjusted to about 10.0 and 8.0, respectively.
Die Konzentrationen an Wasserstoffperoxid betrugen jeweils 6,0 %, die Konzentrationen der Zusätze wurden z. T. zwischen 1% und 10 % variiert (s. Tabelle). Die Lösungen wurden zusätzlich mit 1,5% Turpinal (60%ige Lösung von Hydroxyethandiphosphonsäure) und 0,1 % Dipicolinsäure stabilisiert.The concentrations of hydrogen peroxide were each 6.0%, the concentrations of the additives were z. T. varies between 1% and 10% (see table). The solutions were additionally stabilized with 1.5% turpinal (60% solution of hydroxyethanediphosphonic acid) and 0.1% dipicolinic acid.
Farbmetrische Resultate:Colorimetric results:
pH = 8pH = 8
6 % H2O2 Δ L = 26% H 2 O 2 Δ L = 2
6 % H2O2 + 5 % Triacetin ΔL = 6 ΔΔL = 46% H 2 O 2 + 5% triacetin ΔL = 6 ΔΔL = 4
6 % H2O2 + 5 % Triacetin + 5 % Imidazol ΔL=19 ΔΔL = 176% H 2 O 2 + 5% triacetin + 5% imidazole ΔL = 19 ΔΔL = 17
6 % H2O2 + 1 % Triacetin + 1 % Imidazol ΔL = 5 ΔΔL = 36% H 2 O 2 + 1% triacetin + 1% imidazole ΔL = 5 ΔΔL = 3
pH = 10pH = 10
6% H2O2 ΔL= 106% H 2 O 2 ΔL = 10
6 % H2O2 + 5 % Triacetin ΔL= 13 ΔΔL = 36% H 2 O 2 + 5% triacetin ΔL = 13 ΔΔL = 3
6 % H2O2 + 5 % Triacetin + 5 % Imidazol ΔL= 16 ΔΔL = 66% H 2 O 2 + 5% triacetin + 5% imidazole ΔL = 16 ΔΔL = 6
6 % H2O2 + 1 % Triacetin + 1 % Imidazol ΔL= 12 ΔΔL = 26% H 2 O 2 + 1% triacetin + 1% imidazole ΔL = 12 ΔΔL = 2
Die Messwerte zeigen, dass die Polyolester Wasserstoffperoxid aktivieren, wobei in Kombination mit Imidazol eine deutliche Wirkverstärkung eintritt. The measurements show that the polyolester activates hydrogen peroxide, which, in combination with imidazole, results in a marked increase in activity.

Claims

Patentansprüche: claims:
1. Mittel zum Färben und/oder Aufhellen von Keratinfasern, insbesondere menschlichen Haaren, enthaltend -bezogen auf sein Gewicht - a) 0,5 bis 15 Gew.-%, vorzugsweise 1 bis 12,5 Gew.-%, besonders bevorzugt 2,5 bis 10 Gew.-% und insbesondere 3 bis 6 Gew.-% Wasserstoffperoxid (berechnet als 100%iges H2O2), b) 0,001 bis 15 Gew.-% mindestens eines Polyolesters der Formel (I)1. means for dyeing and / or whitening keratin fibers, in particular human hair, containing-based on its weight - a) 0.5 to 15 wt .-%, preferably 1 to 12.5 wt .-%, particularly preferably 2, From 5 to 10% by weight and in particular from 3 to 6% by weight of hydrogen peroxide (calculated as 100% H 2 O 2 ), b) from 0.001 to 15% by weight of at least one polyol ester of the formula (I)
Figure imgf000083_0001
worin
Figure imgf000083_0001
wherein
R1 und R2 stehen unabhängig voneinander für -H oder einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C-|.24-Alkyl- oder -Alkenylrest, vorzugsweise für -H, -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 R 1 and R 2 independently of one another are -H or a straight-chain or branched, saturated or mono- or polyunsaturated C 1-6. 24 alkyl or alkenyl radical, preferably -H, -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
R3 und R4 stehen unabhängig voneinander für -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 n steht für Werte von 1 bis 12, vorzugsweise für 2, 3, 4, 5, 6.R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3 n is from 1 to 12, preferably from 2, 3, 4, 5, 6.
2. Mittel zum Färben und/oder Aufhellen keratinischer Fasern nach Anspruch 1 , dadurch gekennzeichnet, daß es 0,1 bis 15 Gew.-%, vorzugsweise 1 bis 12,5 Gew.-%, besonders bevorzugt 2,5 bis 10 Gew.-% und insbesondere 5 bis 7,5 Gew.-% mindestens eines Polyolesters der Formel (Ia)
Figure imgf000084_0001
enthält, in der R1 und R2 stehen unabhängig voneinander für -H oder einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C-i-24-Alkyl- oder -Alkenylrest, vorzugsweise für -H, -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 2. Means for dyeing and / or brightening keratinic fibers according to claim 1, characterized in that it contains 0.1 to 15 wt .-%, preferably 1 to 12.5 wt .-%, particularly preferably 2.5 to 10 wt. % and in particular 5 to 7.5% by weight of at least one polyol ester of the formula (Ia)
Figure imgf000084_0001
contains, in which R 1 and R 2 are independently -H or a linear or branched, saturated or mono- or polyunsaturated Ci- 24 alkyl or alkenyl group, preferably -H, -CH 3; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
R3 und R4 stehen unabhängig voneinander für -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
3. Mittel zum Färben und/oder Aufhellen keratinischer Fasern nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß es 0,1 bis 15 Gew.-%, vorzugsweise 1 bis 12,5 Gew.-%, besonders bevorzugt 2,5 bis 10 Gew.-% und insbesondere 5 bis 7,5 Gew.-% mindestens eines Polyolesters der Formel (Ib)3. Agent for dyeing and / or lightening keratinic fibers according to one of claims 1 or 2, characterized in that it is 0.1 to 15 wt .-%, preferably 1 to 12.5 wt .-%, particularly preferably 2.5 to 10% by weight and in particular 5 to 7.5% by weight of at least one polyol ester of the formula (Ib)
Figure imgf000084_0002
enthält, in der R1 und R2 stehen unabhängig voneinander für -H oder einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C-|.24-Alkyl- oder -Alkenylrest, vorzugsweise für -H, -CH3; -CH2CH3, -CH2CH2CH3, t^ H(L/ H 3)2 j ~(L/'~'2)3L/π3, -L/H2~L/H(L/n3)2i L/H(L/H3)L/π2L/π3, -L/(L/H3)3, (CH2)3CH3, -CH2-CH(CHs)2, CH(CH3)CH2CH3, -C(CH3)3
Figure imgf000084_0002
contains, in which R 1 and R 2 are independently of one another -H or a straight-chain or branched, saturated or mono- or polyunsaturated C-. 24 alkyl or alkenyl radical, preferably -H, -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , t ^ H (L / H 3 ) 2 j ~ (L / '-' 2 ) 3 L / π 3 , -L / H 2 ~ L / H (L / n 3 ) 2 i L / H (L / H 3 ) L / π 2 L / π 3 , -L / (L / H 3 ) 3 , (CH 2 ) 3 CH 3 , -CH 2 -CH (CHs) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
R3 und R4 stehen unabhängig voneinander für -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2 R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2
4. Mittel zum Färben und/oder Aufhellen keratinischer Fasern nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es zusätzlich - bezogen auf sein Gewicht - 0,001 bis 5 Gew.-% eines oder mehrerer Oxidationsfarbstoffvorprodukte und/oder direktziehender Farbstoffe enthält.4. An agent for dyeing and / or whitening keratinic fibers according to any one of claims 1 to 3, characterized in that it additionally - based on its weight - from 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes.
5. Mittel zum Färben und/oder Aufhellen keratinischer Fasern nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es als Oxidationsfarbstoffvorprodukt mindestens eine Entwicklerkomponente enthält, wobei bevorzugte Entwicklerkomponenten ausgewählt sind aus p-Phenylendiamin, p-Toluylendiamin, , N,N-Bis-(2-hydroxyethyl)amino-p-phenylendiamin, 1 ,3- Bis-[(2-hydroxyethyl-4'-aminophenyl)amino]-propan-2-ol, 1 ,10-Bis-(2',5'- diaminophenyl)- 1 ,4,7,10-tetraoxadecan, 4-Aminophenol, A- Amino-3-methylphenol, Bis-(5- amino-2- hydroxyphenyl)methan, 2,4,5,6- Tetraaminopyrimidin, 2-Hydroxy-4,5,6- triaminopyrimidin, 4,5- Diamino-1-(2-hydroxyethyl)-pyrazol.5. A dyeing and / or whitening agent for keratinous fibers according to any one of claims 1 to 4, characterized in that it contains as oxidation dye precursor at least one developer component, preferred developer components being selected from p-phenylenediamine, p-toluenediamine,, N, N- bis (2-hydroxyethyl) amino-p-phenylenediamine, 1, 3- bis - [(2-hydroxyethyl-4 'aminophenyl) amino] -propan-2-ol, 1, 10-bis (2', 5 '- diaminophenyl) - 1, 4,7,10-tetraoxadecane, 4-aminophenol, A-amino-3-methylphenol, bis (5-amino-2-hydroxyphenyl) methane, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4,5-diamino-1- (2-hydroxyethyl) pyrazole.
6. Mittel zum Färben und/oder Aufhellen keratinischer Fasern nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es als Oxidationsfarbstoffvorprodukt mindestens eine Kupplerkomponente enthält, wobei bevorzugte Kupplerkomponenten ausgewählt sind aus Resorcin, 2-Methylresorcin, 5-Methyl-resorcin, 2,5-Dimethylresorcin, 4-Chlorresorcin, Resorcinmonomethylether, 5-Aminophenol, 5-Amino-2-methylphenol, 5-(2-Hydroxyethyl)amino- 2-methylphenol, 3- Amino-4-chlor-2-methylphenol, 3-Amino-2-chlor-6-methylphenol, 3-Amino- 2,4-Dichlorphenol, 2,4-Diaminophenoxyethanol, 2-Amino-4-(2'-hydroxyethyl)amino-anisolsulfat, 1 ,3-Bis-(2,4-diaminophenoxy)propan, 2-Amino-3-hydroxypyridin, 2-Methylamino-3-amino-6- methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 3,5-Diamino-2,6-dimethoxypyridin, 1- Naphthol, 2-Methyl-1-naphthol, 1 ,5-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin, 1-Phenyl-3- methylpyrazol-5-on, 2,6-Bis-[(2'-hydroxyethyl)amino]-toluol, 4-Hydroxyindol, 6-Hydroxyindol, 6- Hydroxybenzomorpholin.6. A dyeing and / or whitening agent for keratinous fibers according to any one of claims 1 to 5, characterized in that it contains as oxidation dye precursor at least one coupler component, preferred coupler components are selected from resorcinol, 2-methylresorcinol, 5-methyl-resorcinol, 2nd , 5-dimethylresorcinol, 4-chlororesorcinol, resorcinol monomethyl ether, 5-aminophenol, 5-amino-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 3-amino-4-chloro-2-methylphenol, 3 amino-2-chloro-6-methylphenol, 3-amino-2,4-dichlorophenol, 2,4-diaminophenoxyethanol, 2-amino-4- (2 '-hydroxyethyl) amino-anisolsulfat, 1, 3-bis (2 , 4-diaminophenoxy) propane, 2-amino-3-hydroxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine , 1-naphthol, 2-methyl-1-naphthol, 1, 5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-phenyl-3-methylpyrazole-5-one, 2,6-bis - [(2 '-hydroxyethyl) amino] -toluene, 4-hydroxyindole, 6-hydroxyindole, 6-hydroxyb enzomorpholin.
7. Mittel zum Färben und/oder Aufhellen keratinischer Fasern nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es mindestens einen direktziehenden Farbstoff enthält, der ausgewählt ist aus Nitrophenylendiaminen, Nitroaminophenolen, Azofarbstoffen, Anthrachinonen oder Indophenolen, vorzugsweise aus der Gruppe der unter den internationalen Bezeichnungen bzw. Handelsnamen bekannten Farbstoffe HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1 , Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1 , Disperse Orange 3, Acid Orange 7, HC Red 1 , HC Red 3, HC Red 10, HC Red 11 , HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57:1 , HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1 , Disperse Violet 1 , Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1 , Acid Black 52, Basic Yellow 87, Basic Orange 31 und Basic Red 51 bekannten Verbindungen sowie 1 ,4- Diamino-2-nitrobenzol, 2-Amino-4-nitrophenol, 1 ,4-Bis-(ß-hydroxyethyl)-amino-2-nitrobenzol, 3- Nitro-4-(ß-hydroxyethyl)-aminophenol, 2-(2-Hydroxyethyl)amino-4,6-dinitrophenol, 1-(2'- Hydroxyethyl)amino-4-nnethyl-2-nitrobenzol, 1-Amino-4-(2-hydroxyethyl)-amino-5-chlor-2- nitrobenzol, 4-Amino-3-nitrophenol, 1-(2-Ureidoethyl)amino-4-nitrobenzol, 4-Amino-2- nitrodiphenylamin-2'-carbonsäure, 6-Nitro-1 ,2,3,4-tetrahydrochinoxalin, 2-Hydroxy-1 ,4- naphthochinon, Pikraminsäure und deren Salze, 2-Amino-6-chloro-4-nitrophenol, 4-Ethylamino- 3-nitrobenzoesäure und 2-Chloro-6-ethylamino-1-hydroxy-4-nitrobenzol.7. A dyeing and / or whitening agent for keratinous fibers according to any one of claims 1 to 6, characterized in that it contains at least one substantive dye selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group of the international names or trade names known dyes HC Yellow 2, HC HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3 HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50 , HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, Acid Black 52, Basic Yellow 87, Basic Orange 31 and Basic Red 51 known compounds as well as 1, 4-diamino-2 -nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4- Amino-3-nitrophenol, 1- (2-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy 1, 4-naphthoc hinon, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.
8. Mittel zum Färben und/oder Aufhellen keratinischer Fasern nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es - bezogen auf sein Gewicht - 1 bis 20 Gew.-% mindestens eines gegebenenfalls substituierten, insbesondere benzannellierten Azols, vorzugsweise mindestens ein gegebenenfalls substituiertes und/oder benzannelliertes Pyrrol und/oder Pyrazol und/oder Imidazol und/oder 1 ,2,3-Triazol und/oder 1 ,2,4-Triazol und/oder 1 ,2,3,4- Tetrazol, enthält.8. A composition for dyeing and / or lightening keratinic fibers according to any one of claims 1 to 7, characterized in that it - based on its weight - 1 to 20 wt .-% of at least one optionally substituted, in particular benzannellierten azole, preferably at least one optionally substituted and / or benzannellated pyrrole and / or pyrazole and / or imidazole and / or 1, 2,3-triazole and / or 1, 2,4-triazole and / or 1, 2,3,4-tetrazole.
9. Mittel nach Anspruch 8, dadurch gekennzeichnet, daß es mindestens eine Imidazolverbindung gemäß Formel (VI) und/oder deren physiologisch verträglichen Salzen9. Composition according to claim 8, characterized in that it comprises at least one imidazole compound according to formula (VI) and / or physiologically acceptable salts thereof
Figure imgf000086_0001
enthält, worin
Figure imgf000086_0001
contains, in which
R1 steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe oder eine (d-C6)-Alkylgruppe,R 1 represents a hydrogen atom, an optionally substituted aryl group or a (dC 6 ) -alkyl group,
R2 steht für ein Wasserstoffatom, eine Carboxaldehydgruppe, eine (C1-C6)- Alkylgruppe oder eine Nitrogruppe, R3 steht für ein Wasserstoffatom, eine Carboxy-(d-C6)-alkylgruppe, eine Amino-(C"rC6)-alkylgruppe, eine Carboxylgruppe, eineR 2 represents a hydrogen atom, a carboxaldehyde group, a (C 1 -C 6 ) -alkyl group or a nitro group, R 3 represents a hydrogen atom, a carboxy (dC 6 ) alkyl group, an amino (C "rC 6 ) alkyl group, a carboxyl group, a
Carboxaldehydgruppe, eine (C-ι-C6)-Alkylgruppe, eine Nitrogruppe, eine 2- Amino-3-hydroxypropylgruppe oder eine Gruppe -CH2-CH(NH2)-COOH,Carboxaldehyde group, a (C 1 -C 6 ) -alkyl group, a nitro group, a 2-amino-3-hydroxypropyl group or a group -CH 2 -CH (NH 2 ) -COOH,
R4 steht für ein Wasserstoffatom, eine Carboxaldehydgruppe oder eine Carboxylgruppe.R 4 represents a hydrogen atom, a carboxaldehyde group or a carboxyl group.
10. Mittel zum Färben und/oder Aufhellen keratinischer Fasern nach Anspruch 9, dadurch gekennzeichnet, daß es mindestens eine Imidazolverbindung gemäß Formel (VI) und/oder deren physiologisch verträgliche Salze in Mengen von 2 bis 15 Gew.-%, vorzugsweise von 2,5 bis 12,5 Gew.-%, besonders bevorzugt von 3 bis 10 Gew.-% und insbesondere von 4 bis 8 Gew.-% enthält.10. A composition for dyeing and / or lightening keratinic fibers according to claim 9, characterized in that it comprises at least one imidazole compound according to formula (VI) and / or physiologically acceptable salts thereof in amounts of 2 to 15 wt .-%, preferably of 2, 5 to 12.5 wt .-%, particularly preferably from 3 to 10 wt .-% and in particular from 4 to 8 wt .-%.
11. Mittel zum Färben und/oder Aufhellen keratinischer Fasern nach einem der Ansprüche 9 oder 10, dadurch gekennzeichnet, daß die Imidazolverbindung gemäß Formel (VI) und/oder deren physiologisch verträgliche Salze ausgewählt ist/sind aus Histamin, D-Histidin, L-Histidin, DL- Histidin, D-Histidinol, L-Histidinol, DL-Histidinol, Imidazol, lmidazol-4-essigsäure, lmidazol-4- carbonsäure, lmidazol-4,5-dicarbonsäure, lmidazol-2-carboxaldehyd, lmidazol-4- carboxaldehyd, lmidazol-5-carboxaldehyd, 2-Nitroimidazol, 4-Nitroimidazol, 4-Methylimidazol-5- carboxaldehyd, N-Methylimidazol-2-carboxaldehyd, 4-Methylimidazol, 2-Methylimidazol, N- Methylimidazol, N-(4-Aminophenyl)-imidazol, sowie den physiologisch verträglichen Salze der vorgenannten Verbindungen.11. A composition for dyeing and / or brightening keratinic fibers according to any one of claims 9 or 10, characterized in that the imidazole compound according to formula (VI) and / or their physiologically acceptable salts is / are selected from histamine, D-histidine, L Histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, imidazole, imidazole-4-acetic acid, imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazole-2-carboxaldehyde, imidazole-4 carboxaldehyde, imidazole-5-carboxaldehyde, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole-5-carboxaldehyde, N-methylimidazole-2-carboxaldehyde, 4-methylimidazole, 2-methylimidazole, N-methylimidazole, N- (4-aminophenyl ) -imidazole, as well as the physiologically acceptable salts of the aforementioned compounds.
12. Mittel zum Färben und/oder Aufhellen keratinischer Fasern nach einem der Ansprüche 1 bis 10 dadurch gekennzeichnet, daß es zusätzlich 0,01 bis 2 Gew.-% mindestens einer festen Peroxoverbindung, die ausgewählt ist aus Ammonium- und Alkalimetall-persulfaten und - peroxidisulfaten enthält, wobei bevorzugte Mittel Peroxidisulfate enthalten, die vorzugsweise ausgewählt sind aus Natriumperoxidisulfat und/oder Kaliumperoxidisulfat und/oder Ammoniumperoxidisulfat und wobei besonders bevorzugte Mittel mindestens zwei verschiedene Peroxidislfate enthalten.12. An agent for dyeing and / or lightening keratinic fibers according to any one of claims 1 to 10, characterized in that it additionally 0.01 to 2 wt .-% of at least one solid peroxo compound, which is selected from ammonium and alkali metal persulfates and - peroxidisulfates, preferred agents containing peroxydisulfates, which are preferably selected from sodium peroxydisulfate and / or potassium peroxodisulfate and / or ammonium peroxydisulfate and particularly preferred agents containing at least two different peroxidisulfates.
13. Mittel zum Färben und/oder Aufhellen keratinischer Fasern nach einem der Ansprüche 1 bis 11 , dadurch gekennzeichnet, daß es zusätzlich 0,1 bis 25 Gew.%, vorzugsweise 0,5 bis 20 Gew.%, besonders bevorzugt 1 bis 15 Gew.% und insbesondere 1 ,5 bis 10 Gew.% mindestens eines Stoffes aus den Gruppen der i. Carbonate und/oder ii. Monoalkylcarbonate (Kohlensäuremonoester) und/oder iii. Kohlensäuremonoamide und/oder iv. Silylcarbonate und/oder v. Silylcarbamate enthält.13. A dyeing and / or whitening agent for keratinous fibers according to any one of claims 1 to 11, characterized in that it additionally contains 0.1 to 25 wt.%, Preferably 0.5 to 20 wt.%, Particularly preferably 1 to 15 wt .% And in particular 1, 5 to 10 wt.% Of at least one substance from the groups of i. Carbonates and / or ii. Monoalkyl carbonates (carbonic acid monoesters) and / or iii. Carbonic acid monoamides and / or iv. Silyl carbonates and / or v. Silylcarbamate contains.
14. Verfahren zum Aufhellen von Keratinfasern, insbesondere menschlichen Haaren, dadurch gekennzeichnet, daß gewünschtenfalls ein Vorbehandlungsmittel M1 auf die Faser aufgebracht wird, dann ein Mittel M2 auf der Faser zur Anwendung kommt, wobei gewünschtenfalls dem14. A process for lightening keratin fibers, in particular human hair, characterized in that, if desired, a pretreatment agent M1 is applied to the fiber, then a means M2 on the fiber is used, wherein if desired the
Mittel M2 vor der Anwendung ein weiteres Mittel M3 zugegeben wird, dieses Mittel M2 nach einer Zeit von 5-30 Minuten von der Faser abgespült wird und nach der Behandlung gegebenenfalls ein Nachbehandlungsmittel M4 auf dieAgent M2 is added before use, a further agent M3, this agent M2 is rinsed from the fiber after a period of 5-30 minutes and after treatment optionally a post-treatment agent M4 on the
Faser aufgetragen und nach einer Einwirkzeit von einigen Minuten wieder abgespült wird, wobei mindestens eines der Mittel M1 , M2 oder M3 ein Mittel nach einem der Ansprüche 1 bis 1 1 ist.Fiber is applied and rinsed again after a contact time of a few minutes, wherein at least one of the means M1, M2 or M3 is an agent according to any one of claims 1 to 1 1.
15. Verwendung von Polyolestern der Formel (I)15. Use of polyol esters of the formula (I)
Figure imgf000088_0001
worin
Figure imgf000088_0001
wherein
R1 und R2 stehen unabhängig voneinander für -H oder einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C-ι-24-Alkyl- oder -Alkenylrest, vorzugsweise für -H, -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 R 1 and R 2 independently of one another are -H or a straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 24 -alkyl or -alkenyl radical, preferably -H, -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3
R3 und R4 stehen unabhängig voneinander für -CH3; -CH2CH3, -CH2CH2CH3, CH(CH3)2, -(CH2)3CH3, -CH2-CH(CH3)2, CH(CH3)CH2CH3, -C(CH3)3 n steht für Werte von 1 bis 12, vorzugsweise für 2, 3, 4, 5, 6. in Mitteln zum Färben und/oder Aufhellen keratinischer Fasern.R 3 and R 4 are independently -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2 , - (CH 2 ) 3 CH 3 , -CH 2 -CH (CH 3 ) 2 , CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3 n is from 1 to 12, preferably from 2, 3, 4, 5, 6 in agents for dyeing and / or lightening keratinic fibers.
16. Verwendung nach Anspruch 15 zur i. Steigerung der Aufhell- bzw. Blondierleistung und/oder ii. Steigerung der Hautverträglichkeit von Aufhell- bzw. Blondiermitteln und/oder iii. Erzielung neutraler Farbergebnisse beim Blondieren und/oder iv. Verringerung von gelben Farbtönen beim Blondieren und/oder v. Verringerung von Vergilbungen auf keratinischen Fasern. 16. Use according to claim 15 for i. Increase in the whitening or bleaching performance and / or ii. Increasing the skin compatibility of brightening or bleaching agents and / or iii. Achieving neutral color results when bleaching and / or iv. Reduction of yellow shades when bleaching and / or v. Reduction of yellowing on keratin fibers.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2344990A1 (en) * 1972-09-14 1974-03-21 Kao Corp MIXTURES FOR ACTIVATING INORGANIC PEROXYD BLEACHING AGENTS
EP0525239A1 (en) * 1991-07-31 1993-02-03 AUSIMONT S.p.A. Process for increasing the bleaching efficiency of an inorganic persalt
JPH09169623A (en) * 1995-10-20 1997-06-30 Yamahatsu Sangyo Kk Hair dye
US20030190297A1 (en) * 2002-04-03 2003-10-09 Saroja Narasimhan Method and compositions for bleaching hair
US20040101497A1 (en) * 1997-11-19 2004-05-27 Britesmile Development, Inc. Tooth whitening compositions
DE102004045353A1 (en) * 2004-09-17 2006-04-06 Cognis Ip Management Gmbh Use of a substance e.g. glycerin, or a composition comprising e.g. glycerin carbonate and a mixture of ethoxylated fatty alcohol for removing oxidation hair colors

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2344990A1 (en) * 1972-09-14 1974-03-21 Kao Corp MIXTURES FOR ACTIVATING INORGANIC PEROXYD BLEACHING AGENTS
EP0525239A1 (en) * 1991-07-31 1993-02-03 AUSIMONT S.p.A. Process for increasing the bleaching efficiency of an inorganic persalt
JPH09169623A (en) * 1995-10-20 1997-06-30 Yamahatsu Sangyo Kk Hair dye
US20040101497A1 (en) * 1997-11-19 2004-05-27 Britesmile Development, Inc. Tooth whitening compositions
US20030190297A1 (en) * 2002-04-03 2003-10-09 Saroja Narasimhan Method and compositions for bleaching hair
DE102004045353A1 (en) * 2004-09-17 2006-04-06 Cognis Ip Management Gmbh Use of a substance e.g. glycerin, or a composition comprising e.g. glycerin carbonate and a mixture of ethoxylated fatty alcohol for removing oxidation hair colors

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