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WO1999033947A1 - Utilisation de complexes de metaux de transition avec des ligands dendrimeres pour renforcer l'effet de blanchiment de composes peroxygene - Google Patents

Utilisation de complexes de metaux de transition avec des ligands dendrimeres pour renforcer l'effet de blanchiment de composes peroxygene Download PDF

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Publication number
WO1999033947A1
WO1999033947A1 PCT/EP1998/008251 EP9808251W WO9933947A1 WO 1999033947 A1 WO1999033947 A1 WO 1999033947A1 EP 9808251 W EP9808251 W EP 9808251W WO 9933947 A1 WO9933947 A1 WO 9933947A1
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Prior art keywords
weight
complex
dendrimer
transition metal
ligands
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PCT/EP1998/008251
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German (de)
English (en)
Inventor
Helmut Blum
Lars Züchner
Horst-Dieter Speckmann
Dirk Thissen
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Priority claimed from DE19809713A external-priority patent/DE19809713A1/de
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to JP2000526606A priority Critical patent/JP2002500242A/ja
Priority to EP98966629A priority patent/EP1042444A1/fr
Publication of WO1999033947A1 publication Critical patent/WO1999033947A1/fr

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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 the use of certain transition metal complex compounds for enhancing the bleaching action of, in particular, inorganic peroxygen compounds when bleaching colored stains both on textiles and on hard surfaces, and on detergents and cleaning agents which contain such complex compounds.
  • Inorganic peroxygen compounds in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes.
  • the oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H 2 O 2 or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous suggestions, especially from the classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate, and known became.
  • bleach activators for which numerous suggestions, especially from the classes of the N- or O-acyl compounds, for example multiply acylated alky
  • the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the peroxide liquor alone at 95 ° C.
  • application temperatures significantly below 60 ° C, in particular below 45 ° C, down to the cold water temperature have become increasingly important in recent years.
  • transition metal complex compounds with certain dendrimer ligands make a significant contribution to cleaning performance against colored stains which are found on textiles or on hard surfaces. This contribution can be further increased if the complexes are used in combination with compounds which split off peroxocarboxylic acid under perhydrolysis conditions.
  • the invention relates to the use of complexes of the transition metals cobalt, manganese, iron, ruthenium, vanadium, molybdenum, tungsten or mixtures thereof, which carry one or more dendrimer ligands of the polyamidoamine type, as activators for, in particular, inorganic peroxygen compounds in aqueous solutions for Textile laundry and in aqueous cleaning solutions for hard surfaces, in particular for dishes, and their use in corresponding solutions for bleaching colored stains.
  • Dendrimer ligand molecules of the polyamidoamine type correspond to structure I shown below:
  • the initiator core is preferably ammonia or ethylenediamine. Transition metal complexes with dendrimer ligands of generations 3.5 and 4.0 are preferably used.
  • the dendrimers can be loaded with stoichiometrically different amounts of transition metal. In the maximum case, all nitrogen atoms or carboxylate groups of the dendrimer are saturated with transition metal.
  • the molar ratio of transition metal to dendrimer ligand is preferably in the range from 1: 1 to 2 n + 1 : 1, where n indicates the generation of the dendrimer, that is, in Complexes with generation 2 dendrimer ligands preferably have a molar ratio in the range from 1: 1 to 8: 1, in particular 3: 1 to 7: 1, with generation 3 dendrimer ligands preferably in the range from 1: 1 to 16: 1 , in particular 6: 1 to 14: 1, with generation 4 dendrimer ligands, preferably in the range from 1: 1 to 32: 1, in particular 8: 1 to 28: 1, with the dendrimer ligands Generation
  • transition metals in the complexes to be used according to the invention depending on the metal, have oxidation states in the range from +11 to + V.
  • Cobalt and / or molybdenum are among the particularly preferred transition metals in the complexes to be used according to the invention; in these cobalt is preferably in the oxidation states +11 or + III and molybdenum is preferably in the oxidation states + IV or + V.
  • Dendrimer complexes with metals with mixed oxidation numbers and / or several different transition metals are also possible, the combination of the transition metals cobalt and manganese providing particularly good results.
  • This can be, in particular, the combination of Co (II) with Mn (III), of Co (III) with Mn (II) or preferably the combination of Co (III) with Mn (III).
  • the complexes to be used according to the invention contain different metals or a metal in different oxidation states, the molar ratio of these metals in the complex is preferably 1:30 to 30: 1, in particular 1: 2 to 2: 1 and particularly preferably about 1: 1.
  • corresponding mixtures of several complexes with dendrimer ligand and one metal each can be used.
  • the complex compounds to be used according to the invention can also carry further ligands, generally of a simpler structure, in particular neutral or mono- or polyvalent anion ligands.
  • ligands generally of a simpler structure, in particular neutral or mono- or polyvalent anion ligands. Examples include water, nitrate, acetate, formate, citrate, perchlorate and the halides such as chloride, bromide and iodide as well as complex anions such as hexafluorophosphate.
  • the anion ligands ensure charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible.
  • oligomeric multinuclear complexes are formed with at least one dendrimer ligand.
  • the dendrimer ligand can be reacted with transition metal salts in common solvents such as, for example, acetone or methanol.
  • Bleach-effective mixed metal-containing dendritic transition complexes are also obtained by loading the dendrimers with two or more different transition metals in different mass ratios.
  • the complexes to be used according to the invention as bleaching catalysts generally form already at room temperature and are normally obtained in crystalline form from common solvents.
  • bleaching is understood here to mean both the bleaching of dirt located on the textile surface and the bleaching of dirt located in the wash liquor and detached from the textile surface. The same applies mutatis mutandis to the bleaching of stains on hard surfaces, in particular tea.
  • the invention further relates to a process for cleaning textiles and also hard surfaces, in particular dishes, using the above-mentioned complex compounds in aqueous, optionally further detergent or cleaning agent components, in particular solution containing oxidizing agents based on peroxygen, and detergents and cleaning agents for hard surfaces , in particular cleaning agents for dishes, those which contain such complex compounds being preferred for use in machine processes.
  • the use according to the invention essentially consists in creating, in the presence of a hard surface contaminated with colored soiling or a correspondingly soiled textile, conditions under which a peroxidic oxidizing agent and the complex compound can react with one another with the aim of obtaining secondary products having a more oxidizing effect.
  • Such conditions exist in particular when the reactants meet in aqueous solution.
  • This can be done by adding the peroxygen compound and the complex separately to an optionally detergent-containing solution.
  • the method according to the invention is particularly advantageous when using a detergent according to the invention or detergent.
  • Hard surface cleaning agent which contains the complex compound and optionally a peroxygen-containing oxidizing agent.
  • the peroxygen compound can also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a detergent or cleaning agent free of peroxygen is used.
  • the conditions can be varied widely depending on the intended use. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents are also suitable as the reaction medium.
  • the amounts of peroxygen compounds are generally chosen so that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen, are present in the solutions.
  • the amount of bleach-enhancing complex compound used also depends on the application. Depending on the desired degree of activation, it is used in amounts such that 0.01 mmol to 25 mmol, preferably 0.1 mmol to 2 mmol, of complex per mol of peroxygen compound are used, but in special cases these limits can also be exceeded or fallen below.
  • Washing and cleaning agents according to the invention preferably contain 0.0025% by weight to 0.25% by weight, in particular 0.01% by weight to 0.1% by weight, of the bleach-enhancing complex compound defined above.
  • the detergents and cleaning agents according to the invention which can be present as granules, powdery or tablet-like solids, as other moldings, homogeneous solutions or suspensions, can, in addition to the bleach-boosting active ingredient mentioned, in principle contain all known ingredients which are customary in such agents.
  • the agents according to the invention can in particular contain builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, sequestering agents, enzymes, electrolytes, pH regulators and further auxiliaries, such as silver corrosion inhibitors, foam regulators, additional peroxygen activators as well as colorants and fragrances.
  • a cleaning agent according to the invention for hard surfaces can also contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls and mixtures thereof.
  • Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight.
  • the agents can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • surfactants are present in detergents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, whereas cleaning agents for hard surfaces normally have smaller proportions, ie Amounts up to 20% by weight, in particular up to 10% by weight and preferably in the range from 0.5% by weight to 5% by weight are contained.
  • Extremely low-foaming compounds are normally used in cleaning agents for use in machine dishwashing processes.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • Preferred surfactants of the sulfonate type are C - C ⁇ -alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 2 -C 1 monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates the 2 -C ⁇ 8 alkanes are obtained for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization from Ci.
  • esters of ⁇ -sulfofatty acids esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which have from 8 to by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or Tallow fatty acids are preferably the ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or Tallow fatty acids, it also being possible for sulfonation products of unsaturated fatty acids, for example oleic acid, to be present in small amounts, preferably in amounts not above about 2 to 3% by weight.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the methyl esters of ⁇ -sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.
  • Alk (en) yl sulfates are the alkali metal and especially sodium salts are the Schwefelhoffester of the C 2 -C] fatty alcohols, for example, from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ⁇ o-C 0 oxoalcohols and Half-secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Cj -C 16 alkyl sulfates and Ci 2 -Ci 5 alkyl sulfates and C 4 -C 5 alkyl sulfates are particularly preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, in accordance with US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C -C 2 r alcohols ethoxylated with 1 to 6 mol ethylene oxide such as 2-methyl branched C 9 -C 1 1 alcohols with an average of 3.5 mol ethylene oxide (EO) or C ⁇ 2 - C ⁇ 8 fatty alcohols with 1 to 4 EO. Because of their high foaming behavior, they are normally used in washing and cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred Sulfosuccinates contain C 8 to C 8 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Fatty acid derivatives of amino acids for example of N-methyl taurine (tauride) and / or of N-methyl glycine (sarcoside) are also suitable as further anionic surfactants.
  • the sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred.
  • Soaps for example in amounts of 0.2% by weight to 5% by weight, are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are particularly suitable, 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 or tallow fatty acids.
  • the known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.
  • the anionic surfactants can 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 in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Anionic surfactants are preferably present in detergents according to the invention in amounts of 1% by weight to 30% by weight and in particular in amounts of 5% by weight to 25% by weight.
  • 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 radical has a linear or preferably 2-methyl branching can be or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 1 -C ] alcohols with 3 EO or 4 EO, Cp-C ⁇ alcohols with 7 EO, C 13 -C 5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C I2 -C ⁇ 8 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ⁇ 2 -C ⁇ 4 alcohol with 3 EO and C 12 - C is alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)
  • R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
  • R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred
  • [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that ethoxylated fatty alcohols, especially not more than half of them.
  • So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups per molecule. These groups are usually separated from one another by a so-called "spacer".
  • This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • the term gemini surfactants is understood not only to mean “dimeric” but also "trimeric” surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061.
  • End group-blocked dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are particularly characterized by their bi- and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides as described in international patent applications WO 95/19953, WO 95/19954 and WO 95/19955 can also be used.
  • a detergent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also polyaspartic acid, polyphosphonic acids, in particular aminotris (methylene-phosphinophenonic acid), ethylenediamine (1) ethylenediamine (1) 1-diphosphonic acid, as well as polymeric (poly) carboxylic acids, in particular the polycarboxyla- accessible by oxidation of polysaccharides or dextrins.
  • polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof which can also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form.
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • Terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as monomers can also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an alkylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical , his.
  • Such polymers can be produced in particular by processes which are described in German patents DE 42 21 381 and DE 43 00 772, and generally have a relative molecular weight of between 1,000 and 200,000.
  • copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in pasty or liquid, in particular water-containing agents.
  • Particularly suitable water-soluble inorganic builder materials are alkali silicates and polymeric alkali phosphates, which can be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of this are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • As water-insoluble, water-dispersible inorganic builder materials crystalline or amorphous alkali, in 50 , preferably not more than 40% by weight and in liquid compositions in particular from 1% by weight to 5% by weight.
  • the crystalline sodium aluminosilicates in detergent quality in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from the zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta SpA), are preferred .
  • Amounts close to the above upper limit are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • Their calcium binding capacity which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali silicates which can be used as builders preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Crystalline sheet silicates of the general formula Na 2 Si x O x + ⁇ H 2 O are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 ⁇ 5 y H 2 O
  • ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171.
  • ⁇ -sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
  • Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 425 428 described, can be used.
  • a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0436 835.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention.
  • a granular compound of alkali silicate and alkali carbonate is used, as is described, for example, in international patent application WO 95/22592 or as is commercially available, for example, under the name Nabion® 15.
  • alkali aluminosilicate in particular zeolite
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • Such builder substances are preferably contained in the inventive agents in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • Suitable water-soluble builder components in cleaning agents according to the invention for hard surfaces are in principle all builders commonly used in agents for the mechanical cleaning of dishes, for example the abovementioned alkali metal phosphates. Their amounts can range from up to about 60% by weight, in particular 5% by weight to 20% by weight, based on the total composition.
  • other possible water-soluble builder components are, for example, organic polymers of native or synthetic origin from the type of polycarboxylates listed above, which act in particular in hard water regions as co-builders, and naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic acid, ⁇ - Hydroxypropionic acid and gluconic acid.
  • the preferred organic builder components include the salts of citric acid, especially sodium citrate.
  • Anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable as sodium citrate.
  • Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to the co-builder salts mentioned can also be present.
  • Suitable bleaches based on oxygen are primarily alkali perborate or tetrahydrate and / or alkali percarbonate, with sodium being the preferred alkali metal.
  • the use of sodium percarbonate has advantages in particular in cleaning agents for dishes, since it has a particularly favorable effect on the corrosion behavior on glasses.
  • the oxygen-based bleach is therefore preferably an alkali percarbonate, especially sodium percarbonate.
  • known peroxycarboxylic acids for example dodecanediperic acid or phthalimidopercarboxylic acids, which can optionally be substituted on the aromatic, can also be present.
  • bleach stabilizers such as phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as magnesium sulfate may be useful.
  • bleach activators and / or conventional bleach activators that is to say compounds which, under perhydrolysis conditions, give substituted or unsubstituted perbenzoic acid and / or peroxocarboxylic acids having 1 to 10 C atoms, in particular 2 to 4 C atoms become.
  • Suitable are the conventional bleach activators cited at the outset which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenyls are preferred , in particular nonanoyl or isononanoyloxybenzenesulfonate, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyllactylfactyl and pentaacet
  • the enzymes optionally contained in agents according to the invention include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamyl®.
  • the enzymes used can, as described, for example, in international patent applications WO 92/11347 or WO 94/23005, be adsorbed on carriers and / or be embedded in coating substances in order to protect them against premature inactivation.
  • washing and cleaning agents are contained in washing and cleaning agents according to the invention preferably in amounts of up to 10% by weight, in particular from 0.05% by weight to 5% by weight, particular preference being given to enzymes stabilized against oxidative degradation, such as, for example known from international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350.
  • Machine dishwashing detergents according to the invention preferably contain the customary alkali carriers such as, for example, alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 40% by weight, in particular 3 % By weight to 30% by weight, based on the total composition, may be present.
  • the alkali carrier system preferably used in cleaning agents according to the invention is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which can be present in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight .
  • Another subject matter of the invention is an agent for machine cleaning of dishes, containing 15% by weight to 65% by weight, in particular 20% by weight to 60% by weight of water-soluble builder component, 5% by weight to 25% by weight. %, in particular 8% by weight to 17% by weight, oxygen-based bleaching agent, in each case based on the total agent, and 0.01% by weight to 1% by weight of one or more of the complex compounds defined above.
  • Such an agent is preferably lower alkaline, ie its 1% by weight solution has a pH of 8 to 11.5, in particular 9 to 11.
  • agents for automatic cleaning of dishes according to the invention, 20% by weight to 60% by weight of water-soluble organic builders, in particular alkali citrate, 3% by weight to 20% by weight of alkali carbonate and 3% by weight to 40 Contain wt .-% alkali disilicate.
  • silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
  • Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trivalent phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, molybdenum, vanadium or cerium salts and / or complexes, in which the metals mentioned are present in one of the oxidation states II, III, IV, V or VI, depending on the metal, and salts and / or complexes of the metals present in the complexes suitable according to the invention with ligands other than those specified in formula (I).
  • organic sulfides such as cystine and cysteine, di- or trivalent phenols
  • optionally alkyl- or aryl-substituted triazoles such as benzotriazole
  • isocyanuric acid titanium, zir
  • the agents foam too much during use, for example in the presence of anionic surfactants, they can still contain up to 6% by weight, preferably about 0.5% to 4% by weight, of a foam-regulating compound the group comprising silicone oils, paraffins, paraffin-alcohol combinations, hydrophobized silicas, bisfatty acid amides and their mixtures and other other known commercially available foam inhibitors can be added.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.
  • Other optional ingredients in the agents according to the invention are, for example, perfume oils.
  • the organic solvents which can be used in the agents according to the invention include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms , in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned.
  • Such water-miscible solvents are found in the cleaning agents according to the invention. preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight, is present.
  • the agents according to the invention can contain system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides.
  • Such pH regulators are preferably not contained in the agents according to the invention in excess of 10% by weight, in particular from 0.5% by weight to 6% by weight.
  • compositions of the invention are preferably in pulverulent, granular or tablettenfö '-shaped preparations before that, in per se known manner, for example by mixing, granulation, roll compaction and / or by spray drying the thermally loadable components and admixing the more sensitive components, including in particular enzymes Bleach and the bleaching catalyst can be expected to be produced.
  • Agents according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • Agents according to the invention can be produced in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l by also carrying out the builder components with at least a portion of liquid mixture components in a first process stage mixed by increasing the bulk density of this premix and subsequently - if desired after a Intermediate drying - the other components of the agent, including the bleach catalyst, combined with the premix obtained in this way.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with compression pressures in the range from 200 10 5 Pa to 1 500 10 5 Pa .
  • a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • Example 1 Preparation of a cobalt (H) -polyamidoamine complex
  • a cobalt (III) / Mn (III) - polyamidoamine complex (B6) was produced using a 4th generation polyamidoamine dendrimer, cobalt (II) chloride hexahydrate and Mn (III) chloride in which the molar ratio of Co to Mn to dendrimer ligand was 16: 16: 1.
  • a 1: 1 mixture of the cobalt (III) - polyamidoamine complex (B4) with a corresponding Mn (III) -polyamidoamine complex was prepared (B7), so that the molar ratio of Co to Mn to dendrimer in the mixture Ligand was also 16: 16: 1.

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  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Detergent Compositions (AREA)

Abstract

L'invention vise à améliorer l'effet d'oxydation et de blanchiment de composés peroxygène inorganiques à des températures peu élevées. A cette fin, il est prévu principalement d'utiliser des complexes de métaux de transition, comportant un ou plusieurs ligands dendrimères de type polyamidoamine. Des détergents et des nettoyants, par exemple des agents s'utilisant notamment pour le lavage de vaisselle en machine, contiennent approximativement entre 0,0025 et 0,25 % en poids d'un principe actif de ce type, renforçant l'effet de blanchiment.
PCT/EP1998/008251 1997-12-24 1998-12-16 Utilisation de complexes de metaux de transition avec des ligands dendrimeres pour renforcer l'effet de blanchiment de composes peroxygene WO1999033947A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2000526606A JP2002500242A (ja) 1997-12-24 1998-12-16 過酸素化合物の漂白効果を強化するためのデンドリマー配位子を有する遷移金属錯体の使用
EP98966629A EP1042444A1 (fr) 1997-12-24 1998-12-16 Utilisation de complexes de metaux de transition avec des ligands dendrimeres pour renforcer l'effet de blanchiment de composes peroxygene

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19757918 1997-12-24
DE19809713.1 1998-03-06
DE19809713A DE19809713A1 (de) 1997-12-24 1998-03-06 Verwendung von Übergangsmetallkomplexen mit Dendrimer-Liganden zur Verstärkung der Bleichwirkung von Persauerstoffverbindungen
DE19757918.3 1998-03-06

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WO1999033947A1 true WO1999033947A1 (fr) 1999-07-08

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012000846A1 (fr) 2010-06-28 2012-01-05 Basf Se Composition de blanchiment dépourvue de métal
WO2013060708A1 (fr) 2011-10-25 2013-05-02 Basf Se Utilisation de copolymères en peigne ou séquencés comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie
WO2013060706A1 (fr) 2011-10-25 2013-05-02 Basf Se Utilisation de copolymères d'acrylate comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie
WO2014154508A1 (fr) 2013-03-27 2014-10-02 Basf Se Copolymères blocs comme agents de libération de la saleté dans des procédés de blanchisserie
CN104403839A (zh) * 2014-12-26 2015-03-11 苏州龙腾万里化工科技有限公司 一种清洗剂制造方法
WO2017186480A1 (fr) 2016-04-26 2017-11-02 Basf Se Composition de blanchiment sans métal
US10214606B2 (en) 2013-11-27 2019-02-26 Basf Se Random copolymers as soil release agents in laundry processes
EP3524347A1 (fr) 2008-04-09 2019-08-14 Basf Se Utilisation de composés complexes hydrazides métalliques en tant que catalyseurs d'oxydation

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD141844A1 (de) * 1978-12-28 1980-05-21 Rudolf Opitz Bleichmittel
EP0509787A2 (fr) * 1991-04-17 1992-10-21 Unilever Plc Compositions détergentes concentrées en poudre
US5194416A (en) * 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
US5338532A (en) * 1986-08-18 1994-08-16 The Dow Chemical Company Starburst conjugates
WO1997014443A1 (fr) * 1995-10-19 1997-04-24 Bracco International B.V. Substances chimiotactiques marquees magnetiquement comme agents de contraste pour l'imagerie par rmn de tissus vivants cibles
DE19605688A1 (de) * 1996-02-16 1997-08-21 Henkel Kgaa Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD141844A1 (de) * 1978-12-28 1980-05-21 Rudolf Opitz Bleichmittel
US5338532A (en) * 1986-08-18 1994-08-16 The Dow Chemical Company Starburst conjugates
EP0509787A2 (fr) * 1991-04-17 1992-10-21 Unilever Plc Compositions détergentes concentrées en poudre
US5194416A (en) * 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
WO1997014443A1 (fr) * 1995-10-19 1997-04-24 Bracco International B.V. Substances chimiotactiques marquees magnetiquement comme agents de contraste pour l'imagerie par rmn de tissus vivants cibles
DE19605688A1 (de) * 1996-02-16 1997-08-21 Henkel Kgaa Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3524347A1 (fr) 2008-04-09 2019-08-14 Basf Se Utilisation de composés complexes hydrazides métalliques en tant que catalyseurs d'oxydation
WO2012000846A1 (fr) 2010-06-28 2012-01-05 Basf Se Composition de blanchiment dépourvue de métal
WO2013060708A1 (fr) 2011-10-25 2013-05-02 Basf Se Utilisation de copolymères en peigne ou séquencés comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie
WO2013060706A1 (fr) 2011-10-25 2013-05-02 Basf Se Utilisation de copolymères d'acrylate comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie
WO2014154508A1 (fr) 2013-03-27 2014-10-02 Basf Se Copolymères blocs comme agents de libération de la saleté dans des procédés de blanchisserie
US9790452B2 (en) 2013-03-27 2017-10-17 Basf Se Block copolymers as soil release agents in laundry processes
US10214606B2 (en) 2013-11-27 2019-02-26 Basf Se Random copolymers as soil release agents in laundry processes
CN104403839A (zh) * 2014-12-26 2015-03-11 苏州龙腾万里化工科技有限公司 一种清洗剂制造方法
WO2017186480A1 (fr) 2016-04-26 2017-11-02 Basf Se Composition de blanchiment sans métal

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JP2002500242A (ja) 2002-01-08

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