EP2083067A1 - Use of organic complexing agents and/or polymeric compounds containing carbonic acid groups in a liquid washing or cleaning agent compound - Google Patents

Abstract

Use of at least an acid group containing compound (I), which is an organic complex forming agent and polymer carboxylic acid group containing compound, as additive in an enzyme containing liquid detergent or cleaning composition for improving the washing or cleaning capacity, is claimed. Independent claims are included for: (1) the liquid detergent or cleaning composition; and (2) an additive composition comprising a combination of methyl glycidine acetic acid and at least polymer carboxylic acid group containing compounds, or a combination of at least a polyamine modified by a carboxylic group and at least polymer carboxylic acid group containing compounds.

Description

The present invention relates to the use of at least one acid group-containing compound selected from organic complexing agents and various polymeric carboxylic acid group-containing compounds thereof in an enzyme-containing liquid detergent composition.

Liquid detergents and cleaners, such as liquid laundry detergents, are becoming increasingly popular. This is partly due to aesthetic considerations, such as the ability to formulate transparent, viscous products. At such formulations, however, high demands are made with respect to the washing and cleaning performance. This applies in the field of liquid detergents, especially with regard to the removal of stains by means of enzymes. Thus, e.g. proteinaceous, fatty or starchy stains and graying by the use of suitable enzymes, such as the hydrolases are removed. Soil stains based on proteinaceous materials such as grass, blood, eggs, etc. can be specifically removed by the use of proteases. These are proteolytically active enzymes that are able to hydrolyze peptide bonds, so that corresponding protein-containing impurities can be removed during the cleaning or washing process. Amylases, e.g. α-amylases, hydrolyze glycosidic bonds of starch and starch-like polymers. Their contribution to the washing or cleaning performance of the agent concerned is the breakdown of starchy stains. These are cleaved by the amylase to free oligosaccharide which, if desired, can be further degraded by means of suitable auxiliary enzymes to sugar monomers (for example by means of a glucosidase to glucose). There is therefore a need for additives for enzyme-containing liquid detergent compositions which increase the washing and cleaning performance. These should in particular have a positive effect on the enzymatic and especially the proteolytic removal of impurities. They should be well tolerated with a variety of other detergent and cleaner ingredients and in particular the surfactants used.

Liquid detergents and cleaning compositions are, for example, in WO 00/78906 . WO 95/25782 . DE 36 42 218 A1 . US 6,057,277 . US 4,711,730 . WO 95/07331 . EP-A-0095205 . EP-A-0272033 . US 5,618,465 and EP-A-0413616 described.

The WO 00/01661 describes the use of glycine-N, N-carboxylic acid derivatives with carbonyl-containing side chain in detergents and cleaners, especially in laundry detergents. A use in liquid detergents is not described.

The WO 2007/042450 describes a process for stabilizing liquid detergent compositions against phase separation and for reducing the viscosity by adding to the liquid detergent composition a copolymer obtained by radical copolymerization of (A) 20 to 80% by weight of at least one monomer from the group of monoethylenically unsaturated monocarboxylic acids , Dicarboxylic acids and dicarboxylic anhydrides and (B) 20 to 80 wt .-% of at least one monomer from the group of aliphatic or aromatic monoolefins available.

The WO 2004/009751 describes a stain removal process which employs a mixture of at least two aqueous compositions a) and b) wherein a) contains an active oxygen source and b) an enzyme and does not mix the compositions more than two hours before use become.

The WO 99/00478 describes a nonaqueous liquid cleaning composition containing a bleaching agent and / or a bleach precursor, enzymes and ethylenediamine disuccinic acid.

It has surprisingly been found that compounds containing acid groups, which are selected from organic complexing agents and polymeric compounds containing carboxylic acid groups, have a particularly advantageous effect on the detergency of enzyme-containing liquid washing or cleaning agent compositions. This is especially true for the combination of at least one organic complexing agent and at least one polymeric carboxylic acid group-containing compound thereof.

The invention therefore relates to the use of at least one acid group-containing compound which is selected from organic complexing agents and various polymeric compounds containing carboxylic acid groups, as an additive in an enzyme-containing liquid washing or cleaning composition for improving the washing or cleaning performance.

Another object of the invention is a method for improving the washing or cleaning performance of an enzyme-containing liquid detergent or cleaning composition as defined below, wherein said composition at least one acid group-containing compound which is selected from organic complexing agents and polymeric compounds containing carboxylic acid groups, is added as an additive , With regard to suitable and preferred embodiments of the organic complexing agents used as additive and polymeric carboxylic acid group-containing Compounds are referred to the following details in their entirety. The addition of the additive to an enzyme-containing liquid detergent or cleaner composition is carried out by conventional methods.

Another object of the invention is a liquid detergent or cleaning composition, as defined below.

Another object of the invention is an additive composition consisting of a combination of methylglycinediacetic acid and at least one polymeric carboxylic acid-containing compound. In a first embodiment, an acrylic acid homopolymer is used as the polymeric compound containing carboxylic acid groups. In a second embodiment, the polymeric carboxylic acid group-containing compound used is a copolymer which comprises at least one acrylic acid monomer selected from acrylic acid, acrylic acid salts and mixtures thereof and at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof in copolymerized form. In a third embodiment, the polymeric carboxylic acid group-containing compound used is a copolymer of at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof with at least one C ₂ -C ₈ olefin.

The invention further provides an additive composition consisting of a combination of at least one polyamine modified with carboxylic acid groups and at least one polymeric carboxylic acid group-containing compound thereof. In a first embodiment, an acrylic acid homopolymer is used as the polymeric carboxylic acid group-containing compound other than the polyamine. In a second embodiment, a copolymer containing at least one acrylic acid monomer selected from acrylic acid, acrylic acid salts and mixtures thereof and containing at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof is used as the polymeric carboxylic acid group-containing compound other than the polyamine. In a third embodiment, as the polymeric carboxylic acid group-containing compound other than the polyamine, a copolymer of at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof with at least one C ₂ -C ₈ olefin is used.

Detergent compositions based on the additives used according to the invention have a significantly improved washing or cleaning performance in comparison with detergents and cleaners of the prior art. The additives used according to the invention are particularly suitable for use in improving the washing performance of liquid laundry detergents. An improvement of the washing performance according to the invention comprises above all an increase in the primary washing effect. By primary washing action is meant the actual removal of dirt from the textile laundry. This can be determined, for example, by measuring the whiteness of the soiled fabric before and after washing and indicating the achieved remission (%). The additives used according to the invention can also have a positive effect on the secondary washing action, ie the prevention of negative effects which result from redeposition of the detached soil from the washing liquor to the fabric. The additives used according to the invention have a particularly positive effect on the enzymatic removal of impurities. This is especially true for the proteolytic removal of impurities. The attributable to the enzyme activity washing performance (enzyme performance) is usually limited, ie from a certain enzyme concentration can be achieved by further addition of enzyme no increase in washing performance more. Surprisingly, it has now been found that by the use according to the invention of special compounds containing acid groups as an additive, better enzyme performances can be achieved than with additives known from the prior art. In particular, those from the class of hydrolases are used as enzymes. This is especially true for proteolytic soil removal using proteases, such as Savinase in particular. Surprisingly, the increase in the washing power is essentially independent of the water hardness. In addition, the additives used according to the invention are readily compatible with a large number of other washing and cleaning agent ingredients, especially the surfactants used.

The detergent or cleaning composition preferably contains from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, in particular from 1 to 10% by weight, based on the total weight of the composition, of at least one acid-containing compound, which is selected from organic complexing agents and polymeric compounds containing carboxylic acid groups.

Suitable organic complexing agents generally have up to 4 acid groups, which are preferably carboxylic acid groups, phosphonic acid groups or salts thereof. Preferred salts are the sodium and potassium salts and the ammonium salts.

Suitable polymeric compounds containing carboxylic acid groups are characterized by a higher molecular weight than the organic complexing agents and generally have 5 or more than 5 acid groups, which are carboxylic acid groups, their anhydrides or salts thereof. Preferred salts are water-soluble salts, especially the alkali metal salts, such as the sodium and potassium salts, and the ammonium salts.

Suitable organic complexing agents are C ₄ -C ₃₀ di-, tri- and tetracarboxylic acids such as succinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl and alkenyl succinic acids having C ₂ -C ₂₀ alkyl or alkenyl radicals.

Suitable organic complexing agents are furthermore hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These include C ₄ -C ₂₀ -hydroxycarboxylic acids such as malic acid, tartaric acid, gluconic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid.

Suitable organic complexing agents are furthermore hydroxyalkylphosphonic acids, aminophosphonic acids and the salts thereof. These include, for example, phosphonobutanetricarboxylic acid, aminotris-methylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, hexamethylenediamine tetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, morpholino-methanediphosphonic acid, 1-hydroxy-C ₁ to C ₁₀ -alkyl-1,1-diphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid.

Preferably, the detergent composition contains an organic complexing agent comprising at least one aminopolycarboxylic acid.

Suitable aminopolycarboxylic acids are:

Nitrilotriacetic acid (NTA), nitrile monoolessigipropionic acid, nitrilotriapropionic acid, β-alaninediacetic acid (β-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, N- (alkyl) -ethylenediaminetriacetic acid, N- (hydroxyalkyl) ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, cyclohexylene-1,2-diaminetetraacetic acid, iminodisuccinic acid, ethylenediamine disuccinic acid, serinediacetic acid, isoserinediacetic acid, L-aspartic diacetic acid, L-glutamic diacetic acid, methylglycine diacetic acid (MGDA) and the salts of the aforementioned aminopolycarboxylic acids.

A preferred aminopolycarboxylic acid is methylglycinediacetic acid. In a preferred embodiment, the organic complexing agent comprises or consists of methyl glycine diacetic acid.

Preferred polymeric carboxylic acid group-containing compounds are acrylic acid homopolymers. These preferably have a number average molecular weight in the range from 800 to 70,000 g / mol, particularly preferably from 900 to 50,000 g / mol, in particular from 1,000 to 20,000 g / mol, especially from 1,000 to 10,000 g / mol. The term acrylic acid homopolymer also encompasses polymers in which the carboxylic acid groups are partially or completely neutralized. These include acrylic acid homopolymers in which the carboxylic acid groups are present partially or completely in the form of alkali metal salts or ammonium salts. Preference is given to acrylic acid homopolymers, in which the carboxylic acid groups are protonated or in which the carboxylic acid groups are present partially or completely in the form of sodium salts. Homopolymers of acrylic acid which are particularly suitable as polymeric compounds containing carboxylic acid groups are the Sokalan® PA grades from BASF SE.

Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids, as used, for example, in US Pat EP-A 451 508 and EP-A 396 303 are described.

Preference as polymeric carboxylic acid group-containing compounds are further copolymers which contain in copolymerized form as monomer A) at least one unsaturated mono- or dicarboxylic acid or a dicarboxylic anhydride or a salt thereof and at least one comonomer B).

Preferably, the monomer A) is selected from C ₃ -C ₁₀ monocarboxylic acids, salts of C ₃ -C ₁₀ monocarboxylic acids, C ₄ -C ₈ dicarboxylic acids, anhydrides of C ₄ -C ₈ dicarboxylic acids, salts of C ₄ -C _8- dicarboxylic acids and mixtures thereof. Monomers A) in salt form are preferably used in the form of their water-soluble salts, in particular the alkali metal salts, such as potassium and especially sodium salts or ammonium salts. The monomers A) may each be wholly or partially in anhydride form. Of course, it is also possible to use mixtures of the monomers A).

The monomers (A) are preferably selected from acrylic, methacrylic, crotonic, vinylacetic, maleic, maleic, fumaric, citraconic, citraconic, itaconic and mixtures thereof. Particularly preferred monomers (A) are acrylic acid, methacrylic acid, maleic acid, maleic anhydride and mixtures thereof.

The copolymers used according to the invention preferably comprise at least one monomer A) in an amount of from 5 to 95% by weight, more preferably from 20 to 80% by weight, in particular from 30 to 70% by weight, based on the total weight of the polymerization used Monomers, copolymerized.

The copolymers used according to the invention additionally contain at least one comonomer B) copolymerized, which is preferably selected from C ₂ -C ₃₀ monoolefins, vinylaromatics, esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₃₀ -alkanols, esters of Vinyl alcohol with C ₁ -C ₃₀ monocarboxylic acids, ethylenically unsaturated nitriles, monoethylenically unsaturated sulfonic acids, esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C ₃₀ alkanediols, amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C ₃₀ aminoalcohols having a primary or secondary amino group, primary amides of α, β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, N-vinyl lactams, open-chain N-vinyl amide compounds, esters of allyl alcohol with C ₁ -C ₃₀ monocarboxylic acids, esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, amides α, β-ethylenically unsaturated mono and dicarboxylic acids with diamines having at least one primary or secondary amino group, N, N-diallylamines, N, N-diallyl-N-alkylamines, vinyl- and allyl-substituted nitrogen heterocycles, vinyl ethers, monoethylenically unsaturated polyalkenes having more than 30 carbon atoms, and mixtures from that.

The comonomers B) are preferably selected from C ₂ -C ₃₀ -monoolefins, vinylaromatics, esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₃₀ -alkanols, esters of vinyl alcohol with C ₁ -C ₃₀ -monocarboxylic acids, ethylenically unsaturated nitriles, primary amides of α, β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, N-vinyl lactams, open-chain N-vinyl amide compounds, vinyl ethers, monoethylenically unsaturated polyalkenes and mixtures thereof.

Suitable C ₂ -C ₃₀ monoolefins are ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, diisobutene (2-methyl-4,4-dimethyl 1-pentene), 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docoses and 1-tetracoses, 1-hexacoses and Mixtures thereof. Also suitable are large-scale available olefin mixtures, for example mixtures of C ₁₈ -C ₂₄ -α-olefins, mixtures of C ₂₀ -C ₂₄ -α-olefins, etc.

Suitable vinyl aromatic compounds are styrene, 2-methylstyrene, 4-methylstyrene, 2- (n-butyl) styrene, 4- (n-butyl) styrene, 4- (n-decyl) styrene and particularly preferably styrene.

Suitable esters of vinyl alcohol with C ₁ -C ₃₀ monocarboxylic acids are, for. Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and mixtures thereof.

Suitable esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₃₀ -alkanols are methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl ethacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate , n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n- Octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, Tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, arachinyl (meth) acrylate, behenyl (meth) acrylate, lignoceryl ( meth) acrylate, cerotinyl (meth) acrylate, melissinyl (meth) acrylate, palmitoleinyl (meth) acrylate, oleyl (meth) acrylate, Linolyl (meth) acrylate, linolenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate and mixtures thereof.

Suitable esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C ₃₀ -alkanediols are, for. 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, etc.

Suitable ethylenically unsaturated nitriles are acrylonitrile, methacrylonitrile and mixtures thereof.

Suitable primary amides of α, β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives are acrylic acid amide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide , N- (n-butyl) (meth) acrylamide, N- (tert-butyl) (meth) acrylamide, etc.

Suitable N-vinyl lactams and derivatives thereof are, for. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, etc.

Suitable open-chain N-vinylamide compounds are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide and N-vinylbutyramide.

Suitable vinyl- and allyl-substituted nitrogen heterocycles are N-vinylimidazole, N-vinyl-2-methylimidazole, vinyl- and allyl-substituted heteroaromatic compounds, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.

Suitable monoethylenically unsaturated polyalkenes having more than 30 carbon atoms are e.g. monoethylenically unsaturated polyisobutenes.

The aforementioned comonomers B) can be used in the form of individual comonomers, two or more than any two comonomers from one and the same substance class or two or more than any two comonomers from different classes of substances.

The copolymers used according to the invention preferably comprise at least one comonomer B) in an amount of 5 to 95% by weight, particularly preferably 20 to 80% by weight, in particular 30 to 70% by weight, based on the total weight of the polymerization used Monomers, copolymerized.

In a preferred embodiment, the polymeric carboxylic acid group-containing compounds used are a co- or terpolymer which comprises at least one unsaturated C ₄ -C ₈ -dicarboxylic acid or an anhydride or a salt thereof in copolymerized form.

1. i) monoethylenisch ungesättigten C₃-C₈-Monocarbonsäuren,
2. ii) monoethylenisch ungesättigten C₂-C₂₂-Olefine, Vinylalkylethern mit C₁-C₈-Alkylgruppen, Styrol, Vinylester von C₁-C₈-Carbonsäuren, (Meth)acrylamid, Vinylpyrrolidon und Mischungen davon,
3. iii) (Meth)acrylester von C₁-C₈-Alkoholen, (Meth)acrylnitril, (Meth)acrylamiden von C₁-C₈-Aminen, N-Vinylformamid, Vinylimidazol und Mischungen davon.

Preference is given to copolymers and terpolymers of unsaturated C ₄ -C ₈ -dicarboxylic acids which additionally contain, in copolymerized form, at least one comonomer selected from

1. i) monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids,
2. ii) monoethylenically unsaturated C ₂ -C ₂₂ -olefins, vinylalkyl ethers having C ₁ -C ₈ -alkyl groups, styrene, vinyl esters of C ₁ -C ₈ -carboxylic acids, (meth) acrylamide, vinylpyrrolidone and mixtures thereof,
3. iii) (meth) acrylic esters of C ₁ -C ₈ -alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ -C ₈ -amines, N-vinylformamide, vinylimidazole and mixtures thereof.

Preferably, these contain copolymers and terpolymers
From 5 to 95% by weight of at least one unsaturated C ₄ -C ₈ -dicarboxylic acid,
From 5 to 95% by weight of at least one monomer i),
0 to 60 wt .-% of at least one monomer ii) and
0 to 20% by weight of at least one monomer iii),
in each case based on the total weight of the monomers used for the polymerization, polymerized.

As unsaturated C ₄ -C ₈ dicarboxylic acids, maleic acid, fumaric acid, itaconic acid and citraconic acid are preferred. Particularly preferred is maleic acid.

The group (i) comprises monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. Preferably, from group (i), acrylic acid and methacrylic acid are used.

C ₂ -C ₆ -olefins, vinylalkyl ethers having C ₁ -C ₄ -alkyl groups, vinyl acetate and vinyl propionate are preferably used from group (ii).

If the polymers of group (ii) contain copolymerized vinyl esters, these may also be partially or completely hydrolyzed to vinyl alcohol structural units. Suitable copolymers and terpolymers are for example US-A 3,887,806 such as DE-A 43 13 909 known.

Particularly preferred polymeric carboxylic acid group-containing compounds are copolymers comprising at least one acrylic acid monomer selected from acrylic acid, acrylic acid salts and mixtures thereof and at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof, incorporated in copolymerized form. These preferably have a number-average molecular weight in the range from 2500 to 150000 g / mol, more preferably from 2800 to 70,000 g / mol, in particular from 2900 to 50,000 g / mol, more particularly from 3000 to 30,000 g / mol. Also included are copolymers in which the carboxylic acid groups are partially or completely neutralized. For this purpose, monomers may be used in salt form either for the polymerization or the resulting copolymer is subjected to a partial or complete neutralization. Preferred are copolymers in which the carboxylic acid groups are protonated or partially or completely present in the form of alkali metal salts or ammonium salts. Preferred alkali metal salts are the sodium or potassium salts, especially the sodium salts.

Preferred polymeric carboxylic acid group-containing compounds are copolymers of maleic acid (or maleic acid monomers) and acrylic acid (or acrylic acid monomers) in a weight ratio of 10:90 to 95: 5, particularly preferably in a weight ratio of 30:70 to 90:10.
Preferred polymeric carboxylic acid group-containing compounds are further terpolymers of maleic acid (or maleic acid monomers), acrylic acid (or acrylic acid monomers) and a vinyl ester of a C ₁ -C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid ): 10 (acrylic acid + vinyl ester). The weight ratio of acrylic acid to vinyl ester is preferably in a range of 30:70 to 70:30.

Particularly suitable polymeric carboxylic acid group-containing compounds based on acrylic acid monomers and maleic acid monomers are the corresponding Sokalan® CP grades from BASF SE.

Particularly preferred polymeric carboxylic acid group-containing compounds are copolymers which comprise at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof and at least one C ₂ -C ₈ -olefin in copolymerized form. These preferably have a number average molecular weight in the range from 3000 to 150000 g / mol, particularly preferably from 5000 to 70000 g / mol, in particular from 8000 to 50,000 g / mol, more particularly from 10,000 to 30,000 g / mol. Also included are copolymers in which the carboxylic acid groups are partially or completely neutralized. For this purpose, either maleic acid salts can be used for the polymerization or the resulting copolymer is subjected to a partial or complete neutralization. Preferred are copolymers in which the carboxylic acid groups are protonated or partially or completely present in the form of alkali metal salts or ammonium salts. Preferred alkali metal salts are the sodium or potassium salts, especially the sodium salts.

Preferred polymeric carboxylic acid group-containing compounds are copolymers of maleic acid with C ₂ -C ₈ olefins in a molar ratio of 40:60 to 80:20, with copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50 being particularly preferred. Particularly suitable polymeric carboxylic acid group-containing compounds based on olefins and maleic acid are likewise the corresponding Sokalan® CP grades from BASF SE.

Preferred polymeric carboxylic acid group-containing compounds are further those in the WO 2007/042450 copolymers described by free-radical copolymerization of (A) 20 to 80 wt .-% of at least one monomer selected from the group of monoethylenically unsaturated monocarboxylic acids, dicarboxylic acids and dicarboxylic anhydrides and (B) 20 to 80 wt .-% of at least one monomer from the group aliphatic or aromatic monoolefins are available. The monomer (A) is preferably selected from the group consisting of maleic acid, maleic anhydride and acrylic acid. The monomer (B) is preferably selected from the group of isobutene, diisobutene, 1-dodecene, C ₁₈ -C ₂₄ -α-olefins, C ₂₀ -C ₂₄ -α-olefin mixtures, polyisobutenes having an average of 12 to 100 carbon atoms and styrene. Preferably, a copolymer is used which is based on a mixture of (B1) at least one monoolefin having <8 carbon atoms and (B2) at least one monoolefin having> 10 carbon atoms as component (B). Specifically, a copolymer is used, the radical copolymerization of (A) 30 to 70 wt .-% of maleic acid or maleic anhydride (B1) from 20 to 40 wt .-% of isobutene and (B2) 5 to 20 wt .-% of a C ₁₈ C ₂₄ -α-olefin is available.

Preferred polymeric compounds containing carboxylic acid groups are also graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates, cf. US-A 5,227,446 . DE-A 44 15 623 and DE-A 43 13 909 ,

Examples of suitable unsaturated carboxylic acids are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid and also mixtures of acrylic acid and maleic acid which are grafted in amounts of from 40 to 95% by weight, based on the component to be grafted.

For modification, in addition up to 30% by weight, based on the component to be grafted, of further monoethylenically unsaturated monomers may be present in copolymerized form. Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).

As a graft base are degraded polysaccharides such as acidic or enzymatically degraded starches, inulins or cellulose, protein hydrolysates and reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such as mannitol, sorbitol, aminosorbitol and N-alkylglucamine suitable as well as polyalkylene glycols having molecular weights of up to M _w = 5,000 such as polyethylene glycols, ethylene oxide / propylene oxide or ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyhydric C ₁ -C ₂₂ alcohols, cf. US Pat. No. 5,756,456 ,

Grafted degraded or degraded reduced starches and grafted polyethylene oxides are preferably used from this group, with from 20 to 80% by weight of monomers, based on the grafting component, being used in the graft polymerization. For grafting, a mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90 is preferably used.

Suitable polymeric compounds containing carboxylic acid groups are furthermore polyglyoxylic acids, which are described, for example, in US Pat EP-B 001 004 . US Pat. No. 5,399,286 . DE-A 41 06 355 and EP-A 0 656 914 are described. The end groups of the polyglyoxylic acids can have different structures.

For example, polyamidocarboxylic acids and modified polyamidocarboxylic acids suitable as polymeric carboxylic acid group-containing compounds are known EP-A 454 126 . EP-B 511,037 . WO-A 94/01486 and EP-A 581 452 ,

Suitable polymeric compounds containing carboxylic acid groups are furthermore polyamines modified with carboxylic acid groups, preferably polyalkyleneimines, especially polyethyleneimines. Polyakylenimines modified with carboxylic acid groups are obtainable, for example, by reacting a polyalkylenimine with a chloroalkanoic acid, such as chloroacetic acid. In the polyamines modified with carboxylic acid groups, the carboxylic acid groups may be protonated or partially or completely neutralized. In a suitable embodiment, the carboxylic acid groups are present partially or completely in the form of alkali metal salts or ammonium salts. Preference is given to polyamines modified with carboxylic acid groups in which the carboxylic acid groups are present partially or completely in the form of sodium salts. The number average molecular weight of the carboxylic acid group-modified polyamines is preferably in a range of 1,000 to 200,000, more preferably 10,000 to 100,000. The degree of substitution of nitrogen atoms having substituents bearing a carboxylic acid group is preferably in a range of 1 to 100%, more preferably 5 to 95%. Preference is given to carboxymethylated polyethyleneimines. These preferably have a number-average molecular weight in a range from 1000 to 200,000, particularly preferably 10,000 to 100,000. The degree of carboxymethylation of the nitrogen atoms is preferably in a range of 1 to 100%, more preferably 5 to 95%. A suitable commercial product is Trilon® P from BASF SE (carboxymethylated polyethyleneimine, molecular weight 50,000, degree of substitution 80%).

In particular, polyaspartic acids or cocondensates of aspartic acid with further amino acids, C ₄ -C ₂₅ -mono- or -dicarboxylic acids and / or C ₄ -C ₂₅ -mono- or -diamines are also used as polymeric compounds containing carboxylic acid groups. Particular preference is given to using polyaspartic acids prepared in phosphorus-containing acids and modified with C ₆ -C ₂₂ -mono- or dicarboxylic acids or with C ₆ -C ₂₂ -mono- or -diamines.

Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds which are suitable as polymeric carboxylic-acid-containing compounds are known, for example WO-A 93/22362 and WO-A 92/16493 , Such condensates containing carboxyl groups usually have molecular weights of up to 10,000, preferably up to 5,000.

A preferred embodiment of the invention is the use of a combination of methylglycinediacetic acid and at least one polymeric carboxylic acid group-containing compound as an additive in an enzyme-containing liquid detergent or cleaning composition to improve the washing or cleaning performance.

Preferably, this combination contains as the polymeric carboxylic acid group-containing compound at least one acrylic acid homopolymer. Specifically, this combination consists of methylglycinediacetic acid and at least one acrylic acid homopolymer. Suitable acrylic acid homopolymers are the abovementioned and their alkali metal and ammonium salts, preferably their sodium salts. The acrylic acid homopolymers used in the combination preferably have a number-average molecular weight in the range from 800 to 70,000 g / mol, more preferably from 900 to 50,000 g / mol, in particular from 1,000 to 20,000 g / mol, especially from 1,000 to 10,000 g / mol, on.

Further preferably, the combination of methylglycinediacetic acid and at least one polymeric carboxylic acid-containing compound contains at least one copolymer containing at least one acrylic acid monomer selected from acrylic acid, acrylic acid salts and mixtures thereof and at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof. Specifically, this combination consists of methylglycinediacetic acid and at least one such copolymer. The copolymers used in the combination preferably have a number-average molecular weight in the range from 2500 to 150000 g / mol, more preferably from 2800 to 70,000 g / mol, in particular from 2900 to 50,000 g / mol, more particularly from 3000 to 30,000 g / mol.

Further preferably, the combination of methylglycinediacetic acid and at least one polymeric carboxylic acid-containing compound contains at least one copolymer containing at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof and at least one Contains copolymerized C ₂ -C ₈ olefin. Specifically, this combination consists of methylglycinediacetic acid and at least one such copolymer. The copolymers used in the combination preferably have a number average molecular weight in the range from 3000 to 150000 g / mol, particularly preferably from 5000 to 70000 g / mol, in particular from 8000 to 50,000 g / mol, more particularly from 10,000 to 30,000 g / mol.

A further preferred embodiment of the invention is the use of a combination (hereinafter also referred to as a second combination) of at least one polyamine modified with carboxylic acid groups and at least one polymeric carboxylic acid group-containing compound as an additive in an enzyme-containing liquid washing or cleaning composition for improving the washing composition. or cleaning performance.

Suitable polyamines modified with carboxylic acid groups for this second combination are the abovementioned, preferably polyalkyleneimines, especially polyethyleneimines. The carboxylic acid groups are protonated or partially or completely neutralized. In a suitable embodiment, the carboxylic acid groups are present partially or completely in the form of alkali metal salts or ammonium salts. Preference is given to polyamines modified with carboxylic acid groups in which the carboxylic acid groups are present partially or completely in the form of sodium salts. The number average molecular weight of the carboxylic acid group-modified polyamines is preferably in a range of 1,000 to 200,000, more preferably 10,000 to 100,000. The degree of substitution of nitrogen atoms having substituents bearing a carboxylic acid group is preferably in a range of 1 to 100%, more preferably 5 to 95%. Preference is given to carboxymethylated polyethyleneimines. These preferably have a number-average molecular weight in a range from 1000 to 200,000, particularly preferably 10,000 to 100,000. The degree of carboxymethylation of the nitrogen atoms is preferably in a range of 1 to 100%, more preferably 5 to 95%. A suitable commercial product is Trilon® P from BASF SE.

The second combination preferably contains at least one acrylic acid homopolymer as the polymeric carboxylic acid group-containing compound other than the polyamine. Specifically, this combination consists of a carboxymethylated polyethyleneimine and at least one acrylic acid homopolymer. Suitable acrylic acid homopolymers are the abovementioned and their alkali metal and ammonium salts, preferably their sodium salts. The acrylic acid homopolymers used in the combination preferably have a number-average molecular weight in the range from 800 to 70,000 g / mol, more preferably from 900 to 50,000 g / mol, in particular from 1,000 to 20,000 g / mol, especially from 1,000 to 10,000 g / mol, on.

Further preferably, the second combination contains, as a polymeric carboxylic acid group-containing compound other than the polyamine, at least one copolymer containing at least one acrylic acid monomer selected from acrylic acid, acrylic acid salts and mixtures thereof and at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof in copolymerized form. Specifically, this combination consists of a carboxymethylated polyethylenimine and at least one such copolymer. The copolymers used in the combination which comprise at least one acrylic acid monomer and at least one maleic acid monomer in copolymerized form preferably have a number-average molecular weight in the range from 2500 to 150000 g / mol, more preferably from 2800 to 70,000 g / mol, in particular from 2900 to 50,000 g / mol, more specifically from 3,000 to 30,000 g / mol.

Further preferably, the second combination contains as a non-polyamine polymeric carboxylic acid group-containing compound at least one copolymer containing at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof and at least one C ₂ -C ₈ olefin copolymerized. Specifically, this combination consists of a carboxymethylated polyethylenimine and at least one such copolymer. The copolymers used in the combination which comprise at least one maleic acid monomer and at least one C ₂ -C ₈ -olefin in copolymerized form preferably have a number-average molecular weight in the range from 3000 to 150000 g / mol, more preferably from 5000 to 70000 g / mol, in particular from 8000 to 50,000 g / mol, more specifically 10,000 to 30,000 g / mol.

The abovementioned additives are used according to the invention for improving the washing or cleaning performance of an enzyme-containing liquid washing or cleaning composition. The enzymes are preferably selected from hydrolases such as proteases, esterases, glucosidases, lipases, amylases, cellulases, mannanases, other glycosyl hydrolases and mixtures of the aforementioned enzymes. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents.

Suitable hydrolases include α-glucosidases (EC number 3.2.1.20), β-glucosidases (Ovozyme, EC number 3.2.1.20), amylases (Purastar, Termamyl, Stainzyme, Duramyl), mannanases (Purabrite, Mannastar, Mannaway) and cellulases (Carezyme, Celluzyme, Endolase, Puradax). Suitable amylases include in particular α-amylases (EC number 3.2.1.1), iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

Suitable lipases are esterases, such as Lipex and Lipolase. Examples of lipolytic enzymes are the known cutinases.

Peroxidases or oxidases have also proved suitable in some cases.

Preferably, the additives of the invention are used in detergent or cleaning composition containing at least one protease and / or amylase. In a specific embodiment, these detergent or cleaning compositions contain at least one glucosidase. The additives of the invention are particularly useful for compositions containing at least one subtilisin-type protease (Savinase, Alcalase, Esperase, EC number 3.4.21.62). These include proteases derived from Bacillus lentus.

• Protease und Amylase,
• Protease und Lipase (bzw. lipolytisch wirkenden Enzymen),
• Protease und Cellulase,
• Amylase, Cellulase und Lipase (bzw. lipolytisch wirkenden Enzymen),
• Protease, Amylase und Lipase (bzw. lipolytisch wirkenden Enzymen)
• Protease, Lipase (bzw. lipolytisch wirkenden Enzymen) und Cellulase.

Preferably, the additives of the invention are further used in detergent or cleaning composition containing an enzyme mixture. For example, enzyme mixtures which contain or consist of the following enzymes are preferred:

• Protease and amylase,
• Protease and lipase (or lipolytic enzymes),
• Protease and cellulase,
• Amylase, cellulase and lipase (or lipolytic enzymes),
• Protease, amylase and lipase (or lipolytic enzymes)
• Protease, lipase (or lipolytic enzymes) and cellulase.

Particularly preferred are protease and / or amylase-containing mixtures or mixtures with glucosidases. Preferred proteases in the aforementioned mixtures are subtilisin-type proteases (Savinase, etc .: EC number 3.4.21.62).

The enzymes may be adsorbed to carriers to protect against premature degradation. The proportion of the enzymes is preferably 0.1 to 5 wt .-%, particularly preferably 0.15 to 2.5 wt .-%, in particular 0.2 to 2 wt .-%, based on the total weight of the detergent or cleaning composition ,

In addition to the additives and enzymes used according to the invention, the liquid detergents or cleaners contain surfactant (s), wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants. The total surfactant content of the liquid washing or cleaning agent is preferably from 5 to 60% by weight and more preferably from 15 to 40% by weight, based on the total weight of the detergent or cleaning composition.

As nonionic surfactants are preferably alkoxylated, preferably ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 20, preferably 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used in which the alcohol radical linear or preferably in 2 Position may be methyl-branched or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of 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 -C ₁₄ -alcohols with 3 EO, 4 EO or 7 EO, C ₉ -C ₁₁ -alcohol with 7 EO, C ₁₃ -C ₁₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 EO and C ₁₂ -C 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. Also suitable are alcohol ethoxylates which have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO or 30 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used. Here, 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. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula (1)

R ¹ O (G) _x (1)

in which R ^{1 is} a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is a glycoside unit having 5 or 6 C atoms, preferably for 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.

Another class of preferred 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 as they are For example, in the Japanese patent application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods.

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.

worin R²C(=O) für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (2),

wherein R ^{2 is} C (= O) for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{3 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical 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.

worin R⁴ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁵ für einen linearen, verzweigten oder cyclischen Alkylenrest mit 2 bis 8 Kohlenstoffatomen oder einen Arylenrest mit 6 bis 8 Kohlenstoffatomen und R⁶ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z]¹ für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes. [Z]¹ wird vorzugsweise durch reduktive Aminierung eines Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielweise gemäß WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.The group of polyhydroxy fatty acid amides also includes compounds of the formula (3)

wherein R ^{4 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{5 is} a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene radical having 6 to 8 carbon atoms and R ^{6 is} a linear, branched or is a cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C ₁ -C ₄ alkyl or phenyl radicals being preferred, and [Z] ^{1 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 group. [Z] ¹ is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be prepared, for example, according to WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettsäureamide.

The content of nonionic surfactants in the liquid detergents or cleaners is preferably 0 to 30% by weight, preferably 0 to 20% by weight and in particular 2 to 15% by weight, based in each case on the total weight of the detergent composition.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C ₁₂ -C ₁₈ -monoolefins having terminal or internal double bonds by sulfonation gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. 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. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 which can be obtained as commercial products of the Shell Oil Company under the name DAN® are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ -C ₂₁ -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols having on average 3.5 mol of ethylene oxide (EO) or C ₁₂ - C ₁₈ fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also 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 in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -C ₁₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols having a narrower homolog distribution, are again particularly preferred. Likewise, it is also possible to use 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 including the soaps 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 preferred liquid detergents or cleaning agents on anionic surfactants (including the soaps) is 2 to 50 wt .-%, preferably 3 to 40 wt .-%, each based on the total weight of the detergent or cleaning composition.

The viscosity of the liquid detergents or cleaners can be measured by conventional standard methods (for example Brookfield Viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 100 to 5000 mPas. Preferred agents have viscosities from 300 to 4000 mPas, with values between 1000 and 3000 mPas being particularly preferred.

In addition, the liquid washing or cleaning agents may contain other ingredients that further improve the performance and / or aesthetic properties of the liquid detergent or cleaning agent. In general, in addition to the additives used and at least one enzyme and at least one surfactant, preferred agents comprise one or more substances from the group of builders, bleaches, bleach activators, electrolytes, nonaqueous solvents, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, Hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.

As builders or builders which may be present in the liquid detergents or cleaners, in particular silicates, aluminum silicates (in particular zeolites) and carbonates and mixtures of these substances may be mentioned. However, the use of such builders is not preferred.

As electrolytes 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 manufacturing point of view, the use of NaCl or MgCl ₂ in the compositions is preferred. The proportion of electrolytes is usually 0.5 to 5 wt .-%, based on the total weight of the detergent or cleaning composition.

The washing or cleaning agent composition according to the invention or used according to the invention contains at least one solvent. Suitable solvents are selected from water, non-aqueous solvents and mixtures thereof. Non-aqueous solvents used are preferably nonaqueous organic solvents. Preferred non-aqueous organic solvents are those which are completely miscible under normal conditions (20 ° C, 1013 mbar) with water.

The solvent content of the detergent or cleaner composition is preferably from 5 to 95% by weight, more preferably from 10 to 80% by weight, based on the total weight of the composition.

Non-aqueous solvents which can be used in the liquid detergents or cleaners, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible in the specified concentration range with water. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, 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 glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, i-butoxy-ethoxy-2-propanol, 3-methyl-3 Methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Non-aqueous solvents can be used in the liquid detergents or cleaners in amounts of between 0.5 and 15% by weight, but preferably below 12% by weight and in particular below 9% by weight.

In a preferred embodiment, the liquid detergent or cleaning agent composition according to the invention or the liquid detergent or cleaning agent composition used according to the invention is an aqueous detergent or cleaner composition. Suitable aqueous solvents are water and mixtures of water and at least one water-miscible nonaqueous solvent. The content of non-aqueous solvents is preferably at most 25% by weight, particularly preferably at most 15% by weight, based on the total weight of the solvent.

The content of the washing or cleaning agent composition in aqueous solvents is preferably from 5 to 95% by weight, particularly preferably from 10 to 80% by weight, in particular from 15 to 70% by weight, based on the total weight of the composition.

To bring the pH of the liquid detergents or cleaners into 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 actuating means 7 exceeds Wt .-%, based on the total weight of the detergent or cleaner composition, not.

In order to improve the aesthetic impression of liquid washing or cleaning agents, they can be colored 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 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 liquid detergents or cleaners are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.

Suitable antiredeposition agents, which are also referred to as "soil repellents", are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on nonionic cellulose ether. Suitable soil-release polymers are, for example, polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids; Polyesters of unilaterally end-capped polyethylene oxides with dihydric and / or polyhydric alcohols and dicarboxylic acid, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers. Such polyesters are known, for example US 3,557,039 . GB-A 11 54 730 . EP-A 0 185 427 . EP-A 0 241 984 . EP-A 0 241 985 . EP-A 0 272 033 and US-A 5,142,020 , Further suitable soil-release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (cf. US 4,746,456 . US 4,846,995 . DE-A 37 11 299 . US 4,904,408 . US 4,846,994 and US 4,849,126 ) or modified celluloses such as methylcellulose, hydroxypropylcellulose or carboxymethylcellulose.

Optical brighteners (so-called "whiteners") can be added to the liquid detergents or cleaners to eliminate graying and yellowing of the treated fabrics. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure with the yellowness of the grayed or yellowed wash White results. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenylene, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems, and heterocyclic substituted pyrene derivatives. The optical brighteners are usually used in amounts of between 0.03 and 0.3 wt .-%, based on the finished composition.

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. Also, 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. However, preference is given to using 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 compositions.

Since fabrics, particularly rayon, rayon, cotton and blends thereof, can tend to wrinkle because the individual fibers are susceptible to flexing, buckling, squeezing and squeezing across the grain, the compositions may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty alkylol esters, fatty alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

For controlling microorganisms, the liquid washing or cleaning agents may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, germicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate.

In order to prevent undesirable changes to the liquid detergents or cleansers and / or the treated fabrics caused by oxygen and other oxidative processes, the compositions 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 and phosphonates.

Increased comfort may result from the additional use of antistatic agents added to the compositions. 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. External antistatics are for example in the patent applications FR 1,156,513 . GB 873 214 and GB 839,407 described. The lauryl (or stearyl) -dimethylbenzylammonium chlorides disclosed herein are useful as antistatics for textile fabrics or as an additive to laundry detergents, with a softening effect being additionally achieved.

To improve the water absorbency, the rewettability of the treated fabrics and to facilitate the ironing of the treated fabrics, for example, silicone derivatives may be used in the liquid detergents or cleaners. These additionally improve the rinsing behavior of the 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 in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.

Finally, the liquid detergents or cleaning agents may also contain UV absorbers, which wick on the treated fabrics and improve the light fastness of the fibers. Compounds having these desired properties 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.

The resulting aqueous liquid detergents or cleaning agents have no sediment; in a preferred embodiment, they are transparent or at least translucent. Preferably, the aqueous liquid detergents or cleaning agents have a transmission of visible light of at least 30%, preferably 50%, more preferably 75%, most preferably 90%. Alternatively, the thickeners of the invention may be incorporated into opaque detergents or cleaners.

In addition to these components, an aqueous washing or cleaning agent may contain dispersed particles whose diameter is from 0.01 to 10,000 μm along their greatest spatial extent.

Particles may be microcapsules as well as granules, compounds and fragrance beads, with microcapsules being preferred.

The term "microcapsule" is understood to mean aggregates which contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s). These are usually finely dispersed liquid or solid phases coated with film-forming polymers, during the production of which the polymers precipitate on the material to be enveloped after emulsification and coacervation or interfacial polymerization. The microscopic capsules can be dried like powder. Besides mononuclear microcapsules, multinuclear aggregates, also called microspheres, are known, which contain two or more cores distributed in the continuous shell material. Mono- or polynuclear microcapsules can also be enclosed by an additional second, third, etc., sheath. Preferred are mononuclear microcapsules with a continuous shell. The shell may be made of natural, semi-synthetic or synthetic materials. Naturally, shell materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran , Sucrose and waxes. Semi-synthetic shell materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and also starch derivatives, in particular starch ethers and esters. Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone. Inside the microcapsules sensitive, chemically or physically incompatible and volatile components (= active ingredients) of the aqueous liquid detergent or cleaning agent can be trapped stable storage and transport. The microcapsules may include, for example, optical brighteners, surfactants, complexing agents, bleaching agents, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, graying inhibitors, anti redeposition agents, pH adjusters, electrolytes, foam inhibitors and UV absorbers.

The microcapsules may further contain cationic surfactants, vitamins, proteins, preservatives, detergency boosters or pearlescing agents. The fillings of the microcapsules may be solids or liquids in the form of solutions or emulsions or suspensions.

The microcapsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their largest spatial extent, depending on the components contained in their interior and the application between 0.01 microns (not visually recognizable as a capsule) and 10,000 microns. Preference is given to visible microcapsules having a diameter in the range from 100 μm to 7000 μm, in particular from 400 μm to 5 000 μm. The microcapsules are accessible by known methods, coacervation and interfacial polymerization being the most important. As microcapsules, all surfactant-stable microcapsules available on the market can be used, for example the commercial products (the shell material is indicated in parentheses) Hallcrest microcapsules (gelatin, gum arabic), Coletica thalaspheres (marine collagen), Lipotec millicapsules (alginic acid, agar-agar) , Also unispheres (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified Agar Agar) and Kuhs Probiol Nanospheres (phospholipids).

Alternatively, it is also possible to use particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "speckles".

A preferred matrix-forming material is alginate. To produce alginate-based speckles, an aqueous alginate solution, which also contains the active substance to be enclosed or the active ingredients to be enclosed, is dripped off and then cured in a precipitation bath containing Ca ²⁺ ions or Al ³⁺ ions.

Alternatively, other, matrix-forming materials can be used instead of alginate. Examples of matrix-forming materials include polyethylene glycol, polyvinylpyrrolidone, polymethacrylate, polylysine, poloxamer, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyethoxyoxazoline, albumin, gelatin, acacia, chitosan, cellulose, dextran, ficoll®, starch, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hyaluronic acid, Carboxymethylcellulose, carboxymethylcellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials. The matrix formation takes place with these materials, for example via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions. The production of particles with these matrix-forming materials is known per se.

The particles can be stably dispersed in the aqueous liquid detergent or cleaner. Stable means that the compositions are stable at room temperature and at 40 ° C for a period of at least 4 weeks, and preferably at least 6 weeks, without the medium creaming or sedimenting. Due to the increase in viscosity, the thickeners according to the invention bring about a kinetic slowing down of the sedimentation of the particles and thus their stabilization in the suspended state.

The release of the active ingredients from the microcapsules or speckles is usually carried out during the application of the agents containing them by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action.

The washing or cleaning agents according to the invention can be used for cleaning textile surface fabrics and / or hard surfaces. Detergents of the invention may be in the form of a hand or machine dishwashing detergent, general-purpose cleaners for non-textile surfaces, e.g. made of metal, lacquered wood or plastic, or cleaning agents for ceramic products, such as porcelain, tiles, tiles. The detergents or cleaners according to the invention are preferably in the form of a liquid laundry detergent. If desired, these can also be formulated pasty.

To prepare the liquid detergents or cleaners, the surfactants, the organic complexing agents and / or polymeric carboxylic acid group-containing compounds, enzyme (s) and the optional components may be combined in any order. For example, the acidic components such as the linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, etc. may be initially charged and the nonionic surfactants added. Subsequently, a base such as NaOH, KOH, triethanolamine or monoethanolamine is added followed by the fatty acid, if any. Subsequently, the remaining ingredients and the solvents of the aqueous liquid detergent or cleaning agent are added to the mixture. Then, the additive of the invention is added and, optionally, the pH corrected, z. B. to a value of 8 to 9.5.

A particular advantage of the additives according to the invention is that they are also suitable for subsequent incorporation into a washing or cleaning agent preformulation (post-addition).

Optionally, particles to be dispersed may be finally added and dispersed homogeneously in the aqueous liquid detergent or cleaner by mixing.

The invention is further illustrated by the following examples.

Examples I. Determination of the Washing Performance of Two Detergent Formulations A and B

The washing conditions are shown in Table 1. The detergent formulations are shown in Table 2. Table 1: washing machine Launderometer of the company Atlas, Chicago, USA wash cycles 1 per dirt cloth type rinse cycles 1 wash temperature 40 ° C washing time 30 min. (including heating time) water hardness as specified (0 or 4 mmol / l *)); Ca: Mg = 4: 1 amount of liquor 250 ml liquor ratio 1: 12.5 Detergent concentration 5 g / l soiled fabric EMPA 101 olive oil / soot on cotton EMPA 116 blood / milk / ink on cotton EMPA 112 cocoa on cotton (test fabric from EMPA Testmaterialien AG, Mövenstrasse 12, CH-9015 St. Gallen) wfk 10 D pigment / skin fat on cotton wfk 20 D pigment / skin fat on cotton / polyester blended fabric (test fabric from. wfk-Testgewebe GmbH, Christenfeld 10, D-41379 Brüggen) CFT-C10 pigment / peanut oil / milk on cotton (test fabric from the company Center for Testmaterials Stoomloggerweg 11, NL-3133 KT Vlaardingen) *) corresponds to about 23 ° dH

After rinsing, spinning was carried out and the fabrics were hung one at a time to dry.

To determine the primary washing effect, the whiteness of the soiled fabric was measured before and after washing with a photometer (Elrepho 2000) from Datacolor AG, CH-8305 Dietikon, Switzerland, on the basis of the remission (%). The higher the remission value, the better the primary washing ability. The remission values were determined at 460 nm, wherein in each case 6 measuring points per type of spoil were averaged. Better dirt removal (higher primary wash performance) is indicated by higher readings. Table 2: (in% by weight) detergent formulation A B Dodecylbenzenesulfonic acid Na salt 10% 14.3% C13 / 15-oxoalcohol reacted with 7 moles of ethylene oxide 10% 2.9% Potassium coconut soap ---- 2.8% Monopropylenglykol 6% 6% ethanol 2% 2% Savinase® Ultra Type 16 L (Novozymes A / S, DK-2880 Bagsvaerd) 1 % 1 % Polymer and / or complexing agent (additive) as specified as specified water to 100% to 100%

• Angegeben sind Summe Remissionswerte für 6 Schmutztypen, wie zuvor angegeben.

Tabelle 3: Waschergebnisse Formulierung A Additive Wasserhärte 0 mmol/l 4 mmol/l ohne Additiv (Vergleich) 245,9 263,1 4% Acrylsäure Homopolymer MW 4000 255,8 275,9 4% Maleinsäure/Olefin Copolymerisat MW 12000 255,8 268,4 4% Maleinsäure/Acrylsäure-Copolymer MW 3000 262,5 277,2 4% Methylglycindiessigsäure (MGDA) 266,4 275,2 MW = zahlenmittleres Molekulargewicht Tabelle 4: Waschergebnisse Formulierung B Additive Wasserhärte 0 mmol/l 4 mmol/l ohne Additiv (Vergleich) 249,1 228,7 4% Acrylsäure Homoplymer MW 4000
+3% Methylglycindiessigsäure (MGDA) 283,2 251,3 4% Maleinsäure/Olefin Copolymerisat MW 12000
+3% Methylglycindiessigsäure (MGDA) 278,3 235,3 4% Maleinsäure/Acrylsäure-Copolymer MW 3000
+ 3% Methylglycindiessigsäure (MGDA) 280,6 248,1 MW = zahlenmittleres Molekulargewicht Performance results of the washing tests:

• Given are total reflectance values for 6 types of spoil, as previously stated.

Table 3: Wash Results Formulation A additives water hardness 0 mmol / l 4 mmol / l without additive (comparison) 245.9 263.1 4% acrylic acid homopolymer MW 4000 255.8 275.9 4% maleic acid / olefin copolymer MW 12000 255.8 268.4 4% maleic acid / acrylic acid copolymer MW 3000 262.5 277.2 4% methylglycinediacetic acid (MGDA) 266.4 275.2 MW = number average molecular weight additives water hardness 0 mmol / l 4 mmol / l without additive (comparison) 249.1 228.7 4% acrylic acid Homoplymer MW 4000
+ 3% methylglycinediacetic acid (MGDA) 283.2 251.3 4% maleic acid / olefin copolymer MW 12000
+ 3% methylglycinediacetic acid (MGDA) 278.3 235.3 4% maleic acid / acrylic acid copolymer MW 3000
+ 3% methylglycinediacetic acid (MGDA) 280.6 248.1 MW = number average molecular weight

It can clearly be seen that when the polymers according to the invention or the polymer / complexing agent combinations are added, the washing performance of the liquid, protease-containing detergent formulations can be markedly improved with different water hardness.

II. Dirt removal as a function of the enzyme concentration used

The following detergent formulation C was used: Dodecylbenzenesulfonic acid - Na salt 11.40% C13 / 15-oxoalcohol reacted with 7 moles of ethylene oxide 5.70% Potassium coconut soap 2.90% Monopropylenglykol 6% ethanol 2% Enzyme Savinase Ultra Type 16 L 1 % Additive mixture of polymer and complexing agent to FIG. 1 water to 100%

The additive mixture used was a mixture of polyacrylic acid (sodium salt) having a number-average molecular weight of 1200 g / mol and methylglycinediacetic acid (MGDA) in a weight ratio of 3: 1.

• Temperatur: 40°C (Koch/Buntwäsche-Programm)
• Wasserhärte: 2,5 mmol/l (Ca : Mg = 4 : 1) (14 ° dH)
• Dosierung: 75 ml
• Textilbeladung: 3,5 kg Ballast
  je 2 x Schmutzgewebeproben gemäß Tabelle 5
  2 x Schmutz wfk SBL 2004

The experiments were carried out in a commercially available Miele Novotronic® W 927 washing machine with the following washing conditions:

• Temperature: 40 ° C (cooking / color-washing program)
• Water hardness: 2.5 mmol / l (Ca: Mg = 4: 1) (14 ° dH)
• Dosage: 75 ml
• Textile load: 3.5 kg ballast
  2 x dirt tissue samples according to Table 5
  2 x Dirt wfk SBL 2004

The accompanying dirt and the addition of tissue samples with non-enzymatically removable types of dirt was done to achieve a pollution load of conventional household laundry. Table 5 general wfk 20D Sebum / pigment on mixed tissue soil removal E 101 Olive oil / soot on cotton E 141/2 Lipstick on cotton CFT PCS 4 Olive oil on blended fabric bleachable E 114 Red wine on cotton soiling CFT BC 1 Tea on cotton CFT BC 2 Coffee on cotton CFT PCS 3 Red wine on mixed fabric Enzyme- E 112 IEC Cocoa on cotton soil removal E 116 Blood / milk / ink on cotton CFT CS 1 Blood on cotton CFT CS 8 Grass on cotton CFT CS 10 Butter on cotton CFT AS 10 Pigment / peanut oil / milk on cotton CFT PC 5 Blood / milk / ink on blended fabric CFT CS 28 Rice starch on cotton

To determine the proteolytic wash performance, the whiteness of the soiled fabric was measured before and after washing with a photometer (Elrepho 2000) from Datacolor AG, CH-8305 Dietikon, Switzerland, on the basis of the remission (%). The remission values were determined at 460 nm, wherein in each case 6 measuring points per type of spoil were averaged. Only the remission values of the tissues with enzymatic impurities according to Table 5 were determined. Of the 2 tissues of each type of soiling, the mean was formed. The remission averages for all 8 spoil types were then summed up. FIG. 1 shows the sum of the remission values without and with additive mixture (polyacrylic acid Na salt and MGDA) as a function of the enzyme concentration. It can clearly be seen that a significant improvement in the proteolytic wash performance is achieved with the additive mixture according to the invention at all investigated protease concentrations.

III. Dirt removal depending on the additive used

The following detergent formulation D was used: Dodecylbenzenesulfonic acid - Na salt 11.40% C13 / 15-oxoalcohol reacted with 7 moles of ethylene oxide 5.70% Potassium coconut soap 2.90% Monopropylenglykol 6% ethanol 2% Enzyme Savinase Ultra Type 16 L 1 % Additive (polymer and / or complexing agent) according to Table 6 water to 100%

• Temperatur: 40°C
• Wasserhärte: 2,5 mmol/l (Ca : Mg = 4 : 1) (14 ° dH)
• Dosierung: 5 g/l
• Textilbeladung: Schmutzgewebeproben gemäß Tabelle 6

Tabelle 6 Enzym- E 112 IEC Kakao auf Baumwolle Schmutzentfernung E 116 Blut/Milch/Tusche auf Baumwolle CFT CS 10 Butter auf Baumwolle The experiments were carried out in a launderometer from the company Atlas, Chicago, USA with the following washing conditions:

• Temperature: 40 ° C
• Water hardness: 2.5 mmol / l (Ca: Mg = 4: 1) (14 ° dH)
• Dosage: 5 g / l
• Textile load: Dirt samples according to Table 6

Table 6 Enzyme- E 112 IEC Cocoa on cotton soil removal E 116 Blood / milk / ink on cotton CFT CS 10 Butter on cotton

To determine the proteolytic wash performance, the whiteness of the soiled fabric was measured before and after washing with a photometer (Elrepho 2000) from Datacolor AG, CH-8305 Dietikon, Switzerland, on the basis of the remission (%). The remission values were determined at 460 nm, wherein in each case 6 measuring points per type of spoil were averaged. The remission values for all 3 types of spoilage were then summed up. The results are shown in Table 7. It can clearly be seen that the greatest improvement in the proteolytic wash performance is achieved with additive mixtures according to the invention. Table 7: Ex. Hardness [mmol / l] polymer Amount of polymer [%] complexing Amount of complexing agent [%] Total enzymatic removal of soil 1 2.5 without 0 without 0 121.1 2 2.5 Polymer 1 * 3 without 0 132.1 3 2.5 without 0 Trilon M fl (MGDA) 1 125.7 4 2.5 Polymer 1 * 3 Trilon M fl (MGDA) 1 133.9 5 4 without 0 without 0 110.8 6 4 Polymer 1 * 3 without 0 121.7 7 4 without 0 Trilon M fl (MGDA) 1 110.8 8th 4 Polymer 1 * 3 TrilonM fl. (MGDA) 1 128.6 9 2.5 without 0 without 0 121.1 10 2.5 Polymer 2 ** 3 without 0 128.2 11 2.5 without 0 Trilon M fl (MGDA) 1 125.7 12 2.5 Polymer 2 ** 3 Trilon M fl (MGDA) 1 132.7 13 4 without 0 without 0 110.8 14 4 Polymer 2 ** 3 without 0 122.6 15 4 without 0 Trilon M fl (MGDA) 1 110.8 16 4 Polymer 2 ** 3 Trilon M fl (MGDA) 1 26.3 17 2.5 without 0 without 0 121.1 18 2.5 Polymer 3 *** 3 without 0 136.2 19 2.5 without 0 Trilon M fl (MGDA) 1 125.7 20 2.5 Polymer 3 *** 3 Trilon M fl (MGDA) 1 136.5 21 4 without 0 without 0 110.8 22 4 Polymer 3 *** 3 without 0 125.5 23 4 without 0 Trilon M fl (MGDA) 1 110.8 24 4 Polymer 3 *** 3 Trilon M fl (MGDA) 1 130.0 * Polymer 1 = maleic acid / acrylic acid copolymer, M _n 3000
** Polymer 2 = acrylic acid homopolymer, M _n 1200
*** Polymer 3 = acrylic acid homopolymer M _n 4000

Claims (20)

Use of at least one acid group-containing compound selected from organic complexing agents and polymeric carboxylic acid group-containing compounds as an additive in an enzyme-containing liquid washing or cleaning composition for improving the washing or cleaning performance. Use according to claim 1, wherein the composition is in the form of a laundry detergent. Use according to one of the preceding claims for improving the enzymatic washing or cleaning performance, in particular the proteolytic washing or cleaning performance. Use according to one of the preceding claims, wherein the detergent or cleaning composition is 0.1 to 20 wt .-%, preferably 0.5 to 15 wt .-%, in particular 1 to 10 wt .-%, based on the total weight of the composition, contains at least one acid group-containing compound which is selected from organic complexing agents, polymeric carboxylic acid-containing compounds and mixtures thereof. Use according to any one of the preceding claims, wherein the detergent composition contains a combination of at least one organic complexing agent and at least one polymeric carboxylic acid group-containing compound. Use according to one of the preceding claims, wherein the organic complexing agent comprises or consists of methylglycinediacetic acid. Use according to one of claims 1 to 6, wherein the polymeric carboxylic acid group-containing compound used is an acrylic acid homopolymer. Use according to any one of claims 1 to 6, wherein the polymeric carboxylic acid group-containing compound used is a copolymer containing at least one acrylic acid monomer selected from acrylic acid, acrylic acid salts and mixtures thereof and containing at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof , Use according to any one of claims 1 to 6, wherein the polymeric carboxylic acid group-containing compound is a copolymer of at least one maleic acid monomer, selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof with at least one C ₂ -C ₈ olefin. Use according to one of claims 1 to 6, wherein the polymeric carboxylic acid group-containing compound is a polyamine modified with carboxylic acid groups, preferably a polyakylenimine modified with carboxylic acid groups, especially a polyethylenimine modified with carboxylic acid groups, more particularly a carboxymethylated polyethylenimine. Use of a combination of methylglycinediacetic acid and at least one polymeric carboxylic acid group-containing compound as defined in any one of claims 7 to 10 as an additive in an enzyme-containing liquid detergent composition for improving the washing or cleaning performance. Use of a combination of at least one carboxylic acid group-modified polyamine as defined in claim 10 and at least one polymeric carboxylic acid group-containing compound thereof as defined in any one of claims 7 to 9 as an additive in an enzyme-containing liquid detergent composition to improve detergency or cleaning performance. Use according to any one of the preceding claims, wherein the detergent or cleaner composition contains as enzyme at least one hydrolase, preferably at least one protease and / or amylase. Use according to claim 13, wherein the detergent composition contains as protease at least one subtilisin-type protease, in particular at least one protease derived from Bacillus lentus. Use according to either of claims 13 or 14, wherein the detergent composition contains as additional enzyme at least one glucosidase. Use according to one of the preceding in an aqueous washing or cleaning composition. A process for improving the washing or cleaning performance of an enzyme-containing liquid detergent composition as defined in any one of claims 1 to 16, wherein said composition comprises at least one of acid group-containing compound which is selected from organic complexing agents and polymeric compounds containing carboxylic acid groups, is added as an additive. A liquid detergent composition as defined in any one of claims 1 to 16. An additive composition consisting of a combination of methylglycinediacetic acid and at least one polymeric carboxylic acid group-containing compound as defined in any one of claims 7 to 9. An additive composition consisting of a combination of at least one carboxylic acid group-modified polyamine as defined in claim 10 and at least one polymeric carboxylic acid group-containing compound thereof as defined in any one of claims 7 to 9.

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