WO2001007551A1

WO2001007551A1 - Use of polyvinyl alcohols as detergent additives capable of removing soiling

Info

Publication number: WO2001007551A1
Application number: PCT/EP2000/005539
Authority: WO
Inventors: Jörg Poethkow; Horst-Dieter Speckmann; Paul Birnbrich; Thomas Möller; Christian Block; Herman-Josef Welling
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-07-26
Filing date: 2000-06-16
Publication date: 2001-02-01
Also published as: CA2312154A1; AU5815000A

Abstract

The aim of the invention is to improve the detergent performance of detergents during the laundering of textiles. This is essentially accomplished by using polyvinyl alcohol.

Description

"Use of polyvinyl alcohols as dirt release agents

Detergent additives "

The present invention relates to the use of polyvinyl alcohol as a dirt-releasing polymer for enhancing the cleaning performance of detergents when washing textiles, in particular those which consist of cotton or contain cotton, and detergents which contain polyvinyl alcohol in combination with a specific surfactant system.

In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain other ingredients, which can be summarized under the term washing aids and which include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors. Such auxiliary substances also include substances which impart dirt-repellent properties to the laundry fiber and which, if present during the washing process, support the dirt-removing ability of the other detergent components. The same applies analogously to cleaning agents for hard surfaces. Such soil release agents are often referred to as "soil release" actives or because of their ability to make the treated surface, for example the fiber, dirt repellent, "soil repellents". Because of their chemical similarity to polyester fibers in textiles made from this material, particularly effective dirt-releasing active ingredients are copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil-removing copolyesters of the type mentioned and their use in detergents have been known for a long time.

For example, German published patent application DE 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. The German patent application DE 22 00 911 relates to detergents, nonionic surfactants and contain a copolymer of polyoxyethylene glycol and polyethylene terephthalate. German published patent application DE 22 53 063 mentions acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol. Polymers made from ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights from 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents are described in German patent DE 28 57,292. Polymers with a molecular weight of 15,000 to 50,000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 2: 1 to 6: 1, can be according to the German published patent application DE 33 24 258 can be used in detergents. European patent EP 0 066 944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. European or European patent EP 0 185 427 discloses methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain such a soil release polymer. European patent EP 0 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and glycerol units. Dirt-releasing polyesters are known from European patent EP 0 241 985 which, in addition to oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and are end-capped with Ci to C alkyl groups. European patent EP 0 253 567 relates to soil release polymers with a molecular weight of 900 to 9000 made of ethylene terephthalate and polyethylene oxide terephthalate. wherein the polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95. European patent application EP 0 272 033 discloses dirt-releasing polyesters with poly-propylene terephthalate and polyoxyethylene end groups that are at least partially capped by C alkyl or acyl radicals. terephthalate units known. European patent EP 0 274 907 describes sulfoethyl end group-capped terephthalate-containing soil release polyesters. In European patent application EP 0 357 280, soil-release polyesters with terephthalate, alkylene glycol and poly-C - glycol units are produced by sulfonation of unsaturated end groups. The graft copolymers of polyalkylene oxides based on ethylene oxide known from European patent specification EO 0 219 048. Propylene oxide and / or butylene oxide and optionally partially saponified vinyl acetate have an anti-soiling effect.

The polymers known from this extensive state of the art have the disadvantage that they have no or only inadequate effectiveness in textiles which do not consist, or at least not predominantly, of polyester. A large part of today's textiles consists of cotton or cotton-polyester blended fabrics, so that there is a need for polymers which are more effective at removing soiling, even with greasy soiling on such textiles.

Surprisingly, it has been found that this object can be achieved by using polyvinyl alcohols.

The invention relates to the use of polyvinyl alcohol to enhance the cleaning performance of detergents when washing textiles, in particular if these consist of cotton or contain cotton.

Polyvinyl alcohols are not accessible through direct polymerization processes because the necessary basic monomer vinyl alcohol does not exist. Polyvinyl alcohols are therefore produced in polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (for example methanol) in solution.

Polyvinyl alcohols which are preferably used according to the invention and which are usually commercially available as white-yellowish powders or granules have molar masses in the range from 3000 g / mol to 320,000 g / mol, in particular 8000 g / mol to 200,000 g / mol (corresponding to degrees of polymerization in Range of about 75-8000, especially about 200 up to 5000). They preferably have degrees of hydrolysis of 20% by weight to 100% by weight. in particular from 30% by weight to 90% by weight. Also suitable are polyvinyl alcohols with molecular weights in the range from 10000 g / mol to 100000 g / mol (corresponding degrees of polymerization in the range from 500 to 2500) and degrees of hydrolysis from 85% by weight to 90% by weight.

These polyvinyl alcohols are therefore wholly or partially saponified polyvinyl alcohol esters, in particular polyvinyl acetates, with a residual content of acyl groups, in particular acetyl groups, of up to about 80% by weight, in particular from 10% by weight to 12%. -%. The polyvinyl alcohols can be characterized in more detail by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity. The polyvinyl alcohols are of high purity and contain at most 3% by weight of methanol.

The transition temperatures of the polyvinyl alcohols depend on the acetyl group content, the distribution of the acetyl groups along the chain and the tacticity of the polymers. Fully hydrolyzed polyvinyl alcohols have a glass transition temperature of 85 ° C, whereby the value for partially hydrolyzed (87-89%) products is significantly lower at approx. 58 ° C. Depending on the degree of hydrolysis, polyvinyl alcohols, which normally have a density of approximately 1.2-1.3 g / cm ³ , are normally soluble in water and strongly polar organic solvents such as formamide, dimethylformamide and dimethyl sulfoxide, (chlorinated) hydrocarbons, esters, fats and oils are not attacked. Polyvinyl alcohols are classified as toxicologically safe and are biodegradable.

In addition to the polyvinyl alcohols, other dirt-releasing polymers, in particular polyester-active dirt-releasing polymers, can be used if desired. These include copolyesters from dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. The preferred dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR ^π -) _a OH, which can also be present as a polymeric diol H- (O- (CHRιι-) _a ) _b OH. In this, Ph denotes an o-, m- or p-phenylene radical which has 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms. Sulphonic acid groups, carboxyl groups and mixtures thereof, R ^{11 can be} hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof, a a number from 2 to 6 and b a number from 1 to 300. They are preferably in the These available polyesters have both monomer diol units -O- (CHRπ-) _a O- and polymer diol units - (O- (CHR ^π -) _a ) bO-. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. The degree of polymerization b in the polymer diol units is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred dirt-releasing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000 The acid on which the radical Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among them, the sodium and potassium salts are particularly preferred. If desired, instead of the HOOC-Ph-COOH monomer, small amounts, in particular not more than 10 mol%, based on the amount of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the dirt-releasing polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, beπisteinsäure, fumaric acid. Maleic acid. Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO- (CHR ^π -) _a OH include those in which R ^{1 1 is} hydrogen and a is a number from 2 to 6, and those in which a is 2 and R ^{1 1} is hydrogen and the Alkyl radicals with 1 to 10, in particular 1 to 3 carbon atoms is selected. Among the latter diols, those of the formula HO-CH ₂ -CHR ^π -OH, in which R ^{11 has} the abovementioned meaning, are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol. 1,4-butanediol. 1,5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1,2-decane diol, 1,2-dodecanediol and neopentyl glycol. Polyethylene glycol with an average molecular weight in the range from 1000 to 6000 is particularly preferred among the polymeric diols. If desired, these polyesters can also be end group-closed, alkyl groups with 1 to 22 C atoms and esters of monocarboxylic acids being suitable as end groups. The end groups bonded via ester bonds can be alkyl. Alkenyl and aryl monocarboxylic acids with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, are the basis. These include valeric acid, caproic acid, enanthic acid. Caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, aric acid, linoleic acid, linoleic acid, arenol acid, arenostolic acid, arenol acid, arenol acid, arenol acid, arenol acid, arenol acid, Brassidic acid, clupanodonic acid, lignoceric acid, cerotinic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 C atoms, in particular 1 to 12 C atoms, for example tert-butylbenzoic acid. The end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids can in turn be connected to one another via their hydroxyl group and their carboxyl group and can therefore be present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is preferably in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used in combination with polyvinyl alcohol. In a further preferred embodiment of the invention, graft copolymers of polyalkylene oxides based on ethylene oxide, propylene oxide and / or butylene oxide and optionally partially saponified vinyl acetate, in which the weight ratio of polyalkylene oxides to vinyl acetate is 1: 0.2 to 1:10, in combination with Polyvinyl alcohol is used. In the presence of other dirt-releasing polymers, weight ratios of polyvinyl alcohol are too another soil release polymer in the range of 10: 1 to 1:10. in particular 5: 1 to 1: 5 particularly preferred.

The use according to the invention can take place in the course of a washing process in such a way that the polyvinyl alcohol is added separately to a detergent-containing liquor, or the polyvinyl alcohol is introduced into the liquor as part of the detergent. The invention therefore furthermore relates to a detergent which contains polyvinyl alcohol and 5% by weight to 30% by weight, in particular 10% by weight to 25% by weight, of surfactant, the content of polyvinyl alcohol being in particular 0.1% by weight % to 10% by weight, particularly preferably 1% by weight to 4% by weight and, in a further preferred embodiment of agents according to the invention and also the use according to the invention, the weight ratio of surfactant to polyvinyl alcohol is in the range from 20: 1 to 5: 1, in particular 15: 1 to 7: 1. It is possible to use the polyvinyl alcohol in an intimate mixture with the other detergent ingredients. In a preferred embodiment of the invention, a detergent product is used which has at least a part of the polyvinyl alcohol in the form of a bag comprising polyvinyl alcohol or material containing polyvinyl alcohol and optionally the remaining part of the polyvinyl alcohol. Films or capsules made of polyvinyl alcohol for packaging, in particular for portions of detergent pre-portioned for one washing cycle, are known, for example, from international patent applications WO 98/30670, WO 97/35955, WO 95/18215 or WO 91/7202 or German patent applications DE 195 21 140 or DE 44 16 481 known. The introduction of such packaged amounts of detergent into water, in which both the polyvinyl alcohol in the packaging material dissolves and the remaining detergent dissolves or disperses, makes it particularly easy to use the polyvinyl alcohol according to the invention.

Solid detergents according to the invention or solid detergents packaged in polyvinyl alcohol-containing material can be prepared in a traditional manner by spray drying an aqueous slurry of these constituents or else can be obtained by agglomeration granulation of the more or less solid constituents. A particularly preferred manufacturing process is granulation under pressure, preferential in extruders to form endless strands, which are then cut to the desired grain size with the help of knives. Such a method is described in detail in European patent EP 0 486 592. An example of the production of granular agents in high-speed mixers can be found in international patent application WO 93/23523. The agent preferably has a bulk density of more than 500 g / 1, a practical upper limit being set at about 1400 g / 1, but this can also be exceeded in individual cases. The bulk density of the composition is preferably in the range from 600 g / 1 to 1200 g / 1 and in particular in the range from 700 g / 1 to 1000 g / 1. The average grain size of the agent is preferably in the range from 0.8 mm to 6 mm, in particular in the range from 1 mm to 3 mm and particularly preferably between 1.2 mm and 2 mm.

Detergents which contain a polyvinyl alcohol to be used according to the invention can contain all the usual other constituents of such compositions which do not interact undesirably with the soil-release polymer. For use in accordance with the invention, polyvinyl alcohol is preferably incorporated into detergents in amounts of 0.1% by weight to 5% by weight, in particular 0.5% by weight to 2.5% by weight, and unfolds its properties when detergents of this type are used A good amount of dirt-removing effect. Since this effect is less pronounced in the presence of larger amounts of nonionic surfactants, it is preferred that agents or agents according to the invention which are to be used together with the polyvinyl alcohol used according to the invention contain no more than 60% by weight of nonionic surfactant, such nonionic surfactant is selected in particular from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, especially ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof.

The nonionic surfactants suitable for use in agents according to the invention or in those in the presence of which polyvinyl alcohol is used according to the invention include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched chain alcohols with 10 up to 22 carbon atoms, preferably 12 to 18 carbon atoms Atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the alkoxylates, in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used. Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used. In addition, there are the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as in accordance with the processes of US Pat. No. 1 985 424, US 2 016 962 and US 2 703 798 and international patent application WO 92/06984 can be considered. So-called alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) _n -OR, in which R is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. Such compounds and their preparation are described, for example, in European patent applications EP 0 092 355, EP 0 301 298, EP 0 357 969 and EP 0 362 671 or the US Pat. No. 3,547,828. The glycoside component (G) _n is an oligomer or polymer from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose. Talose, Gulose, Altrose, Allose, Idose, Ribose, Arabinose, Xylose and Lyxose belong. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization. The degree of oligomerization n generally assumes fractional numerical values as the quantity to be determined analytically: it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its good availability. The alkyl or Alkenyl part R of the glycosides preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl and tetradecyl are particularly useful. Hexadecyl or octadecyl residues and mixtures thereof. Particularly preferred alkyl glycosides contain a coconut fatty alkyl radical, that is to say mixtures with essentially R = dodecyl and R = tetradecyl.

Instead or in addition, such agents can each be based on additional surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight on total means included. Synthetic anionic surfactants which are particularly suitable for use in agents of this type are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms and carrying an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation , The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched chain analogs, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. Such alkyl and / or alkenyl sulfates are present in the agents according to the invention or in the agents used in combination with the polyvinyl alcohol used according to the invention, preferably in amounts of 0.1% by weight to 20% by weight, in particular 0.5%. -% to 18 wt .-% contain.

The sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the .alpha.-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 8 to 22 carbon atoms. preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, sulfonation products, as well as the sulfofatty acids resulting from these by formal saponification.

Soaps can be considered as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable. In particular, those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C ₈ -C ₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. However, in particular in liquid compositions which contain a polymer used according to the invention, higher amounts of soap, as a rule up to 20% by weight, can also be present.

In a further embodiment, an agent which contains a polymer to be used according to the invention contains water-soluble and or water-insoluble builders, in particular selected from alkali alumosilicate, crystalline alkali silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range of 2 .5% to 60% by weight.

An agent which contains polyvinyl alcohol to be used according to the invention preferably contains 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110 accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances in copolymerized form without carboxylic acid functionality. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000 on. 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. Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C -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 ₈ -C ₈ -dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, vinyl alcohol derivatives are preferred which are an ester of short-chain carboxylic acids, for example C 1 -C 8 -carboxylic acids, with vinyl alcohol. Preferred polymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% vinyl alcohol and / or vinyl acetate. Tepolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2, are very particularly preferred. 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an AUylsulfonic acid which, in the 2-position, has an alkyl radical, preferably a C 1 -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives. is substituted. Preferred polymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight. %, preferably 15% by weight to 25% by weight of methallylsulfonic acid or methallylsulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate. This carbohydrate can, for example, be a mono-, di-, oligo or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. The use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer. These polymers can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. They can be used, in particular for the preparation of liquid compositions, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents in which the polymer according to the invention is contained.

The water-insoluble, water-dispersible inorganic builder materials used are, in particular, crystalline or amorphous alkali alumosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions, in particular from 1% by weight to 5% by weight, used. Among these, the crystalline aluminosilicates in detergent quality, in particular zeolite NaA and optionally NaX, 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 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12 837, is in the range from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the alumosilicate 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 in the compositions preferably assign a molar ratio of alkali oxide SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12 and can be amoφh or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 0: SiO molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a molar ratio Na O: SiO of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0 425 427. They are preferably added as a solid and not in the form of a solution during production. Crystalline layered silicates of the general formula Na Si _x O _2x + ι yH 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. In particular, both β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ -yH ₂ O) are preferred, whereby β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. δ-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. Also practically anhydrous crystalline alkali silicates of the general formula mentioned above, in which x is a number from 1.9 to 2.1, can be produced from amorphous alkali silicates, as in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428 described, can be used in agents containing a polymer according to the invention. In a further preferred embodiment of agents according to the invention, 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 0 436 835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent EP 0 164 552 and or European patent application EP 0 294 753, are used in a further preferred embodiment of washing or Detergents containing a polymer according to the invention are used. Their alkali silicate content is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on anhydrous active substance. If alkali alumosilicate is used as an additional builder. in particular zeolite, the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on the anhydrous active substance. The weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is then preferably 4: 1 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, 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.

In addition to the inorganic builder mentioned, other water-soluble or water-insoluble inorganic substances can be used in the compositions which contain a polyvinyl alcohol used according to the invention as a soil-release polymer. In this context, the alkali carbonates, alkali hydrogen carbonates and alkali sulfates and mixtures thereof are suitable. Such additional inorganic material can be present in amounts up to 70% by weight, but is preferably absent entirely.

In addition, the agents can contain further constituents customary in washing and cleaning agents. These optional constituents include, in particular, enzymes, enzyme stabilizers, bleaching agents, bleach activators, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, graying inhibitors, for example cellulose ethers, color transfer inhibitors, for example polyvinyl ether inhibitors, for example polyvinyl indenone inhibitors, for example polyvinyl indenone inhibitors, for example polyvinylinhibin, for example polyvinyl indenone, for example polyvinylinhibin, for example polyvinylinhibin, for example polyvinylinhibin, for example polyvinyl inh Organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Up to 1% by weight are preferred in agents which contain a polymer according to the invention. in particular 0.01% by weight to 0.5% by weight of optical brighteners, in particular compounds from the class of the substituted 4,4'-bis (2.4.6-triamino-s-triazinyl) -stilbene-2,2 '-disulfonic acids, up to 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts, up to 3% by weight, in particular 0.5% by weight up to 2% by weight of graying inhibitors and up to 2% by weight, in particular 0.1% by weight contain up to 1% by weight of foam inhibitors, the proportions by weight in each case referring to the total average.

Solvents which are used in particular in the case of liquid compositions which contain a polymer used according to the invention are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols. for example ethylene and propylene glycol, and the ethers which can be derived from the compound classes mentioned. In such liquid compositions, the polymers used according to the invention are generally in solution or in suspended form.

Any enzymes present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof. Protease obtained from microorganisms, such as bacteria or fungi, is primarily suitable. It can be obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German patent applications DE 19 40 488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and US 4,264,738, European patent application EP 006 638 and international patent application WO 91/02792 are described. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase which can be used can be obtained from Humicola lanuginosa, as described, for example, in European patent applications EP 0 258 068, EP 0 305 216 and EP 0 341 947, from Bacillus species, such as, for example, in international patent application WO 91/16422 or European patent application EP 0 384 717, from Pseudomonas species, as for example in European patent applications EP 0 468 102, EP 0 385 401, EP 0 375 102, EP 0 334 462, EP 0 331 376, EP 0 330 641, EP 0 214 761 EP 0 218 272 or EP 0 204 284 or the international patent application WO 90/10695, from Fusarium species, as described for example in the European patent application EP 0 130 064, from Rhizopus species, as for example in the European patent application EP 0 117 553, or from AspergiUus species, as described, for example, in European patent application EP 0 167 309, be won. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase. Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm. The cellulase which can be used can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5. Such cellulases are known, for example, from German patent applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 0 265 832, EP 0 269 977, EP 0 270 974, EP 0 273 125 and EP 0 339 550 are known.

The usual enzyme stabilizers which are optionally present, in particular in liquid agents, include amino alcohols, for example mono-, di-, triethanol- and propanolamine and mixtures thereof, lower carboxylic acids, for example from European patent applications EP 0 376 705 and EP 0 378 261 known, boric acid or alkali borates, boric acid-carboxylic acid combinations, such as known from European patent application EP 0 451 921, boric acid esters, such as known from international patent application WO 93/11215 or European patent application EP 0 511 456, boronic acid derivatives, such as known, for example, from European patent application EP 0 583 536, calcium salts, for example the Ca-formic acid combination known from European patent EP 0 028 865, magnesium salts, such as known from European patent application EP 0 378 262, and / or sulfur-containing reducing agents, like that known for example from European patent applications EP 0 080 748 or EP 0 080 223.

Suitable foam inhibitors include long-chain soaps, especially behen soap. Fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and their mixtures, which may also contain microfine, optionally silanized or otherwise hydrophobized silica. For use in particulate compositions, such foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German Offenlegungsschrift. The publication DE 34 36 194, the European patent applications EP 0 262 588, EP 0 301 414, EP 0 309 931 or the European patent EP 0 150 386.

This can also be an agent which contains a polymer used according to the invention. Graying inhibitors included. Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the graying of the fibers. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example partially hydrolyzed starch. Na carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof are preferably used.

A further embodiment of such an agent, which contains a soil-release polymer to be used according to the invention, contains bleaching agents based on peroxygen, in particular in amounts in the range from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts in the range from 2% to 10% by weight. These bleaching agents that can be used are the per compounds generally used in detergents, such as hydrogen peroxide, perborate, which can be present as tetra- or monohydrate, percarbonate, pyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts. Such bleaching agents are in detergents which contain a polymer used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight, in each case on all means, available. The optional component of the bleach activators includes the commonly used N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines and sulfuryl amides, sulfuryl amides , especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyl or -isononanoyloxybenzenesulfonate, and acylated sugar derivatives, especially pentaacetyl glucose. To avoid the interaction with the peroxygen compounds during storage, the bleach activators may have been coated or granulated with coating substances in a known manner, with tetraacetylethylenediamine granulated with carboxymethyl cellulose having average grain sizes of 0.01 mm to 0.8 mm, as described, for example, by can be prepared in the European patent EP 0 037 026, and / or granulated 1,5-diacetyl-2,4-dioxohexahydro-1,5,5-triazine, as described in the German patent DD 255 884 Process can be produced, is particularly preferred. Such bleach activators are preferably in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight. in each case based on the total mean.

In a preferred embodiment, an agent into which the soil release polymer to be used according to the invention is incorporated is particulate and contains 20% by weight to 55% by weight of inorganic builder, up to 15% by weight, in particular 2% by weight. % to 12% by weight water-soluble organic builder, 2.5% to 20% by weight synthetic anionic surfactant, 1% to 20% by weight nonionic surfactant, up to 25% by weight, in particular 1% by weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5% by weight to 6% by weight of bleach activator and up to 20% by weight, in particular 0.1% by weight to 15% by weight of inorganic salts, in particular alkali carbonate and / or sulfate.

Another preferred embodiment comprises a liquid agent containing 5% by weight to 35% by weight of water-soluble organic builder, up to 15% by weight, in particular 0.1% by weight to 5% by weight of water-insoluble inorganic builder , up to 25% by weight, in particular 0.5% by weight to 15% by weight of synthetic anionic surfactant, 1% by weight to 45% by weight, in particular 15% by weight to 25% by weight nonionic surfactant, up to 25% by weight, in particular 4% by weight to 15% by weight of soap and up to 30% by weight, in particular 1% by weight to 25% by weight of water and / or water-miscible Solvent. Examples

Example 1:

The polyvinyl alcohols given in Table 1 were converted into particulate detergents (E1 to E6) containing 2% by weight of the respective polyvinyl alcohol (P1 to P6) and 7% by weight of ethoxylated fatty alcohol and 1% by weight of soap by admixing the other constituents , 20% by weight alkylbenzenesulfonate, 35% by weight zeolite Na-A, 7% by weight sodium citrate, 7% by weight polymeric polycarboxylate, 5% by weight sodium carbonate, 2% by weight enzyme granules (protease, lipase , Cellulase, amylase), rest on 100% water and neutral salts, and the resulting agents were tested for their washing performance against greasy soiling. In addition, for comparison, a detergent (VI) composed as described above, which lacked the addition of polyvinyl alcohol, and which was packed into a film bag made of polyvinyl alcohol (proportion of polyvinyl alcohol film in the entire product also 2% by weight), was tested agent VI (E7). For this purpose, the standardized test stains A (lipstick) and B (creme rouge) listed in the table below were cleaned on patches of cotton, polyester or polyester-cotton blended fabrics in a Miele Novotronic® W918 washing machine in a 1-lye program together with 3.5 kg cleaner Filled laundry washed at 40 ° C (water hardness 16 ° dH, detergent dosage 80 g). The test fabrics were then dried and their degree of cleanliness was determined by reflectance measurement (at 460 nm). The reflectance increases (ddE) are given in Tables 2, 3 and 4 below. Table 1: Polyvinyl alcohols

Table 2: Increase in remission (ddE) for soiling on cotton

Table 3: Increase in reflectance (ddE) for soiling on cotton-polyester

Table 4: Increase in reflectance (ddE) for soiling on polyester

n.a .: not determined.

Example 2:

Analogous to Example 1, but using polyvinyl alcohols (P9, P10) which were obtained by partial acetylation of the polyvinyl alcohol Polyviol 05/290 (P8) (commercial product from Wacker). The partially acetylated polyvinyl alcohols P1 and P12 are blown films with the following composition. Pl 1: 83.0% polyviol 05/290, 11.3% glycerin, 5.1% sorbitol, 0.5% Aerosil, 0.1% stearic acid. P12: 37.6% Polyviol 05/290, 37.6% Mowilith 8/88 (polyvinyl alcohol, commercial product from Clariant), 16.7% glycerin, 4.6% sorbitol, 2.8% distilled water, 0.5 % Aerosil. 0.2% stearin. The mixtures were processed at 50 rpm and granulated. The granules obtained were processed in a film blowing system (Brabender single-screw kneader). The temperature profile from the feed zone to the nozzle was set as follows: Heating zones 1 to 6: 180, 175, 160, 150, 120, 120 ° C. The snail was with 50 rpm operated, this resulted in a torque of 80 Nm. A film removal speed of 1.3 was set. E8 to E12 are the particulate detergents obtained by adding the other constituents analogously to Example 1 and containing the respective polyvinyl alcohol (P8 to P12). In addition, a detergent (V2) composed as described in Example 1, which lacked the addition of polyvinyl alcohol, was also tested for comparison.

Table 5: partially acetylated polyvinyl alcohols

Table 6: Increase in remission (ddE) for soiling on cotton

Table 7: Increase in remission (ddE) for soiling on cotton-polyester

Table 8: Increase in reflectance (ddE) for soiling on polyester

n.a .: not determined

Claims

claims

1. Use of polyvinyl alcohol to enhance the cleaning performance of detergents when washing textiles.

2. Use of polyvinyl alcohol to enhance the cleaning performance of detergents when washing textiles made of or containing cotton.

3. Use according to claim 1 or 2, characterized in that the polyvinyl alcohol has a molar mass in the range from 3000 g / mol to 320000 g / mol, in particular 8000 g / mol to 200000 g / mol.

4. Use according to one of claims 1 to 3, characterized in that the polyvinyl alcohol is a partially saponified polyvinyl alcohol ester, in particular a polyvinyl acetate, with a residual content of acyl groups, in particular acetyl groups, up to about 80% by weight, in particular of 10% to 70% by weight.

5. Use according to one of claims 1 to 4, characterized in that the polyvinyl alcohol is used simultaneously with surfactant, the weight ratio of surfactant to polyvinyl alcohol in the range from 20: 1 to 5: 1, in particular 15: 1 to 7: 1 lies.

6. Laundry detergent which contains polyvinyl alcohol and 5% by weight to 30% by weight, in particular 10% by weight to 25% by weight, of surfactant.

7. Composition according to claim 6, characterized in that it contains 0.1 wt .-% to 10 wt .-%, in particular 1 wt .-% to 4 wt .-% polyvinyl alcohol.

8. Composition according to claim 6 or 7, characterized in that the weight ratio of surfactant to polyvinyl alcohol is in the range from 20: 1 to 5: 1, in particular 15: 1 to 7: 1.

9. Composition according to one of claims 6 to 8, characterized in that it has at least a part of the polyvinyl alcohol in the form of a bag comprising the remaining detergent components and optionally the remaining part of the polyvinyl alcohol made of polyvinyl alcohol or material containing polyvinyl alcohol.

10. Composition according to one of claims 6 to 9, characterized in that it has a bulk density in the range from 600 g / 1 to 1200 g / 1, in particular in the range from 700 g / 1 to 1000 g / 1.

11. Agent according to one of claims 7 to 11, characterized in that it has an average grain size in the range from 0.8 mm to 6 mm, in particular in the range from 1 mm to 3 mm.