EP1592763B2 - 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 for enhancing the cleaning performance of bleach-containing detergents in the washing of textiles made of cotton or containing cotton, as well as bleach-containing detergents and cleaners containing such soil release-capable 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 under 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". For example, from the US Pat. No. 4,136,038 the soil release ability of methyl cellulose is known. The 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. From the European Patent Application EP 0 213 730 Textile treatment agents are known which contain cationic surfactants and nonionic cellulose ethers with HLB values of 3.1 to 3.8. The US Pat. No. 4,000,093 discloses 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 is substantially consists of C ₁₀ - to C ₁₃ alkyl sulfate and up to 5% by weight of C ₁₄ alkyl sulfate and less than 5 wt .-% alkyl sulfate having alkyl radicals of C ₁₅ and higher. The US Pat. No. 4,174,305 discloses 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 is substantially consists of C ₁₀ - to C ₁₂ -alkylbenzenesulfonate and less than 5 wt .-% alkylbenzenesulfonate having alkyl radicals of C ₁₃ and higher. The European Patent 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 methylcellulose and ethylcellulose, with weight ratio of peroxygen bleach (based on the active oxygen content of the bleach) of 10: 1 to 1 : 10 should be used. The 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. From the European Patent EP 0 948 591 B1 For example, a laundry detergent in liquid or granular form is known which imparts textile appearance benefits such as pill / lint reduction, anti-color fading, improved abrasion resistance and / or enhanced softness to fabrics and textiles washed therewith, and from 1 to 80 weight percent 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 must be present in amounts of 0.1-5 wt .-%, based on the cellulose ether material.

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 German Offenlegungsschrift DE 33 24 258 be used in detergents. The European patent EP 066 944 relates to textile treatment compositions comprising a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. From the European patent EP 185 427 For example, methyl or ethyl group-end capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer are known. The 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 glycerol units. From the European patent EP 241 985 are known polyester containing in addition to oxyethylene groups and terephthalic acid units 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene and glycerol units and endgruppenverschlossen with C ₁ - to C ₄ alkyl groups are. The European patent EP 253 567 concerns. 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. From the European patent application EP 272 033 are at least partially by C _1-4 alkyl or acyl radicals end-capped polyester with poly-propylene terephthalate and polyoxyethylene terephthalate units known. The European patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. In the European patent application EP 357,280 are prepared by sulfonation of unsaturated end groups soil release polyester 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 repulping of dirt during the washing of synthetic fibers. From the German patent DE 28 46 984 Detergents are known which contain, as a soil-removing-capable polymer, a reaction product of a polyester having a terminal isocyanate group-containing prepolymer obtained from a diisocyanate and a hydrophilic nonionic macrodiol.

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. In addition, such soil release agents must not only be stable in the presence of bleaches normally present in laundry detergents, but should have particularly good efficacy in such bleach-containing compositions and desirably even improve or at least not compromise the effectiveness of the bleach.

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 obtainable by alkylation and hydroxyalkylation of cellulose, and bleaching agent for enhancing the cleaning performance of detergents in the washing of textiles made of cotton or containing 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 in the context of a fabric 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 prepared 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 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 a significantly better detachment of, in particular, grease and cosmetic stains on cotton or cotton-containing fabrics than is the case with the use of compounds previously known 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 softener. 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 which may be used 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 as sodium salts. 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 in the European patent specification EP 37 026 granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as described in the German Patent DD 255,884 described method can be prepared, and / or according to those in the international Patent Applications WO 00/50553 . WO 00/50556 . WO 02/12425 . WO 02/12426 or WO 02/26927 Particularly preferred is the trialkylammonium acetonitrile formulated in particulate form. 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 used together with it or used in the process according to the invention may contain all customary other constituents of such agents which are not undesirable with the interact with the cellulose derivative of the invention. The cellulose derivative is preferably incorporated in amounts of from 0.1% by weight to 5% by weight, in particular from 0.5% by weight to 2.5% by weight, in bleach-containing detergents.

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. 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 described in the international Patent Application WO 90/13533 as well as fatty acid polyhydroxyamides, as prepared according to the methods of U.S. Pat. Nos. 1,985,424 . US 2 016 962 and US 2,703,798 as well as the international ones Patent Application WO 92/06984 can be prepared. So-called alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) _n -OR ¹² , in which R ^{12 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 the European patent applications EP 92 355 . EP 301 298 . EP 357 969 and EP 362,671 or the US Pat. No. 3,547,828 described. The glycoside component (G) _n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include 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 containing a soil-release agent used according to the invention, or used in the process according to the invention, preferably in amounts from 1 wt% to 30 wt%, especially from 1 wt% to 25 wt%, with amounts in the upper part of this range being more likely to be found in liquid detergents and particulate detergents preferably being smaller amounts up to to 5 wt .-% contained.

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 the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, 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% by weight to 7% by weight. Among them, the esterquats discussed below are particularly preferred.

In a further embodiment, the composition 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, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.

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 of the international, which are obtainable by oxidation of polysaccharides Patent Application WO 93/16110 , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances copolymerized 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 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% 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 .-% 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 methods which are described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1000 and 200,000, 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 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. 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 according to the data of German patent DE 24 12 837 can be determined ranges from 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 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 getting produced. 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 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, for example, in the European Patent Application EP 0 164 514 described. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. 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 is described. δ-Sodium silicates with a modulus between 1.9 and 3.2 can according to the Japanese Patent Application JP 04/238809 or JP 04/260 610 getting produced. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be prepared 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 with a modulus of 2 to 3 is used, as is obtained by the process of European Patent Application EP 0 436 835 made from sand and soda. Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as determined by the methods of European patents EP 0 164 552 and / or the European Patent Application EP 0 294 753 are available are used in a further preferred embodiment of detergents which contain a cellulose derivative used in 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 in this context are 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 common 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 the German Offenlegungsschriften DE 19 40 488 . DE 20 44 161 . DE 21 01 803 and DE 21 21 397 , the US Pat. No. 3,623,957 and US 4,264,738 , the European patent application EP 006 638 as well as the international ones 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 for example in European patent applications EP 258,068 . EP 305 216 and EP 341 947 described from Bacillus species, such as in the international Patent Application WO 91/16422 or the European patent application EP 384 717 described, from Pseudomonas species, such as 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 one Patent Application WO 90/10695 described, from Fusarium species, such as in the European patent application EP 130 064 described from Rhizopus species, such as in the European patent application EP 117 553 described or from Aspergillus species, such as in the European patent application EP 167,309 be described. 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 for example from the German Offenlegungsschriften DE 31 17 250 . DE 32 07 825 . DE 32 07 847 . DE 33 22 950 or the European patent applications EP 265 832 . EP 269 977 . EP 270 974 . EP 273 125 such as EP 339,550 and the international Patent Applications WO 95/02675 and WO 97/14804 known and commercially available under the names Celluzyme®, Carezyme® and Ecostone®.

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

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, such as in the German Offenlegungsschrift DE 34 36 194 , the European patent applications EP 262 588 . EP 301 414 . EP 309 931 or the European patent specification EP 150 386 described.

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% by weight, in particular 12% by weight to 22.5% by weight, of 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 .-% bis 12.5 wt .-% soap, 0.5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 4 wt .-% organic builder, in particular 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 perfume 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 of 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- and also polymeric 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 and esters of monocarboxylic acids being suitable as end groups. 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, pelargonic, capric, undecanoic, undecenoic, lauric, lauric, tridecanoic, myristic, pentadecanoic, palmitic, stearic, petroselic, petroselaidic, oleic, linoleic, linoleic 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, as a laundry softening active ingredient, a so-called esterquat, that is to say 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, be on the international Patent Application WO 91/01295 referenced, after which triethanolamine partially esterified in the presence of hypophosphorous acid with fatty acids, air passes and then quaternized with dimethyl sulfate or ethylene oxide. From the German patent DE 43 08 794 moreover, a process for the preparation of solid ester quats is known 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, as well as elaidic acid-rich C _16/18 fatty acid 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 esterquats are also used Ester salts of carboxylic acids with diethanolalkylamines of the formula (II) into consideration,

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 lacking the cellulose derivative (S0) 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 (13)

1. Use of soil release-capable cellulose derivatives obtainable by alkylating and hydroxyalkylating cellulose and in which an average of 0.5 to 2.5 alkyl groups and from 0.02 to 0.5 hydroxyalkyl groups per anhydroglycose monomer unit are comprised, for enhancing the cleaning performance of bleaching agent-containing washing agents in the washing of textiles that consist of cotton or comprise cotton.
2. Use of soil release-capable cellulose derivatives obtainable by alkylating and hydroxyalkylating cellulose for enhancing the cleaning performance of bleaching agent-containing washing agents in the washing of textiles that consist of cotton or comprise cotton, and had already been washed and/or post treated in the presence of the cellulose derivative before they became soiled.
3. Use of a combination of soil release-capable cellulose derivative that is obtainable by alkylating and hydroxyalkylating cellulose and in which an average of 0.5 to 2.5 alkyl groups and from 0.02 to 0.5 hydroxyalkyl groups per anhydroglycose monomer unit are comprised, and a polyester-active soil release-capable polymer composed of a dicarboxylic acid and an optionally polymeric diol for enhancing the cleaning performance of bleaching agent-containing washing agents in the washing of textiles.
4. Use according to one of claims 1 to 3, characterised 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. Use according to one of claims 1 to 4, characterised in that the cellulose derivative comprises on average 1 to 2 alkyl groups and 0.05 to 0.3 hydroxyalkyl groups per anhydroglycose monomer unit.
6. Use according to one of claims 1 to 5, characterised 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 particularly preferably in the range from 80 000 D to 110 000 D.
7. Use according to one of claims 1 to 6, characterised in that the bleaching agent-containing washing agent comprises 5 wt.% to 70 wt.% bleaching agent as well as optionally bleach activator, in particular in amounts in the range of 2 wt.% to 10 wt.%.
8. A method for washing textiles that consist of cotton or comprise cotton, in which method are used a bleaching agent-containing washing agent and a soil release-capable cellulose derivative that is obtainable by alkylating and hydroxyalkylating cellulose and that comprises an average of 0.5 to 2.5 alkyl groups and from 0.02 to 0.5 hydroxyalkyl groups per anhydroglycose monomer unit, characterised in that the textile, after the actual washing process that is carried out with the aid of a bleaching agent-containing washing agent, is contacted with a post-treatment agent that comprises a cellulose derivative that is obtainable by alkylation and hydroxyalkylation of cellulose.
9. The method according to claim 8, characterised in that a laundry post-treatment agent is used that comprises a soil release-capable cellulose derivative that is obtainable by alkylation and hydroxyalkylation of cellulose, and esterquat.
10. The method according to claim 9, characterised in that the agent comprises the esterquat in amounts of 5 wt.% to 25 wt.%, in particular 8 wt.% to 20 wt.%.
11. The method according to one of claims 8 to 10, characterised in that the agent comprises the cellulose derivative in amounts of 0.1 wt.% to 5 wt.%, particularly 0.5 wt.% to 2.5 wt.%.
12. The method according to one of claims 8 to 11, characterised in that the bleaching agent-containing washing agent comprises 5 wt.% to 70 wt.% bleaching agent as well as optionally bleach activator, in particular in amounts in the range of 2 wt.% to 10 wt.%.
13. A particulate washing agent comprising a soil release-capable cellulose derivative that is obtainable by alkylating and hydroxyalkylating cellulose and that comprises an average of 0.5 to 2.5 alkyl groups and from 0.02 to 0.5 hydroxyalkyl groups per anhydroglycose monomer unit, 5 wt.% to 20 wt.% bleaching agent, 1 wt.% to 10 wt.% bleach activator, 20 wt.% to 55 wt.% inorganic builder, up to 10 wt.% water-soluble organic builder, 10 wt.% to 25 wt.% synthetic anionic surfactant, 1 wt.% to 5 wt.% nonionic surfactant and up to 25 wt.% inorganic salts.