EP1592763B1 - Washing product containing bleaching agents and a cellulose derivative which acts on cotton and has a dirt removing capacity - Google Patents

Abstract

Textile materials comprised at least partially of cotton are cleaned with a laundry detergent comprising bleach and an alkylated and/or hydroxyalkylated soil release-capable cellulose derivative having an average of from 0.5 to 2.5 alkyl groups and/or from 0.02 to 0.5 hydroxyalkyl groups per anhydroglycose monomer unit. The textile materials are cleaned more effectively with a laundry detergent containing the alkylated and/or hydroxyalkylated soil release-capable cellulose derivative.

Description

The present invention relates to the use of certain soil release cellulose derivatives to enhance the cleaning performance of bleach-containing detergents in the washing of textiles, especially those made of cotton or containing cotton, and bleach-containing detergents and cleaners containing such soil release cellulose derivatives.

Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builder materials usually further ingredients that can be summarized by the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and dye transfer inhibitors. Such adjuvants also include substances which impart soil repellency properties to the laundry fiber and, if present during the wash, aid the soil release properties of the remaining detergent ingredients. The same applies mutatis mutandis to cleaners for hard surfaces. Such soil release agents are often referred to as "soil release" agents or because of their ability to impart soil repellency to the treated surface, such as the fiber, as "soil repellents". Thus, for example, US Pat. No. 4,136,038 discloses the soil release activity of methylcellulose. European Patent Application EP 0 213 729 discloses the reduced redeposition when using detergents containing a combination of soap and nonionic surfactant with alkyl hydroxyalkyl cellulose. European Patent Application EP 0 213 730 discloses textile treatment compositions containing cationic surfactants and nonionic cellulose ethers having HLB values of from 3.1 to 3.8. US Pat. No. 4,000,093 discloses laundry detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or Alkyl-hydroxyalkyl cellulose and 5 wt .-% to 50 wt .-% surfactant, wherein the surfactant component consists essentially of C ₁₀ - to C ₁₃ alkyl sulfate and up to 5 wt .-% C ₁₄ alkyl sulfate and less than 5 wt .-% alkyl sulfate having alkyl radicals of C ₁₅ and higher. US Pat. No. 4,174,305 discloses laundry detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and from 5% to 50% by weight. % Surfactant, wherein the surfactant component consists essentially of C ₁₀ - to C ₁₂ alkylbenzenesulfonate and less than 5 wt .-% alkylbenzenesulfonate having alkyl radicals of C ₁₃ and higher. European Patent Specification EP 0 271 312 relates to soil release agents, among these cellulose alkyl ethers and cellulose hydroxyalkyl ethers (having DS 1.5 to 2.7 and molecular weights of 2,000 to 100,000) such as methyl cellulose and ethyl cellulose, which are weighted peroxygen bleach (based on the active oxygen content of the bleaching agent ) from 10: 1 to 1:10. European patent application EP 0 634 481 relates to a detergent containing alkali metal percarbonate and one or more nonionic cellulose derivatives. The latter expressly disclose only hydroxyethylcellulose, hydroxypropylcellulose and methylcellulose and, in the examples, the methylhydroxyethylcellulose Tylose® MH50, the hydroxypropylmethylcellulose Methocel® F4M and hydroxybutylmethylcellulose. European Patent EP 0 948 591 B1 discloses a detergent in liquid or granular form which imparts textile appearance advantages such as pilling / lint reduction, anti-color fading, improved abrasion resistance and / or increased softness to fabrics and textiles washed therewith, and provides 1 to 80 wt .-% of surfactant, 1 to 80 wt .-% organic or inorganic builder, 0.1 to 80 wt .-% of a hydrophobically modified nonionic cellulose ether having a molecular weight of 10,000 to 2,000,000, wherein the modification in the Presence of optionally oligomerized (degree of oligomerization up to 20) ethyleneoxy or 2-propyleneoxy ether units and C _8-24 alkyl substituents and the alkyl substituents in amounts of 0.1-5 wt .-%, based on the cellulose ether material, must be present.

Because of their chemical similarity to polyester fibers in textiles of this material particularly effective soil release agents are copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Dirt-releasing copolyesters of the type mentioned as well as their use in detergents have been known for a long time.

For example, German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. German laid-open specification DT 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. In the German patent application DT 22 53 063 acidic textile finishing agents are mentioned which contain a copolymer of a dibasic carboxylic acid and an alkylene or Cycloalkylenpolyglykol and optionally an alkylene or cycloalkylene glycol. 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 50:50 to 90:10, and their use in detergents are in the German patent DE 28 57,292. Polymers having a molecular weight of 15,000 to 50,000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: 1 to 6: 1, can according to the German Offenlegungsschrift DE 33 24 258 are used in detergents. European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. European Patent EP 185,427 discloses methyl or ethyl end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer. European Patent EP 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerol units. European Patent EP 241 985 discloses polyesters which, in addition to oxyethylene groups and terephthalic acid units containing 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and end-capped with C ₁ - to C ₄ alkyl groups. The European patent EP 253 567 relates. Soil-release polymers having a molecular weight of 900 to 9000 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 272 033 discloses, at least in part, polyesters having poly-propylene terephthalate and polyoxyethylene terephthalate units which are end-capped by C _1-4 -alkyl or acyl radicals. European Patent EP 274,907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. In the European patent application EP 357 280 soil-release polyesters are prepared by sulfonation of unsaturated end groups with terephthalate, alkylene glycol and Foly-C _2-4 glycol units. The German patent application DE 26 55 551 describes the reaction of such polyesters with isocyanate group-containing polymers and the use of the polymers thus prepared against the re-raising of dirt during the washing of synthetic fibers. Detergents are known from German Patent DE 28 46 984 which contain a reaction product of a polyester with a prepolymer containing terminal isocyanate groups, obtained from a diisocyanate and a hydrophilic nonionic macrodiol, as a dirt-absorbent-capable polymer.

The polymers known from this extensive prior art have the disadvantage that they have no or only insufficient effectiveness in textiles which are not or at least not predominantly made of polyester. However, a large part of today's textiles is made of cotton or cotton-polyester blend fabrics, so that there is a need for particularly greasy soiling on such textiles more effective soil release agents. Moreover, such soil release agents must not only be stable in the presence of bleaches normally present in laundry detergents, but should also have particularly good efficacy in such bleach-containing compositions, and desirably even improve or at least not impair the effectiveness of the bleaching agent.

Surprisingly, it has been found that this object can be achieved by the use of certain cellulose derivatives.

The invention relates to the use of a combination of soil release cellulose derivative which is obtainable by alkylation and hydroxyalkylation of cellulose, and bleaching agent for enhancing the cleaning performance of detergents in the washing of textiles, which in particular consist of cotton or contain cotton.

Another object of the invention is a process for laundering textiles using a bleach-containing detergent and a soil release cellulose derivative obtainable by alkylation and hydroxyalkylation of cellulose. This method can be carried out manually or preferably by means of a conventional household washing machine. It is possible to use the bleach-containing detergent and the soil release-capable cellulose derivative simultaneously or successively. The simultaneous application can be particularly advantageous by the use of a bleach-containing detergent, which contains the soil release wealthy cellulose derivative perform.

Particularly pronounced is the washing performance-enhancing effect of the cellulose derivatives to be used according to the invention with repeated use, that is to say in particular for removing soiling of corresponding textiles which had already been washed and / or post-treated in the presence of the cellulose derivative before being provided with the soil. In connection with the aftertreatment it should be noted that the positive aspect referred to can also be realized by a washing process in which the textile after the actual washing process, with the help of a bleach-containing detergent - which may contain a called cellulose derivative, but in this case also can be free of this - is carried out with an aftertreatment agent, for example, under a Softening step, which contains a cellulose derivative to be used according to the invention, is brought into contact. Also in this procedure occurs during the next washing process, although again if desired, although a bleach-containing detergent, but no detergent is used with a cellulose derivative mentioned, the washing performance enhancing effect of the present invention to be used cellulose derivatives.

Preferred cellulose derivatives are those which are alkylated with C ₁ to C ₁₀ groups, in particular C ₁ to C ₃ groups, and additionally carry C ₂ to C ₁₀ hydroxyalkyl groups, in particular C ₂ to C ₃ hydroxyalkyl groups. These can be obtained in known manner by reaction of cellulose with appropriate alkylating agents, for example alkyl halides or alkyl sulfates, and subsequent reaction with corresponding alkylene oxides, such as, for example, ethylene oxide and / or propylene oxide. In a preferred embodiment of the invention, a mean of 0.5 to 2.5, in particular 1 to 2, alkyl groups and 0.02 to 0.5, in particular 0.05 to 0.3, hydroxyalkyl groups per anhydroglycosemonomer unit are contained in the cellulose derivative. The average molar mass of the cellulose derivatives used according to the invention is preferably in the range from 10,000 D to 150,000 D, in particular from 40,000 D to 120,000 D and particularly preferably in the range from 80,000 D to 110,000 D. The determination of the degree of polymerization or of the molecular weight of the soil release-capable cellulose derivative is based on the determination of the limiting viscosity number of sufficiently dilute aqueous solutions by means of an Ubbelohde capillary viscometer (capillary 0c). Using a constant [H. Staudinger and F. Reinecke, "On Molecular Weight Determination on Cellulose Ethers", Liebigs Annalen der Chemie 535, 47 (1938)] and a Correction Factor [F. Rodriguez and LAGoettler, "The Flow of Moderately Concentrated Polymer Solutions in Water", Transactions of the Society of Rheology VIII, 3 17 (1964)] can be calculated from the degree of polymerization and, taking into account the degrees of substitution (DS and MS), the corresponding molecular weight.

As described, the cellulose derivatives used according to the invention can be prepared in a simple manner and are ecologically and toxicologically harmless. They lead to one Significantly better detachment of particular grease and cosmetic stains on cotton or cotton-containing tissues than is the case when using previously known compounds for this purpose. Alternatively, significant amounts of surfactants can be saved while maintaining fat removal capability.

The use according to the invention can be carried out as part of a washing process by adding a bleaching agent and the cellulose derivative of a detergent-containing liquor, adding the cellulose derivative of a bleach-containing and detergent-containing liquor separately, or preferably introducing the cellulose derivative as a constituent of a lead-containing detergent into the liquor. Another object of the invention is therefore a bleach-containing detergent containing a cellulose derivative described above.

The use according to the invention in the context of a laundry aftertreatment process can be carried out in such a way that the cellulose derivative is added separately to the rinse liquor which is used after the wash cycle using a bleach-containing detergent or it is incorporated as a component of the laundry aftertreatment agent, in particular a fabric conditioner. In this aspect of the invention, said bleach-containing detergent may also contain, but may be free from, a cellulose derivative to be used in accordance with the invention. Conversely, said laundry aftertreatment agent may also contain a bleach, but may be free of it.

An agent which contains a cellulose derivative to be used according to the invention or is used together or is used in the process according to the invention contains bleaching agents, preferably peroxygen-based, in particular in amounts ranging from 5% by weight to 70% by weight optionally bleach activator, especially in amounts ranging from 2% to 10% by weight. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanediperic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular when Sodium salts present. Such bleaching agents are in detergents which contain a cellulose derivative used according to the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, respectively on total agent, present, in particular percarbonate is used. The optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl-pienolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammoniumacetonitrile salts. The bleach activators may have been coated or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm, as for example according to the granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as can be prepared according to the process described in the German patent DD 255,884 , and / or according to the in particulate form described in International Patent Applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927 described method trialkylammoniumacetonitrile is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.

Bleach-containing detergents which contain a cellulose derivative to be used according to the invention or are used together or used in the process according to the invention may contain all customary other constituents of such agents which do not interact in an undesired manner with the cellulose derivative of the invention. Preferably, the Cellulose derivative in amounts of 0.1 wt .-% to 5 wt .-%, in particular 0.5 wt .-% to 2.5 wt .-% incorporated in bleach-containing detergent.

It has surprisingly been found that such cellulose derivatives having the abovementioned properties have a positive effect on the action of certain other detergent ingredients and, conversely, that the action of the cotton-active soil-release cellulose derivative is additionally intensified by certain other detergent ingredients. These effects occur in particular with enzymatic active substances, in particular proteases and lipases, with water-soluble organic builders, in particular based on oxidized carbohydrates or polymeric polycarboxylates, with synthetic anionic surfactants of the sulfate and sulfonate type, with color transfer inhibitors, for example vinylpyrrolidone, vinylpyridine or vinylimidazole polymers or Copolymers or corresponding Polybetainen, and in grayness inhibitors, for example other, in particular anionic cellulose ethers such as carboxymethylcellulose, which is why the use of at least one of said further ingredients is preferred together with cellulose derivatives to be used according to the invention.

In a preferred embodiment, an agent used according to the invention or used in the process according to the invention comprises nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular 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, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.

Another embodiment of such agents comprises the presence of sulfate and / or sulfonate synthetic anionic surfactant, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty acid ester and / or sulfo fatty acid salt, in particular in an amount in the range from 2% to 25% by weight. The anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms has. These are usually not individual substances, but cuts or mixtures. Of these, preference is given to those whose content of compounds having longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight.

Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C 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. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, as can be prepared according to the process disclosed in International Patent Application WO 90/13533, and fatty acid polyhydroxyamides, as prepared according to the processes of US Pat. Nos. 1,985,424, US 2 016 962 and US 2 703 798 and international patent application WO 92/06984. For incorporation into the inventive compositions suitable Alkyl polyglycosides are compounds of the general formula (G) _n -OR ^12, wherein R ¹² is an alkyl or alkenyl group having 8 to 22 carbon atoms, G is a glycose unit and n is a number from 1 to 10 mean. Such compounds and their preparation are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828. The glycoside component (G) _n is oligo- or polymers of naturally occurring ones Aldose or ketose monomers, which include, in particular, glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomerisierungsgrad. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R ^{12 of} the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can also be used for the preparation of useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a Kokosfettalkylrest, that is, mixtures having substantially R ¹² = dodecyl and R ¹² = tetradecyl.

Nonionic surfactant is used according to the invention in agents which contain a soil-release agent used according to the invention, or used in the process according to the invention, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 Wt .-%, with amounts in the upper part of this range are more likely to be found in liquid detergents and particulate detergents preferably contain rather lower amounts of up to 5 wt .-%.

The agents may instead or additionally contain other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as, for example, alkylbenzenesulfonates, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight. %, in each case based on total resources. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogues, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.

Other optional surface-active ingredients are soaps, suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Preferably, soap is included in amounts of from 0.1% to 5% by weight. However, especially in liquid compositions containing a polymer used according to the invention, higher amounts of soap, as a rule up to 20% by weight, can also be present.

If desired, the compositions may also contain betaines and / or cationic surfactants which, if present, are preferably used in amounts of from 0.5% to 7% by weight. Among them, the esterquats discussed below are particularly preferred.

In a further embodiment, the agent contains water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, especially in amounts ranging from 2.5% to 60% by weight.

The agent preferably contains from 20% 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 the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides of the international patent application WO 93/16110, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers of these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. It is also possible to use as water-soluble organic builder substances terpolymers which contain two carboxylic acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably Acrylic acid or acrylate, and maleic acid or maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (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 , 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 allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. The use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer. These terpolymers can be prepared in particular by processes which are described in German Patent DE 42 21 381 and German Patent Application DE 43 00 772, and generally have a molecular weight between 1000 and 200,000, preferably between 200 and 50,000 and in particular between 3000 and 10000 on. They can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All 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. contain. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.

Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these, the detergent-grade crystalline aluminosilicates, especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 mm and preferably consist of at least 80% by weight of particles having a size of less than 10 mm. Their calcium binding capacity, which can be determined according to the specifications of the German patent DE 24 12 837, is in the range of 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ 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 of Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 can be prepared by the process of European Patent Application EP 0 425 427. They are preferably added in the course of the production as a solid and not in the form of a solution. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x O _{2x + 1} yH ₂ O used in the x, the so-called module 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 in the abovementioned general formula has the values 2 or 3 accepts. In particular both β- and δ-sodium (Na ₂ Si ₂ O ₅ · yH ₂ O) are preferred, with β-sodium disilicate being obtainable, 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 prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the above general formula in which x is a number from 1.9 to 2.1, preparable as in the European patent applications EP 0 548 599, EP 0 502 325 and EP 0 425 428 can be used in agents which contain a polymer according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate having 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 having a modulus in the range from 1.9 to 3.5, as obtainable by the processes of European patents EP 0 164 552 and / or European patent application EP 0 294 753, are in another preferred embodiment of detergents, which contain a cellulose derivative used according to the invention. Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In agents containing both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 1 to 2: 1.

In addition to the mentioned inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the compositions which contain a cellulose derivative to be used according to the invention together with it or used in processes according to the invention. Suitable are in this context, the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.

In addition, the agents may contain other ingredients customary in detergents and cleaners. These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably, in compositions which comprise a cellulose derivative used according to the invention, up to 1% by weight, 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 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for Heavy metals, in particular Aminoalkylenphosphonsäuren and their salts and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight fractions refer to the total agent.

Solvents which can be used in particular for liquid agents 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, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether. In such liquid agents, the cellulose derivatives used in the invention are usually dissolved or in suspended form.

Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms, for example in German Offenlegungsschriften DE 19 40 488, DE 20 44 161, DE 21 01 803 and DE 21 21 397, US Pat. Nos. 3,623,957 and 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 prepared from Humicola lanuginosa, as described, for example, in European Patent Applications EP 258 068, EP 305 216 and EP 341 947, from Bacillus species, as described, for example, in International Patent Application WO 91/16422 or European Patent Application EP 384 717 , from Pseudomonas species, as for example in the European patent applications EP 468 102, EP 385 401, EP 375 102, EP 334 462, EP 331 376, EP 330 641, EP 214 761, EP 218 272 or EP 204 284 or the international Patent application WO 90/10695, from Fusarium species, as described for example in the European patent application EP 130,064, from Rhizopus species, as described for example in the European patent application EP 117 553, or from Aspergillus species, such as in the European Patent application EP 167 309 described, are obtained. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, 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 usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5. Such cellulases are known, for example, from German Offenlegungsschriften DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 and international patent applications WO 95/02675 and WO 97/14804 and commercially available under the names Celluzyme®, Carezyme® and Ecostone®.

To the optionally present in particular liquid agents usual enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, such as those from the European Patent Applications EP 376 705 and EP 378 261 discloses boric acid or alkali borates, boric acid-carboxylic acid combinations, such as boric acid esters known for example from European patent application EP 451 921, for example from international patent application WO 93/11215 or European patent application EP 511 456 known, boronic acid derivatives, as known for example from European Patent Application EP 583 536, calcium salts, for example the known from European Patent EP 28 865 Ca-formic acid combination, magnesium salts, as known for example from European Patent Application EP 378 262, and / or sulfur-containing Reducing agent, as known for example from European patent applications EP 080 748 or EP 080 223.

Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German Offenlegungsschrift DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309 931 or European patent EP 150 386.

In a preferred embodiment, an agent which is incorporated into the cellulose derivative to be used according to the invention is particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, up to 15% by weight. %, in particular from 1% by weight to 10% by weight of bleach activator, from 20% by weight to 55% by weight of inorganic builder, up to 10% by weight, in particular from 2% by weight to 8% by weight % water-soluble organic builder, 10 wt.% to 25 wt.% of synthetic anionic surfactant, 1 wt.% to 5 wt.% of nonionic surfactant and up to 25 wt.%, in particular 0.1 wt 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate.

In a further preferred embodiment, an agent which is incorporated into the cellulose derivative to be used according to the invention is liquid and contains 10% by weight to 25 wt .-%, in particular 12 wt .-% to 22.5 wt .-% nonionic surfactant, 2 wt .-% to 10 wt .-%, in particular 2.5 wt .-% to 8 wt .-% synthetic Anionic surfactant, 3 wt .-% to 15 wt .-%, in particular 4.5 wt .-% to 12.5 wt .-% soap, 0.5 wt .-% to 5 wt .-%, in particular 1 wt. -% to 4 wt .-% organic builder, especially polycarboxylate such as citrate, up to 1.5 wt .-%, in particular 0.1 wt .-% to 1 wt .-% complexing agent for heavy metals, such as phosphonate, and in addition to optionally contained enzyme, enzyme stabilizer, color and / or fragrance water and / or water-miscible solvent.

It is also possible to use a combination of said cotton-active soil release cellulose derivative with a polyester active soil release polymer of a dicarboxylic acid and an optionally polymeric diol to enhance the cleaning performance of bleach-containing detergents in the washing of textiles. Also within the scope of the inventive composition and the process according to the invention, such combinations of said cotton-active soil release cellulose derivative with a polyester-active soil release-capable polymer are possible.

The known polyester-active soil release polymers which can be used in addition to the cellulosic derivatives essential to the invention include copolyesters of 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. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR ¹¹ -) _a OH, also known as polymeric Diol H- (O- (CHR ₁₁ -) _a ) _b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ denotes hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -O- (CHR _11- ) _a O- as well as polymer diol units - (O- (CHR ¹¹ -) _a ) _b O-. 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. In the polymer diol units, the degree of polymerization b is preferably in the range of 4 to 200, especially 12 to 140. The molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000 The acid underlying the remainder Ph 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 alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO- (CHR ¹¹ -) _a OH include those in which R ^{11 is} hydrogen and a is a number from 2 to 6, and those in which a is 2 and R ¹¹ is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH ₂ -CHR ¹¹ -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-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000.

If desired, the polyesters synthesized as described above may also be end-capped, alkyl groups having from 1 to 22 carbon atoms being used as end groups and esters of monocarboxylic acids come into question. The ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonsäuren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid , The end groups may 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 may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is 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 the cellulose derivatives.

The soil release polymers are preferably water-soluble, the term "water-soluble" being understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8. However, preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.

Preferred laundry aftertreatment compositions containing a cellulose derivative to be used according to the invention have a so-called fabric softening agent Esterquat, that is a quaternized ester of carboxylic acid and aminoalcohol. These are known substances that can be obtained by the relevant methods of preparative organic chemistry. In this context, reference is made to international patent application WO 91/01295, according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. German Patent DE 43 08 794 moreover discloses a process for preparing solid ester quats, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Reviews on this topic are, for example, by R. Puchta et al. in Tens.Surf.Det., 30, 186 (1993), M.Brock in Tens.Surf.Det. 30, 394 (1993), R. Lagerman et al. in J.Am.Oil.Chem.Soc., 71, 97 (1994) and I.Shapiro in Cosm.Toil. 109, 77 (1994).

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² und R³ unabhängig voneinander für Wasserstoff oder R¹CO, R⁴ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- beziehungsweise Palmfettsäuren sowie elaidinsäure-reiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin in der Regel im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugt eingesetzten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18- Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Quaternierte Fettsäuretriethanolaminestersalze der Formel (I), in der R¹CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R² für R¹CO, R³ für Wasserstoff, R⁴ für eine Methylgruppe, m, n und p für 0 und X für Methylsulfat steht, haben sich als besonders vorteilhaft erwiesen.Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow formula (I),

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ² and R ^{3 are} independently hydrogen or R ¹ CO, R ^{4 is} an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H Group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils. Preferably technical _{C12 / 18} coconut fatty acids and in particular partly hydrogenated C _16/18 tallow or palm oil fatty acids and elaidic acid-rich C _16/18 fatty acid cuts used. To prepare the quaternized esters, the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1. In view of the performance properties of the esterquats, an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred esterquats used are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm oil fatty acid (iodine value 0 to 40) , Quaternized fatty acid triethanolamine ester salts of the formula (I) in which R ^{1 is} CO for an acyl radical having 16 to 18 carbon atoms, R ^{2 is} R ¹ CO, R ^{3 is} hydrogen, R ^{4 is} a methyl group, m, n and p is 0 and X is Methyl sulfate is, have proven to be particularly advantageous.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴ und R⁵ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized carboxylic acid triethanolamine ester salts, quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (II) are also suitable as esterquats.

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ¹ CO, R ⁴ and R ^{5 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴, R⁶ und R⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyldialhylamines of the formula (III) should be mentioned as a further group of suitable esterquats.

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ^{7 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the exemplary statements given for (I) apply mutatis mutandis to the esterquats of the formulas (II) and (III). Usually, the esterquats are marketed in the form of 50 to 90 weight percent alcoholic solutions, which can also be easily diluted with water, with ethanol, propanol and isopropanol being the usual alcoholic solvents.

Esterquats are preferably used in amounts of from 5% by weight to 25% by weight, in particular from 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent. If desired, the laundry aftertreatment agents used in the present invention may additionally contain detergent ingredients listed above, unless they unduly interact negatively with the esterquat. It is preferably a liquid, water-containing agent.

Examples Example 1:

A detergent (V1) containing SECTION 12 parts by weight FAS 5 parts by weight C12 / 14 7 EO 3 parts by weight TAED 7 parts by weight percarbonate 17 parts by weight soda 13 parts by weight zeolite 28 parts by weight Sokalan® CP 5 ^a) 5 parts by weight Tinopal® DMS-X ^b) 0.2 parts by weight a) Polymeric polycarboxylate, manufacturer BASF AG
b) Optical brightener, manufacturer Ciba was added with 2 parts by weight of methyl hydroxyethyl cellulose, average molecular weight 95 000 (W1) or with 2 parts by weight of methyl hydroxypropyl cellulose, average molecular weight 50,000 (W2) . For comparison, a detergent V2 was prepared by addition of 2 parts by weight of polyethylene terephthalate-polyoxyethylene glycol copolymer (Repel-O-Tex®) from V1 . Pure cotton, finished cotton, and 50/50 polyester / cotton blend fabrics were treated as follows: Washer: Miele W 918 Novotronic® Primary washing power: Single-lye procedure normal program Washing temperature: 40 ° C Determination: 5 times Fleet size: 181 Water hardness: 16 ° dH filling laundry: 3.5 kg of clean laundry

• 0,10 g Lippenstift
• 0,10 g schwarze Schuhcreme
• 0,10 g Staub / Hautfett

The fabrics were undeluted washed three times with each detergent to be tested under the conditions given above and dried after each wash. After prewashing three times, the fabrics were soiled by hand with the following standardized soiling:

• 0.10 g lipstick
• 0.10 g black shoe polish
• 0.10 g of dust / skin fat

The soiled fabrics were measured with a Minolta CR 200 and then aged at RT for 7 days. Thereafter, the soiled cloths were stapled on towels and washed under the conditions given above.

The fabrics were dried and measured again with a Minolta CR 200. This resulted in the following wash results (dde values): <u> Table 1: Pure cotton </ u> lipstick Shoe polish black Dust / skin fat V1 60.5 54.9 55.6 V2 57.5 54.8 57.9 W1 66.0 58.0 59.7 W2 66.5 60.2 61.0 lipstick Shoe polish black Dust / skin fat V1 70.0 56.0 48 V2 67.9 55.9 48.7 W1 77.5 58.8 61.1 W2 81.1 59.9 60.8 lipstick Shoe polish black Dust / skin fat V1 66.2 54.4 46.7 V2 71.2 55.1 58.0 W1 73.2 58.2 60.7 W2 77.2 57.4 58.8

It can be seen that the detergents containing the cellulose derivative (W1 and W2) to be used according to the invention show a significantly better washing performance than the agent lacking it (V1) or containing a polyester in its place (V2).

Example 2:

Washing tests were carried out as described in Example 1, the fabrics being washed unspun three times with the detergent V1 , but additionally with Softener S1 containing cellulose derivative (15% by weight of esterquat and 2% by weight of the methylhydroxyethylcellulose used in Example 1) water), or with the same Softener, the cellulose derivative lacked (S0) rinsed and dried after each wash. Subsequently, the fabrics were soiled with the standardized stains, the soiled fabrics were measured with a Minolta CR 200, aged at RT for 7 days, then stapled on towels and washed with V1 under the conditions given in Example 1 and rinsed with S1 or S0 .

The fabrics were dried and measured again with a Minolta CR 200. This resulted in the following wash results (dde values): <u> Table 4: Pure cotton </ u> lipstick Shoe polish black Dust / skin fat S0 60.5 54.9 55.6 S1 77.8 57.1 61.2 lipstick Shoe polish black Dust / skin fat S0 70.0 56.0 48.8 S1 88.2 58.5 54.2 lipstick Shoe polish black Dust / skin fat S0 66.2 54.4 46.7 S1 80.3 56.9 65.3

It can be seen that, when using the laundry aftertreatment agent with the cellulose derivative to be used according to the invention, a significantly better washing performance results than when using the laundry aftertreatment agent which lacks the cellulose derivative.

Example 3:

A detergent (V3) containing SECTION 11 parts by weight FAS 5 parts by weight C12 / 14 7 EO 4 parts by weight soda 4 parts by weight zeolite 22 parts by weight sodium citrate 2 parts by weight Sokalan® CP 5 ^a) 2 parts by weight Enzyme ^b ) 1.5 parts by weight a) Polymeric polycarboxylate, manufacturer BASF AG
b) Combination of protase, amylase and cellulase was mixed with 18 parts by weight of sodium percarbonate and 8 parts by weight of TAED (detergent V4) . By adding 2 parts by weight of methyl hydroxyethyl cellulose (DS 1.89, MS 0.15, average molecular weight 100,000) to V3 or V4 , the detergents V5 and W3 were prepared from these. As described in Example 1, washing tests were carried out with these agents. This resulted in the following wash results (dde values): <u> Table 7: Pure cotton </ u> lipstick Dust / skin fat V3 53.4 56.6 V4 66.7 57.7 V5 51.7 57.1 W3 72.8 63.1 lipstick Dust / skin fat V3 54.6 47.3 V4 66.7 44.2 V5 55.4 48.6 W3 78.9 53.2 lipstick Dust / skin fat V3 63.6 51.4 V4 71.1 48.5 V5 67.9 56.9 W3 76.3 58.3

It can be seen that the detergents containing the cellulose derivative (V5 and W3) show, in most cases, a better washing performance than the corresponding agents lacking them ( V3 and V4 ), but that the lead-containing agent contains the cellulose derivative (W3) used according to the invention. the best performance results.

Claims (14)

1. The use of soil release-capable cellulose derivatives which are obtainable by alkylation and hydroxyalkylation of cellulose and contain on average from 0.5 to 2.5 alkyl groups and from 0.02 to 0.5 hydroxyalkyl groups per anhydroglycose monomer unit for enhancing the cleaning performance of bleach-containing laundry detergents in the washing of textiles which in particular consist of cotton or comprise cotton.
2. The use of soil release-capable cellulose derivatives which are obtainable by alkylation and hydroxyalkylation of cellulose for enhancing the cleaning performance of bleach-containing laundry detergents in the washing of textiles which in particular consist of cotton or comprise cotton, and have already been washed and/or aftertreated in the presence of the cellulose derivative before they have been soiled.
3. The use of a combination of soil release-capable cellulose derivative which is obtainable by alkylation and hydroxyalkylation of cellulose and contains an average from 0.5 to 2.5 alkyl groups and from 0.02 to 0.5 hydroxyalkyl group per anhydroglycose monomer unit, and a polyester-active soil release-capable polymer composed of a dicarboxylic acid and an optionally polymeric diol for enhancing the cleaning performance of bleach-containing laundry detergents in the washing of textiles.
4. The use as claimed in one of claims 1 to 3, characterized in that the cellulose derivative has been alkylated with C₁ to C₁₀ groups, in particular C₁ to C₃ groups, and additionally bears C₂ to C₁₀ hydroxyalkyl groups, in particular C₂ to C₃ hydroxyalkyl groups.
5. The use as claimed in one of claims 1 to 4, characterized in that the cellulose derivative contains on average from 1 to 2 alkyl groups, and from 0.05 to 0.3 hydroxyalkyl group per anhydroglycose monomer unit.
6. The use as claimed in one of claims 1 to 5, characterized in that the mean molar mass of the cellulose derivative is in the range from 10 000 D to 150 000 D, in particular from 40 000 D to 120 000 D, and more preferably in the range from 80 000 D to 110 000 D.
7. The use according to one of claims 1 to 6, characterized in that the bleach-containing laundry detergent contains from 5% by weight to 70% by weight of bleach, and also optionally bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight.
8. A process for washing textiles, in which a bleach-containing laundry detergent and a soil release-capable cellulose derivative which is obtainable by alkylation and hydroxyalkylation of cellulose and contains on average from 0.5 to 2.5 alkyl groups and from 0.02 to 0.5 hydroxyalkyl group per anhydroglycose monomer unit are used.
9. The process as claimed in claim 8, characterized in that the textile, after the actual washing operation which is performed with the aid of a bleach-containing laundry detergent, is contacted with an aftertreatment composition which comprises a cellulose derivative which is obtainable by alkylation and hydroxyalkylation of cellulose.
10. The process as claimed in claim 9, characterized in that a laundry aftertreatment composition is used which comprises a soil release-capable cellulose derivative which is obtainable by alkylation and hydroxyalkylation of cellulose, and ester quat.
11. The process as claimed in claim 10, characterized in that the composition comprises ester quat in amounts of from 5% by weight to 25% by weight, in particular from 8% by weight to 20% by weight.
12. The process as claimed in one of claims 8 to 11, characterized in that the composition comprises cellulose derivative in amounts of from 0.1% by weight to 5% by weight, in particular from 0.5% by weight to 2.5% by weight.
13. The process as claimed in one of claims 8 to 12, characterized in that the bleach-containing laundry detergent contains from 5% by weight to 70% by weight of bleach, and also optionally bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight.
14. A bleach-containing laundry detergent comprising a soil release-capable cellulose derivative which is obtainable by alkylation and hydroxyalkylation of cellulose and contains on average from 0.5 to 2.5 alkyl groups and from 0.02 to 0.5,hydroxyalkyl group per anhydroglycose monomer unit.