WO2008017668A1 - Agent de lavage et de nettoyage contenant des oxydoréductases et des activateurs de blanchiment - Google Patents
Agent de lavage et de nettoyage contenant des oxydoréductases et des activateurs de blanchiment Download PDFInfo
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- WO2008017668A1 WO2008017668A1 PCT/EP2007/058178 EP2007058178W WO2008017668A1 WO 2008017668 A1 WO2008017668 A1 WO 2008017668A1 EP 2007058178 W EP2007058178 W EP 2007058178W WO 2008017668 A1 WO2008017668 A1 WO 2008017668A1
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- Prior art keywords
- washing
- bleach
- hydrogen peroxide
- cleaning agent
- producing
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- 0 CC(C*(C)(C)ICC(C)O[N+](*)[O-])O[N+](*)[O-] Chemical compound CC(C*(C)(C)ICC(C)O[N+](*)[O-])O[N+](*)[O-] 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
Definitions
- the present invention relates to detergents and cleaners containing hydrogen peroxide-producing oxidoreductases and bleach activators.
- the bleaching agent used may be, for example, directly hydrogen peroxide or peroxygen, alternatively or as a further auxiliary component is the use of bleach catalysts and bleach activators into consideration, the addition to detergents in situ during the washing process allows the formation of bleach-active compounds or . facilitated.
- enzymes for generating hydrogen peroxide in situ are oxidoreductases, especially glucose oxidase.
- the catalyzed reaction is the transfer of electrons from the organic substrate, such as glucose, to oxygen as the electron acceptor to form the desired hydrogen peroxide.
- the glucose oxidase in combination with its substrate glucose can be used in detergents and cleaners for the production of hydrogen peroxide. It is particularly emphasized here that can be dispensed with the use of bleach activators, since the hydrogen peroxide is apparently already produced in an active form, so that the use of bleach activators to activate the hydrogen peroxide is not required. On the one hand, the person skilled in the art will be able to deduce from this document that the addition of glucose is absolutely necessary in order to generate a sufficient amount of hydrogen peroxide and, secondly, the use of bleach activators is not necessary since the hydrogen peroxide already forms in a reactive form.
- WO 89/09813 hydrogen peroxide-producing enzymes can be used in combination with their substrate in detergents and cleaners. This document also shows that the use of substrate to achieve a useful effect is imperative. Furthermore, it is found that these enzymes are actually only conditionally suitable for use in detergents and cleaners, since the amount of hydrogen peroxide produced is very low.
- WO 98/20136 describes a novel glucose oxidase for which it is stated that it can also be used, inter alia, in detergents and cleaners. It is further stated that the detergents and cleaners can also contain bleaches, it also being possible to use, in particular, peracids as the bleaching agent, for the activation of which in turn bleach activators can be used.
- WO 99/02640 describes detergents containing a haloperoxidase.
- a hydrogen peroxide source and an organic acid are necessarily included in the cleaning agents.
- the cleaning agents for activating the peroxy compounds may contain bleach activators.
- a first subject of the present invention is therefore a washing or cleaning agent containing a hydrogen peroxide-producing oxidoreductase and a bleaching assistant selected from bleach activators and bleach catalysts, characterized in that it contains no substrate for the hydrogen peroxide-producing oxidoreductase or is substantially free thereof. Because it is surprising that with a small amount of substrate, as determined by the soiling, by adding bleach activators or bleach catalysts, a significant improvement in the bleaching performance can be effected.
- a further subject of the present invention is furthermore a washing or cleaning agent containing a hydrogen peroxide-producing and sugar oxidizing oxidoreductase and a bleach activator or bleach catalyst, characterized in that it does not contain or is substantially free of a peroxy compound.
- a washing or cleaning agent containing a hydrogen peroxide-producing and sugar oxidizing oxidoreductase and a bleach activator or bleach catalyst characterized in that it does not contain or is substantially free of a peroxy compound.
- the present invention therefore also provides the use of bleaching assistants selected from bleach activators and bleach catalysts for enhancing the action of hydrogen peroxide-producing oxidoreductases, especially in detergents and cleaners, and, conversely, the use of hydrogen peroxide-producing oxidoreductases for enhancing the activity of bleach activators and bleach catalysts, in particular in detergents and cleaners and in particular for removing soiling of textiles, in particular selected from food, beverage, blood and grass stains, especially tea and / or blueberry stains, wherein the washing and cleaning agents are preferably free of substrates for the Oxidoreductase are and / or preferably contain no peroxy compounds or are each substantially free thereof.
- the present invention furthermore relates to the use of bleaching assistants selected from bleach activators and bleach catalysts in combination with oxidoreductases, in particular in detergents and cleaners, for cleaning textiles or surfaces, in particular for removing stains from textiles, in particular selected from foodstuffs, Beverage, blood and grass stains, especially tea and / or blue pepper stains, wherein the washing or cleaning agent preferably contains no peroxy compounds and / or no oxidoreductase substrate or each is substantially free thereof.
- the present invention furthermore relates to the use of bleaching assistants selected from bleach activators and bleach catalysts in combination with oxidoreductases, in particular in detergents and cleaners, for effecting an improved bleaching effect, in particular with regard to food, beverage, blood and grass stains, especially tea and / or blueberry stains, wherein the washing or cleaning agent preferably contains no peroxy compounds and / or no oxidoreductase substrate or each is substantially free thereof.
- composition is “substantially free” of these substances, this possibility should be taken into account. “Substantially free” in this sense means, in particular, that the composition is less than 0.2% by weight, preferably less as 0.1 wt .-%, more preferably less than 0.05 wt .-%, especially less than 0.02 wt .-%, of the respective components.
- the hydrogen peroxide-producing oxidoreductase is preferably an oxidoreductase which produces hydrogen peroxide by using oxygen as an electron acceptor.
- oxidoreductases of EC classes EC 1.1.3 CH-OH as electron donor
- EC 1.2.3 aldehyde or oxo group as electron donor
- EC 1.4.3 CH-NH 2 as donor
- EC 1.7 are used.
- 3 N-containing group as donor
- EC 1.8.3 S-containing group as donor
- Preferred enzymes are in particular selected from the group consisting of malate oxidase (EC 1.1.3.3), glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), cholesterol oxidase (EC 1.1.3.6), Galactose oxidase (EC 1.1.3.9), pyranose oxidase (EC 1.1 .3.10), alcohol oxidase (EC 1.1.3.13), choline oxidase (EC 1.1.3.17, see in particular WO 04/58955), oxidases for long-chain Alcohols (EC 1.1.3.20), glycerol-3-phosphate oxidase (EC 1.1.3.21), cellobiose oxidase (EC 1.1.3.25), Nucleoside oxidase (EC 1.1.3.39), D-mannitol oxidase (EC 1.1.3.40), xylitol oxidase (EC 1.1.3.41), alde
- the hydrogen peroxide-producing oxidoreductase in a preferred embodiment, is one which uses a sugar as an electron donor.
- the hydrogen peroxide-producing and sugar oxidizing oxidoreductase according to the invention is preferably selected from glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), galactose oxidase (EC 1.1.3.9) and pyranose oxidase (EC 1.1.3.10 ).
- Particularly preferred according to the invention is the glucose oxidase (EC 1.1.3.4).
- organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
- the hydrogen peroxide-producing oxidoreductase is preferably used in the detergents and cleaners according to the invention in an amount such that the total composition has an oxidoreductase-related enzyme activity of from 30 U / g to 20,000 U / g, in particular from 60 U / g to 15,000 U / g.
- the unit 1 U corresponds to the activity of that amount of enzyme which converts 1 ⁇ mol of its substrate at pH 7 and 25 0 C in one minute.
- oxidases In addition to the hydrogen peroxide-producing oxidoreductase, it is also possible for further oxidoreductases to be present in the compositions according to the invention, in particular oxidases, oxygenases, laccases (phenol oxidase, polyphenol oxidases) and / or dioxygenases. Suitable commercial products for laccases may be mentioned Denilite® ® 1 and 2 from Novozymes.
- the further oxidoreductase is selected from enzymes which use peroxides as electron acceptors (EC Class 1.11 or 1.11.1), in particular from catalases (EC 1.11.1.6), peroxidases (EC 1.11.1.7), glutathione peroxidases (EC 1.11.1.9), chloride peroxidases (EC 1.11.1.10), manganese peroxidases (EC 1.11.1.13) and / or lignin peroxidases (EC 1.11.1.14), which are generally also summarized under the term peroxidases. Instead or next to these Peroxidases can also be used perhydrolases.
- Perhydrolases formerly also called metal-free haloperoxidases, usually contain the catalytic triad Ser-His-Asp in the reaction center and catalyze the reversible formation of peracids starting from carboxylic acids and hydrogen peroxide.
- perhydrolases which can be used according to the invention, reference may be made in particular to the applications WO 98/45398, WO 04/58961, WO 05/56782 and PCT / EP05 / 06178.
- carboxylic acids, their salts and / or their esters and / or derivatives thereof are accordingly preferably also present in the compositions according to the invention.
- Examples which may be mentioned in general are compounds of the formula R 1 - (R 2 ) m -OR 3 , where
- R 1 is R 4 C (O) - or R 4 C (NR 5 ) -,
- R 3 is hydrogen or optionally substituted, in particular by optionally substituted
- R 4 is hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, heteroaryl or alkylheteroaryl or a group -YR 1a - (R 2a ) o -OR 3a ,
- X and Y are optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, heteroaryl or
- R 2 , R 2a and R 2b represent an alkoxy group
- R 1a represents -C (O) - or -C (NR 5 ) -
- R 1b is R 6 C (O) - or R 6 C (NR 5 ) -,
- R 3a and R 6 represent hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl,
- R 5 is hydrogen or alkyl, m, n and o independently of one another assume a value of 0 to 12.
- carboxylic acids which may optionally be used in the form of their esters and / or salts according to the invention include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, maleic acid, oxalic acid, benzoic acid, citric acid, lactic acid, fruit acids and phthalic acid.
- the carboxylic acids, their salts and / or their esters, if perhydrolases are used preferably in an amount of 0.1 to 20% by weight, more preferably in an amount of 0.5 to 10 wt .-% in the inventive Contain compositions.
- Particularly suitable bleach activators are 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 are substances which carry O- and / or N-acyl groups of said 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 1, 3,4,6 Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetylcitrate (TEOC), Carboxylic acid anhydrides, in particular phthalic anhydride, isoic anhydride and / or succinic an
- Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Likewise, nitrile derivatives such as cyanopyridines, nitrile quats, for example N-alkylammonium acetonitriles, and / or cyanamide derivatives can be used.
- Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate ( OBS 12), as well as N-methylmorpholinum acetonitrile (MMA).
- n-nonanoyl or isononanoyloxybenzenesulfonate n- or isononanoyloxybenzenesulfonate
- UOBS undecenoyloxybenzenesulfonate
- DOBS dodecanoyloxybenzenesulfonate
- bleach activators which can be used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula
- R 1 is -H, -CH 3 , a C 2 - 24 -alkyl or alkenyl radical, a substituted C 2 _ 24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, one
- the bleach activator in a particularly preferred embodiment is TAED.
- the bleach activator is preferably present in the detergents and cleaners according to the invention in an amount of from 0.01 to 20% by weight, preferably in an amount of from 0.1 to 15% by weight, in particular in an amount of from 1 to 10% by weight. -%, especially in an amount of 2 to 5 wt .-%, based on the total composition.
- bleach catalysts may also be included. These substances are bleach-enhancing transition metal salts or transition metal complexes. Suitable transition metals here are in particular Mn, Fe, Co, Ru, Mo, Ti, V or Cu in different oxidation states. Guanidines (Sundermeyer et al., Journal of Molecular Catalysis A: Chemical (2001) 175, 51-63), aminophenols, amine oxides (WO97 / 48786), salenes (EP0846156, EP0630964), sodimines (EP912690), are particularly suitable as complexing ligands. Heterocycles of the phenanthroline type (Chem. Rev.
- lactams (EP1520910), monocyclic and cross-bridged polycyclic polyazaalkanes (EP0458397, EP977828), terpyridines (WO02 / 088289), dendrimers (EP1148117), tetraamido ligands (EP918840), bis- and tetrakis ( pyridylmethyl) alkylamines (EP783035), other N-containing heterocycles (EP1445305, EP0765381), secondary amines (EP0892846), polyoxometalates (EP0761809) and other possible ligands described in the literature.
- complexes of manganese in the oxidation state II, IM, IV or V which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
- ligands are used which have nitrogen donor functions.
- bleach catalyst (s) in the inventive compositions which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1, 4,7-triazacyclononane (Me / TACN).
- macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-
- Bleach catalysts may be used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt. %, in each case based on the total weight of the washing or cleaning agent used. In special cases, however, more bleach catalyst can be used.
- the detergents and cleaning agents according to the invention may be any conceivable type of cleaning agent, both concentrates and agents to be used undiluted, for use on a commercial scale, in the washing machine or in hand washing or cleaning.
- These include, for example, detergents for textiles, carpets, or natural fibers, for which according to the present invention the term laundry detergent is used.
- laundry detergent includes, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather; for such is according to the present Invention uses the term detergent.
- sterilizing and disinfecting agents are to be regarded as detergents and cleaners in the sense of the invention.
- Embodiments of the present invention include all of the prior art and / or all suitable administration forms of the washing or cleaning agents according to the invention. These include, for example, solid, powdery, liquid, gelatinous or pasty agents, optionally also of several phases, compressed or uncompressed; further include, for example: extrudates, granules, tablets or pouches, packed both in large containers and in portions. According to the invention, the use of oxidoreductase and bleach activator in liquid detergents for cleaning textiles has proven to be particularly advantageous, in which hitherto only insufficient bleaching activities could be achieved.
- the washing or cleaning agent contains in addition to the oxidoreductase and the bleach activator surfactant (s), wherein anionic, nonionic, zwitterionic and / or amphoteric surfactants can be used. Preference is given to mixtures of anionic and nonionic surfactants.
- the total surfactant content of the liquid washing or cleaning agent is preferably below 40% by weight and more preferably below 35% by weight, based on the total liquid detergent.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
- alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C 12 .i 4 -alcohols with 3 EO, 4 EO or 7 EO, C 9 . ir alcohol containing 7 EO, C. 13 15- alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 -alcohol with 3 EO and C 12 . 18- alcohol with 7 EO.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
- block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
- nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol representing a glycose moiety having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
- Alkyl glycosides are known, mild surfactants.
- nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
- surfactants are polyhydroxy fatty acid amides of the formula (I)
- RCO for an aliphatic acyl radical having 6 to 22 carbon atoms
- R1 for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or branched one Polyhydroxyalkyl having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
- R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
- R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
- [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- the content of nonionic surfactants in the washing or cleaning agent is preferably 5 to 30 wt .-%, preferably 7 to 20 wt .-% and in particular 9 to 15 wt .-%, each based on the detergent or cleaning agent.
- the washing or cleaning agent may also contain anionic surfactants.
- anionic surfactants for example, those of the sulfonate type and sulfates are used.
- surfactants of the sulfonate type preferably Cg ⁇ -Alkylbenzol- sulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C 12 .i 8 monoolefins having terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
- alkanesulfonates from C 12 - obtained I8 -Al kanen for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
- esters of .alpha.-sulfo fatty acids for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
- sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
- Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
- Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 - preferably C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are suitable anionic surfactants.
- 21 -alcohols such as 2-methyl-branched C ⁇ 11 -AlkOhOIe with an average of 3.5 moles of ethylene oxide (EO) or C 12th 18 fatty alcohols with 1 to 4 EO are suitable. Due to their high foam behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 . 18- fatty alcohol residues or mixtures of these.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
- Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
- alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Particularly preferred anionic surfactants are soaps.
- Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
- the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- the content of anionic surfactants in a washing or cleaning agent may be from 0.1 to 30% by weight, based on the total washing or cleaning agent. However, it is preferred that the amount of anionic surfactants is relatively low to minimize interactions of the anionic surfactants with a possibly present color transfer inhibitor which reduce its effect.
- the washing or cleaning agent therefore contains anionic surfactants in amounts of up to 5 wt .-%. In a particular embodiment, the washing or cleaning agent contains no anionic surfactants at all.
- the washing or cleaning agent may contain exclusively nonionic surfactants.
- the washing or cleaning agent may contain other ingredients which further improve the performance and / or aesthetic properties of the detergent or cleaning agent.
- the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, further enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents , Graying inhibitors, shrinkage inhibitors, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, neutral filler salts, plasticizing components and UV absorbers.
- the group of builders further enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents , Graying inhibitors, shrinkage inhibitors, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides,
- Suitable color transfer inhibitors are, in particular, nitrogen-containing dye transfer inhibitors. It is particularly preferred here for the dye transfer inhibitor to be a polymer or copolymer of cyclic amines, for example vinylpyrrolidone and / or vinylimidazole.
- Suitable color transfer inhibiting polymers include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, and mixtures thereof. Particular preference is given to using polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) as color transfer inhibitor.
- the polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53 available.
- copolymers of vinylpyrrolidone and vinylimidazole used preferably have a molecular weight in the range from 5,000 to 100,000.
- PVP / PVI copolymer for example from BASF under the name Sokalan® HP 56th
- fatty alkyl dialkylhydroxyethylammonium salts as color transfer inhibitors, in particular in admixture with the abovementioned nitrogenous dye transfer inhibitors.
- the fatty alkyl dialkyl hydroxyethyl ammonium salt is in this case preferably a fatty alkyldimethylhydroxyethylammonium salt, more preferably a C 12 -C 18 fatty alkyldimethylhydroxyethylammonium salt. It is particularly preferred that the Fettal kyldimethylhydroxyethylammonium salt C 12 -C 14 -FeWaI kyldimethylhydroxyethylammonium chloride.
- the amount of second color transfer inhibitor, if present, based on the total amount of detergent or cleaning agent is preferably in the range from 0.01 to 2 wt .-%, preferably from 0.05 to 1 wt .-% and particularly preferably from 0, 1 to 0.5 wt .-%.
- Suitable builders which may be present in the washing or cleaning agent are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
- Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
- Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
- amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
- the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
- the term "amorphous” is also understood to mean "X-ray amorphous”.
- the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
- the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
- zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
- zeolite X and mixtures of A, X and / or P are particularly preferred.
- Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) which is sold by SASOL under the brand name VEGOBOND AX ® and by the formula),
- the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
- the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
- Organic builders which may be present in the washing or cleaning agent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
- these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their Offspring as well as mixtures of these.
- Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
- the acids themselves can also be used.
- the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
- citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
- Further useable acidulants are known pH regulators, such as sodium bicarbonate and sodium hydrogen sulfate.
- polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 500 to 70,000 g / mol.
- the molecular weights indicated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were fundamentally determined by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
- Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.
- Suitable polymers may also include substances consisting partly or wholly of units of vinyl alcohol or its derivatives.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
- Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
- Their relative molecular weight, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
- the (co) polymeric polycarboxylates can be used either as an aqueous solution or, preferably, as a powder.
- the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomer.
- biodegradable polymers of more than two different monomer units for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
- copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
- polymeric aminodicarboxylic acids their salts or their precursors.
- polyaspartic acids or their salts and derivatives which, in addition to builder properties, also have a bleach-stabilizing action.
- polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic 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.
- Suitable organic builders are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
- the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
- it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol.
- a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
- DE dextrose equivalent
- oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Also suitable is an oxidized oligosaccharide. A product oxidized to C 6 of the saccharide ring may be particularly advantageous.
- Oxydisuccinates and other derivatives of disuccinates are also other suitable builders.
- ethylenediamine-N, N'-disuccinate (EDDS) preferably in Form of its sodium or magnesium salts used.
- glycerol disuccinates and glycerol trisuccinates are also preferred.
- acetylated hydroxycarboxylic acids or their salts which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
- the washing or cleaning agent is a softening detergent or "2in1."
- the washing or cleaning agent also contains a softening component besides the dye transfer inhibitor and the surfactants.
- the softening component includes, for example, quaternary ammonium compounds such as monoalk (en) yltrimethylammonium compounds, dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines.
- quaternary ammonium compounds such as monoalk (en) yltrimethylammonium compounds, dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines.
- R is an acyclic alkyl radical having 12 to 24 carbon atoms
- R 1 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical
- R 2 and R 3 are either R or R 1 or are an aromatic radical
- X ⁇ represents either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these.
- Examples of cationic compounds of the formula (III) are monotaltrimethylammonium chloride, monostearyltrimethylammonium chloride, didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
- R 4 is an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and / or optionally with substituents
- R 5 is H, OH or O (CO) R 7
- R 6 is, independently of R 5, H, OH or O (CO) R 8
- R 7 and R 8 are each independently an aliphatic alk (ene) ylrest having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
- m, n and p can each independently have the value 1, 2 or 3.
- X can be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these anions.
- R 5 represents the group 0 (CO) R 7 .
- R 5 is the group 0 (CO) R 7 and R 4 and R 7 are alk (en) yl radicals having 16 to 18 carbon atoms.
- R 6 is also OH.
- Examples of compounds of the formula (IV) are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate, bis (palmitoyloxyethyl) hydroxyethyl methyl ammonium methosulfate, 1, 2-bis [tallowloxy] -3-trimethylammonium propane chloride or methyl N, N-bis (stearoyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulphate.
- the acyl groups are preferred whose corresponding fatty acids have an iodine number between 1 and 100, preferably between 5 and 80, more preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular equal to or greater than 60:40.
- Stepan under the tradename Stepantex ® methylhydroxyalkyldialkoyloxyalkylammonium or those known under Dehyquart ® Cognis products, known under Rewoquat ® products from Degussa or those known under Tetranyl® products of Kao.
- Further preferred compounds are the diester quats of the formula (V) which are obtainable under the name Rewoquat® W 222 LM or CR 3099.
- R 21 and R 22 are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
- ester group 0 (CO) R where R is a long-chain alk (en) yl radical
- softening compounds which have the following groups: RO (CO), N (CO) R or RN (CO), where of these groups, N (CO) R groups are preferred.
- R may alternatively be 0 (CO) R, where R is an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X ⁇ is an anion.
- q can take integer values between 1 and 4.
- R 14 is CH 2 - O (CO) R 16 where R 12 , R 13 and R 14 are independently C 1-4 alkyl, alkenyl or hydroxyalkyl, R 15 and R 16 are each independently C 8 . 28 alkyl, X "is an anion and r is a number between O and 5.
- a preferred example of a cationic deposition aid according to formula (VII) is 2,3-bis [tallowacyloxy] -3-trimethylammonium propane chloride.
- plasticizing components which can be used according to the invention are quaternized protein hydrolyzates or protonated amines.
- cationic polymers are also suitable softening component.
- Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, Polyquaternium, also referred to as Merquats.
- polymers Polymer JR, LR and KG series from Amerchol
- polyquaternium-4 copolymers such as graft copolymers having a cellulose backbone and quaternary ammonium groups attached via allyldimethylammonium chloride, cationic cellulose derivatives such as cationic guar such as guar hydroxypropyltriammonium chloride, and similar quaternized guar Derivatives (eg Cosmedia Guar from Cognis or the Jaguar series from Rhodia), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), eg the commercial product Glucquat® 100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride", copolymers of PVP and dimethylaminomethacrylate, copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymers.
- polyquaternized polymers e.g., Luviquat® Care from BASF
- chitin-based cationic biopolymers and their derivatives for example, the polymer available under the trade name Chitosan® (manufacturer: Cognis).
- Some of the cited cationic polymers additionally have skin and / or textile care properties.
- R 17 can be an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, s can assume values between 0 and 5.
- R 18 and R 19 are each independently H, C ⁇ 4 -alkyl or hydroxyalkyl and X ⁇ is an anion.
- softening components include protonated or quaternized polyamines.
- the detergent or cleaning agent may also contain a fabric softening clay, such as bentonite, as a softening component.
- a fabric softening clay such as bentonite
- plasticizing components are alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group.
- alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group.
- Very particular preference is given to N-methyl-N- (2-hydroxyethyl) -N, N- (ditallowacyloxyethyl) ammonium methosulfate or bis (palmitoyloxyethyl) -hydroxyethyl-methylammonium methosulfate.
- the washing or cleaning agent may contain a thickening agent.
- the thickener may, for example, a polyacrylate thickener, xanthan gum, gellan gum, guar gum, alginate, Carrageenan, carboxymethylcellulose, bentonites, wellan gum, locust bean gum, agar-agar, tragacanth, gum arabic, pectins, polyoses, starch, dextrins, gelatin and casein.
- modified natural substances such as modified starches and celluloses, examples which may be mentioned here include carboxymethylcellulose and other cellulose ethers, hydroxyethyl and -propylcellulose and core flour ethers, can be used as thickeners.
- polyacrylic and polymethacrylic thickeners include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry and Fragrance Association (CTFA) ": carbomer), also referred to as carboxyvinyl polymers.
- CFA Cosmetic, Toiletry and Fragrance Association
- Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from BF Goodrich under the trade name Carbopol®, for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight about 250,000) or Carbopol 934 (molecular weight about 3,000,000).
- acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C ⁇ alkanols formed esters (INCI acrylates copolymer), such as the copolymers of methacrylic acid Butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are available, for example, from Rohm & Haas under the trade names Aculyn® and Acusol ® as well as from the company Degussa (Goldschmidt) under the trade name Tego® polymer are available, for example the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (cross-linked), Acusol 810, Acusol 820, Acusol 823 and Acusol 830 (CAS 25852 37-3
- 3 o-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C ⁇ alkanols formed ester include and the example of the Fa. BF Goodrich available under the trade name Carbopol®, for example the hydrophobized Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / C 10 - 30 alkyl acrylate crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473).
- xanthan gum a microbial anionic heteropolysaccharide derived from Xanthomonas campestris and some other species produced under aerobic conditions and has a molecular weight of 2 to 15 million daltons.
- Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
- the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
- a fatty alcohol is also suitable.
- Fatty alcohols may be branched or unbranched, of native origin or of petrochemical origin.
- Preferred fatty alcohols have a C chain length of 10 to 20 C atoms, preferably 12 to 18. Preference is given to using mixtures of different C chain lengths, such as tallow fatty alcohol or coconut fatty alcohol. Examples are Lorol ® Special (C 12 - M -ROH) or Lorol® Technically (C 12 _i 8 -ROH) (both ex Cognis).
- the washing or cleaning agent may contain from 0.01 to 3% by weight and preferably from 0.1 to 1% by weight of thickener.
- the amount of thickener used depends on the type of thickener and the desired degree of thickening.
- Agents according to the invention may comprise further enzymes in addition to the abovementioned oxidoreductases in order to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, Hembellulasen or cellulases, and preferably mixtures thereof. These enzymes are usually of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5 percent by weight based on active protein.
- subtilisin type ones are preferred. Examples thereof are the subtilisin BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense the proteases TW3 and TW7.
- Subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvasrd, Denmark.
- subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 (WO 91/02792) derived under the name BLAP ® variants are derived, which are described in particular in WO 92/21760, WO 95/23221, WO 02/088340 and WO 03/038082 , Other useful proteases from various Bacillus sp. and B. g / ⁇ so / 7 // strains are found in patent applications WO 03/054185, WO 03/056017, WO 03/055974 and WO 03/054184.
- proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP, Purafect Prime ® and Properase.RTM ® from Genencor, that under the trade name Protosol® ® from Advanced Biochembals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, the P under the trade names Proleather® ® and protease ® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzymes available under the name proteinase K-16 from Kao Corp., Tokyo, Japan.
- amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners.
- the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST. Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
- the ⁇ - amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes.
- Further usable commercial products are, for example, the Amylase-LT®, Stainzyme® and Stainzyme Ultra®, the latter also from Novozymes.
- ⁇ -amylase from Bacillus sp. Disclosed in the application WO 02/10356 for this purpose.
- a 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) described in the application WO 02/44350.
- the amylolytic enzymes belonging to the sequence space of ⁇ -amylases defined in the application WO 03/002711 and those described in the application WO 03/054177 can be used.
- fusion products of the molecules mentioned can be used, for example those from application DE 10138753.
- compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
- Lipases are sold, for example, by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
- the cutinases can be used, which were originally isolated from Fusa ⁇ um solani pisi and Humicola insolens.
- useable lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp.
- Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available.
- the Genencor company uses the lipases or cutinases whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusahum solanii.
- Other important commercial products are the originally marketed by Gist-Brocades preparations M1 Lipase ® and Lipomax® ® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ®, Lipase OF ® and lipase PL ® to mention also the product Lumafast® ® from Genencor.
- Detergents according to the invention may contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects.
- These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone washed" effect.
- EG endoglucanase
- Novozymes under the trade name Celluzyme ®.
- the products Endolase® ® and Carezyme ® likewise available from Novozymes, are based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800.
- Further commercial products of this company are Cellusoft® ® and Renozyme ®. The latter is based on the application WO 96/29397 A1.
- Performance-enhanced cellulase variants are disclosed, for example, in the application WO 98/12307 A1.
- the cellulases disclosed in the application WO 97/14804 A1 can be used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ® and Biotouch ®. Further commercial products from AB Enzymes are Econase® ® and ECOPULP ®. Other suitable Cellulases from Bacillus sp. CBS 670.93 and CBS 669.93 are disclosed in WO 96/34092 A2, wherein those derived from Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ® is available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and lndiAge ® Neutra.
- compositions according to the invention may also contain enzymes, which are grouped together under the term hemicellulases, in particular for the removal of certain problem soiling.
- Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 L from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA ,
- a suitable ⁇ -glucanase from a B. alcalophilus is disclosed, for example, in the application WO 99/06573 A1.
- the obtained from B. subtilis beta-glucanase is available under the name Cereflo ® from Novozymes.
- the enzymes used in agents according to the invention are either originally derived from microorganisms, such as the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.
- the purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
- the oxidoreductases as well as the optionally additionally used enzymes can be added in any form established according to the prior art.
- these include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
- these proteins can be adsorbed and / or encapsulated on a solid support for both the solid and liquid dosage forms.
- Encapsulation can be carried out, for example, by spray drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules in which the enzymes are entrapped as in a solidified gel or in core-shell type an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
- further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
- Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
- such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
- the encapsulated form lends itself to protecting the enzymes or other ingredients from other ingredients, such as bleaches, or to allow for controlled release.
- Such capsules are disclosed, for example, in patent applications WO 97/24177 and DE 19918267.
- Another possible encapsulation method is that the proteins are encapsulated in this substance, starting from a mixture of the protein solution with a solution or suspension of starch or a starch derivative. Such an encapsulation process is described in the application WO 01/38471.
- granulation of the enzymes in particular of the oxidoreductase to be used according to the invention, can also be carried out, as described in the application DE 102006018780.
- further sensitive detergent or cleaning agent ingredients such as fragrances, optical brighteners or the bleach activators to be used according to the invention in order to protect them from other components, in particular from any bleaching agents present.
- the sensitive detergent or cleaning agent ingredient is granulated together with a chemically inert carrier material and a chemically inert binder.
- the support material may in this case be selected from inorganic substances, such as, for example, clays, silicates or sulfates, in particular talc, silicic acids, metal oxides, in particular aluminum oxides and / or titanium dioxide, silicates, in particular phyllosilicates, sodium aluminum silicates, bentonites and / or aluminosilicates (zeolites).
- inorganic substances such as, for example, clays, silicates or sulfates, in particular talc, silicic acids, metal oxides, in particular aluminum oxides and / or titanium dioxide, silicates, in particular phyllosilicates, sodium aluminum silicates, bentonites and / or aluminosilicates (zeolites).
- PVA polyvinyl alcohol
- a binder is a solid, waxy or liquid material which is solid at room temperature and which is chemically inert to such an extent that it can not be mixed with any of the ingredients of the production, processing and storage conditions of the granules Granules or agent in an affecting the overall efficiency of the granules extent reacts. It is a different material from the substrate. It is or becomes at least so viscous under the conditions of granule production that it virtually sticks the other ingredients together.
- Suitable binders are inorganic or organic substances which have the properties described, for example non-crosslinked, polymeric compounds selected from the group of polyacrylates, polymethacrylates, methacrylic acid-ethyl acrylate copolymers, polyvinylpyrrolidones, polysaccharides or substituted polysaccharides, in particular cellulose ethers, and / or polyvinyl alcohols (PVA), preferably partially hydrolyzed polyvinyl alcohols and / or ethoxylated polyvinyl alcohols and their copolymers and mixtures.
- PVA or its derivatives are suitable both as a carrier material and as a binder component due to their adsorption properties and their co-existing binding effect. They can therefore be used as binders, if they are not already used as a carrier material.
- a protein contained in an agent according to the invention in particular also the oxidoreductase according to the invention, can be protected during storage against damage such as for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage.
- damage such as for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage.
- inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
- Preferred agents according to the invention contain stabilizers for this purpose.
- One group of stabilizers are reversible protease inhibitors.
- Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted Phenylboronic, in particular 4-formylphenyl-boronic acid, or the salts or esters of said compounds.
- peptide aldehydes that is, oligopeptides with reduced C-terminus, in particular those of 2 to 50 monomers are used for this purpose.
- the peptidic reversible protease inhibitors include ovomucoid and leupeptin.
- specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.
- enzyme stabilizers are aminoalcohols, such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to Ci 2, such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.
- Lower aliphatic alcohols but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers.
- Di-glycerol phosphate also protects against denaturation due to physical influences.
- calcium and / or magnesium salts are used, such as calcium acetate or calcium formate.
- Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
- Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors.
- Other polymeric stabilizers are linear C 8 -C 8 polyoxyalkylenes.
- alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and are able, preferably, to additionally increase their performance.
- Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase.
- Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation;
- sulfur-containing reducing agents are familiar.
- Other examples are sodium sulfite and reducing sugars.
- peptide-aldehyde stabilizers for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate Polyols or polyamino compounds and with reducing salts.
- the effect of peptide-aldehyde stabilizers is favorably enhanced by the combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions.
- the proteins - polypeptides according to the invention as well as optionally contained further enzymes - can be used, for example, in dried, granulated and / or encapsulated form. They may be added separately, ie as a separate phase, or with other ingredients together in the same phase, with or without compaction. If microencapsulated enzymes are to be processed in solid form, the water can be removed by methods known from the prior art from the aqueous solutions resulting from the workup, such as spray drying, centrifuging or by solubilization. The particles obtained in this way usually have a particle size between 50 and 200 microns.
- the proteins may be added to liquid, gelatinous or pasty agents according to the invention in a concentrated aqueous or non-aqueous solution, suspension or emulsion starting from a protein recovery and preparation carried out in the prior art, but also in gel form or encapsulated or as a dried powder.
- Such detergents or cleaners according to the invention are generally prepared by simple mixing of the ingredients which can be added in bulk or as a solution in an automatic mixer.
- the proportion of the enzymes, the enzyme liquid formulation (s) or the enzyme granules in a washing or cleaning agent may, for example, be about 0.01 to 5% by weight, preferably 0.12 to about 2.5% by weight.
- electrolyte ⁇ from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl 2 in the textile treatment agents is preferred. The proportion of electrolytes in the washing or cleaning agent is usually 0.1 to 5 wt .-%.
- Non-aqueous solvents that can be used in the washing or cleaning agent, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range.
- the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, Propanediol or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, -ethyl or -propyl ether, dipropylene glycol monomethyl- or ethyl ether, di-isopropylene
- pH adjusters In order to bring the pH of the washing or cleaning agent in the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 10% by weight of the total formulation.
- the pH of the washing or cleaning agent is preferably between 4 and 10 and preferably between 5.5 and 8.8.
- the washing or cleaning agent contains one or more perfumes in an amount of usually up to 10 wt .-%, preferably 0.01 to 5 wt .-%, in particular 0.3 to 3 wt .-%.
- perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
- perfume oils may also contain natural fragrance mixtures as are available from plant sources.
- Suitable dyes In order to improve the aesthetic impression of the washing or cleaning agent, they can be dyed with suitable dyes.
- Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the textile treatment agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
- Suitable foam inhibitors which can be used in the detergents or cleaners are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.
- Suitable soil release polymers also referred to as "anti-redeposition agents” include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose having a methoxy group content of 15 to 30 wt% and hydroxypropyl groups of 1 to 15 wt%, respectively based on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionic and / or nonionic modified derivatives of Suitable derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers.
- Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
- Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
- cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the total amount of detergent or cleaning agent ,
- the detergents or cleaning agents may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
- the textile treatment agents may contain antimicrobial agents.
- bacteriostatic agents and bactericides, fungistatics and fungicides, etc.
- Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with in these detergents or cleaners ,
- the textile treatment agents according to the invention may contain preservatives, it being preferred to use only those which have no or only a low skin-sensitizing potential.
- preservatives examples are sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, formic acid and its salts, 3-iodo-2-propynyl-butylcarbamate, sodium N- (hydroxymethyl) glycinate, biphenyl-2-ol and Mixtures thereof.
- a suitable preservative is the solvent-free, aqueous combination of diazolidinyl urea, sodium benzoate and potassium sorbate (available as Euxyl® K 500 ex Schuelke & Mayr), which can be used in a pH range up to 7.
- the detergents or cleaners may contain antioxidants.
- This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites, phosphonates and vitamin E.
- Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
- External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as anti- Statika for textile fabrics or as an additive to textile treatment agents, wherein additionally a softening effect is achieved.
- silicone derivatives may be used in the fabric treatment agents. These additionally improve the rinsing behavior of the washing or cleaning agents by their foam-inhibiting properties.
- Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
- Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
- the viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C., wherein the silicones can be used in amounts of between 0.2 and 5% by weight, based on the total amount of detergent or cleaning agent.
- the washing or cleaning agent may also contain UV absorbers, which are applied to the treated fabrics and improve the light resistance of the fibers.
- UV absorbers include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
- Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), methylglycinediacetic acid trisodium salt (MGDA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
- EDTA ethylenediaminetetraacetic acid
- NTA nitrilotriacetic acid
- MGDA methylglycinediacetic acid trisodium salt
- anionic polyelectrolytes such as polymaleates and polysulfonates.
- a preferred class of complexing agents are the phosphonates present in the detergent or cleaning agent in amounts of 0.01 to 2.5% by weight, preferably 0.02 to 2% by weight and in particular 0.03 to 1, 5 wt .-% are included.
- These preferred compounds include in particular organophosphonates such as, for example, 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2,4-tricarboxylic acid ( PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
- organophosphonates such as, for example, 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2,
- the washing or cleaning agents according to the invention can be used for washing and / or cleaning textile fabrics, in particular dyed textile fabrics, and in particular for removing tea and / or blueberry stains.
- a base formulation can be prepared first by conventional methods and methods in which, for example, the constituents of the base formulation are simply mixed in stirred tanks, water, non-aqueous solvents and surfactants are advantageously presented and the other components, hydrogen peroxide oxidoreductase and bleach activator and / or bleach catalyst (optionally in encapsulated form) to be produced. Separate heating in the production is not required. If desired, the temperature of the mixture should not exceed 80 ° C.
- FIG. 1 shows the washing performance of the glucose oxidase in relation to the soils blueberry and tea, in each case in the presence of glucose and / or TAED. Specifically, from left to right: a) Washing performance of the glucose oxidase in the absence of glucose and TAED, b) Washing performance of the glucose oxidase in the presence of glucose without TAED, c) Washing performance of the glucose oxidase in the presence of TAED without glucose , d) Washing power of the glucose oxidase in the presence of glucose and TAED.
- the left bar shows the washing performance in relation to blueberry, the right one the washing performance in relation to tea.
- Table 1 Formulations of detergents and cleaners according to the invention
- Oxygo HPL5000 (Genencor) was used as oxidase in the following oxidase wash test and TAED (technical product) as bleach activator.
- the soils tested in the washing test were blueberry juice on cotton (product no. C15 from CFT BV Viaardingen, Holland) and tea on cotton (product no. 167, Swiss Federal Institute of Materials and Testing (EMPA) Testmaterialien AG, St. Gallen, Switzerland) Washing tests, the detergent matrix shown in Table 1 was used.
- Table 1 Frame formulation for a laundry detergent
- Nonionic surfactant (FAEO, APG, et al.) 24-28
- test tissues round pieces of the test tissues (diameter 10 mm) were incubated in a 48-well microtiter plate in 1 ml of wash liquor for 60 min at 40 ° C. and a shaking frequency of about 600 rpm. After incubation, triple rinsing of the test tissues followed by drying and fixation.
- the whiteness of the laundered fabrics was measured in comparison with a white standard (d / 8, 8 mm, SCI / SCE) which had been normalized to 100% (determination of the L value).
- the measurement was carried out on a colorimeter (Minolta Cm508d) with an illumination setting of 107D65. The results obtained are reported as percent power, normalizing the difference in remission values from the base detergent without enzymes to that with oxidase and substrate with bleach booster or catalyst to 100%.
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Abstract
La présente invention concerne un agent de lavage et de nettoyage contenant des oxydoréductases produisant du peroxyde d'hydrogène et des activateurs de blanchiment et/ou des catalyseurs de blanchiment.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE200610037440 DE102006037440A1 (de) | 2006-08-09 | 2006-08-09 | Wasch- und Reinigungsmittel enthaltend Oxidoreduktasen und Bleichaktivatoren |
DE102006037440.1 | 2006-08-09 |
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WO2008017668A1 true WO2008017668A1 (fr) | 2008-02-14 |
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PCT/EP2007/058178 WO2008017668A1 (fr) | 2006-08-09 | 2007-08-07 | Agent de lavage et de nettoyage contenant des oxydoréductases et des activateurs de blanchiment |
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WO (1) | WO2008017668A1 (fr) |
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CN113046196A (zh) * | 2019-12-27 | 2021-06-29 | 张家港迪克汽车化学品有限公司 | 固态清洗液浓缩剂及其制备方法和应用 |
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DE102007036392A1 (de) * | 2007-07-31 | 2009-02-05 | Henkel Ag & Co. Kgaa | Zusammensetzungen enthaltend Perhydrolasen und Alkylenglykoldiacetate |
DE102010039814A1 (de) * | 2010-08-26 | 2012-03-01 | Henkel Ag & Co. Kgaa | Enzym-haltiges maschinelles Geschirrspülmittel |
DE102021114332A1 (de) | 2021-06-02 | 2022-12-08 | Henkel Ag & Co. Kgaa | Stabilisierung von enzymen durch phenoxyethanol |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0538228A1 (fr) * | 1991-10-14 | 1993-04-21 | The Procter & Gamble Company | Détergents avec additifs pour éviter le transfert de colorant |
US5288746A (en) * | 1992-12-21 | 1994-02-22 | The Procter & Gamble Company | Liquid laundry detergents containing stabilized glucose/glucose oxidase as H2 O2 generation system |
WO1995029996A1 (fr) * | 1994-05-03 | 1995-11-09 | Novo Nordisk A/S | Glucose-oxydase alcaline |
WO1996002623A1 (fr) * | 1994-07-18 | 1996-02-01 | Genencor International Inc. | Compositions enzymatiques d'activateur de blanchiment |
US20050256016A1 (en) * | 2004-05-17 | 2005-11-17 | The Procter & Gamble Company | Bleaching composition comprising a carbohydrate oxidase |
-
2006
- 2006-08-09 DE DE200610037440 patent/DE102006037440A1/de not_active Withdrawn
-
2007
- 2007-08-07 WO PCT/EP2007/058178 patent/WO2008017668A1/fr active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0538228A1 (fr) * | 1991-10-14 | 1993-04-21 | The Procter & Gamble Company | Détergents avec additifs pour éviter le transfert de colorant |
US5288746A (en) * | 1992-12-21 | 1994-02-22 | The Procter & Gamble Company | Liquid laundry detergents containing stabilized glucose/glucose oxidase as H2 O2 generation system |
WO1995029996A1 (fr) * | 1994-05-03 | 1995-11-09 | Novo Nordisk A/S | Glucose-oxydase alcaline |
WO1996002623A1 (fr) * | 1994-07-18 | 1996-02-01 | Genencor International Inc. | Compositions enzymatiques d'activateur de blanchiment |
US20050256016A1 (en) * | 2004-05-17 | 2005-11-17 | The Procter & Gamble Company | Bleaching composition comprising a carbohydrate oxidase |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113046196A (zh) * | 2019-12-27 | 2021-06-29 | 张家港迪克汽车化学品有限公司 | 固态清洗液浓缩剂及其制备方法和应用 |
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