DE10351322A1 - Bleach-containing detergent with a cotton-active, dirt-releasing cellulose derivative - Google Patents

Abstract

The cleaning performance of detergents containing bleach when washing textiles that consist in particular of cotton or contain cotton should be improved. This was essentially achieved by incorporating a cellulose derivative.

Description

The present invention relates to the use of certain dirt-releasing cellulose derivatives reinforcement the cleaning performance of detergents containing bleach Washing textiles, especially those made of cotton or contain cotton, as well as detergents and cleaning agents containing bleach, which such dirt-releasing cellulose derivatives contain.

In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain other ingredients, which can be summarized under the term washing aids and which include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors. Such auxiliary substances also include substances which impart dirt-repellent properties to the laundry fiber and which, if present during the washing process, support the dirt-removing ability of the other detergent components. The same applies analogously to cleaning agents for hard surfaces. Such soil release agents are often referred to as "soil release" actives or because of their ability to make the treated surface, for example the fiber, dirt repellent, "soil repellents". For example, from the US patent US 4 136 038 known the dirt-releasing effect of methyl cellulose. The European patent application EP 0 213 729 discloses the reduced redeposition when using detergents which contain 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 U.S. patent US 4,000,093 discloses detergents which contain 0.1% by weight to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and 5% by weight to 50% by weight of surfactant, the surfactant component essentially consists of C ₁₀ to C _{1 3} alkyl sulfate and has up to 5% by weight of C ₁₄ alkyl sulfate and less than 5% by weight of alkyl sulfate with alkyl radicals of C _{1 5} and higher. The U.S. patent US 4,174,305 discloses detergents which contain 0.1% by weight to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and 5% by weight to 50% by weight of surfactant, the surfactant component essentially consists of C ₁₀ to C ₁₂ alkylbenzenesulfonate and has less than 5% by weight of alkylbenzenesulfonate with alkyl radicals of C _{1 3} and higher. The European patent specification EP 0 271 312 concerns anti-soiling agents, among these cellulose alkyl ethers and cellulose hydroxyalkyl ethers (with DS 1.5 to 2.7 and molecular weights from 2000 to 100000) such as methyl cellulose and ethyl cellulose, which are mixed with peroxygen bleach in a weight ratio (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 percarbonate and one or more nonionic cellulose derivatives. Are disclosed expressly latter only hydroxyethyl cellulose, hydroxypropyl cellulose and methyl cellulose, as well as - in the examples - the methyl hydroxyethyl cellulose Tylose MH50 ^®, hydroxypropylmethylcellulose Methocel ^® F4M, and hydroxybutyl methylcellulose. From the European patent specification EP 0 948 591 B1 a detergent in liquid or granular form is known which gives fabrics and textiles which are washed therewith textile appearance advantages such as pill / lint reduction, anti-color fading, improved abrasion resistance and / or increased softness and the 1 to 80% by weight surfactant, 1 to Contains 80 wt .-% organic or inorganic builder, 0.1 to 80 wt .-% of a hydrophobically modified nonionic cellulose ether with a molecular weight of 10,000 to 2,000,000, the modification in the presence of optionally oligomerized (degree of oligomerization up to 20 ) Ethyleneoxy or 2-propyleneoxy ether units and of 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 particularly effective for polyester fibers in textiles made from this material active substances capable of releasing dirt are copolyesters, the dicarboxylic acid units, Contain alkylene glycol units and polyalkylene glycol units. Soil-removing copolyesters the type mentioned as well as their use in detergents have been known for a long time.

For example, the German published specification DT 16 17 141 a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. The German publication 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 cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol. Polymers made from ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights from 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents are described in the German patent DE 28 57 292 described. Polymers with a molecular weight of 15,000 to 50,000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 2: 1 to 6: 1, according to the German laid-open publication DE 33 24 258 be used in detergents. The European patent EP 066 944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. From the European patent EP 185 427 are known methyl- or ethyl group-end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain such a soil release polymer. 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 Polyesters are known which, in addition to oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and are end-capped with C ₁ - to C ₄ -alkyl groups are. The European patent specification EP 253 567 relates to soil-release polymers with a molecular weight of 900 to 9000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 0.6 to 0.95. From the European patent application EP 272 033 are known at least partly by C _1-4 alkyl or acyl residues end-capped polyesters with polypropylene terephthalate and polyoxyethylene terephthalate units. The 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 with terephthalate, alkylene glycol and poly-C _2-4 glycol units are produced by sulfonation of unsaturated end groups. 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 prepared in this way against the re-absorption of dirt when washing synthetic fibers. From the German patent specification DE 28 46 984 Detergents are known 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 the dirt-removing polymer.

The from this extensive stand Polymers known in the art have the disadvantage that they Textiles that are not or at least not predominantly made of polyester exist, have no or insufficient effectiveness. On greater Part of today's textiles, however, consists of cotton or cotton-polyester blended fabrics, so that a Need for especially greasy soiling on such Textiles are effective anti-soiling agents. About that have to go out such dirt-releasing active ingredients in the presence of bleaches normally found in detergents not only be stable, but should be especially in those containing bleach Agents have a particularly good effectiveness and desirably even improve or at least improve the effectiveness of the bleach do not interfere.

Surprisingly it was found that this Task to be solved by using certain cellulose derivatives can.

The invention relates to Use of a combination of dirt-releasing cellulose derivative, the available is by alkylation and hydroxyalkylation of cellulose, and Bleaching agents for reinforcement the cleaning performance of detergents when washing textiles, which consist in particular of cotton or contain cotton.

Another object of the invention is a process for washing textiles, which contains a bleach Detergent and a dirt-releasing cellulose derivative, that available is by alkylation and hydroxyalkylation of cellulose, to Come into play. This process can be manual or preferred with the help of a usual Household washing machine running become. It is possible the detergent containing bleach and the dirt-releasing cellulose derivative to use simultaneously or sequentially. Simultaneous use let yourself particularly advantageous through the use of a bleaching agent Carry out detergent that contains the dirt-releasing cellulose derivative.

The washing performance-enhancing effect is particularly pronounced those to be used according to the invention Cellulose derivatives with multiple use, that is, in particular for the removal of soiling from corresponding textiles, which have already been washed and / or aftertreated in the presence of the cellulose derivative before they were soiled. in the In connection with the aftercare it should be pointed out that the Realize the designated positive aspect through a washing process lets, at which the textile after the actual washing process, which with the help of a detergent containing bleach - which is a called cellulose derivative can contain, but in this case can also be free of this - executed, with an aftertreatment agent, for example as part of a fabric softening step, which is to be used according to the invention Contains cellulose derivative, is brought into contact. This procedure also occurs when next Washing process, even if necessary again a detergent containing bleach, but not a detergent is used with a cellulose derivative, the washing performance-enhancing effect those to be used according to the invention 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 a known manner by reacting cellulose with appropriate alkylating agents, for example alkyl halides or alkyl sulfates, and then reacting with corresponding alkylene oxides, such as ethylene oxide and / or propylene oxide. In a preferred embodiment of the invention, the cellulose derivative contains on average 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 anhydroglycosomer monomer unit. The average molecular weight 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 degree of polymerization or the molecular weight is determined of the dirt-releasing cellulose derivative is based on the determination of the intrinsic viscosity of sufficiently dilute aqueous solutions using an Ubbelohde capillary viscometer (capillary 0c). Using a constant [H. Staudinger and F. Reinecke, "About 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 used to calculate the degree of polymerization and the corresponding molecular weight, taking into account the degrees of substitution (DS and MS).

The cellulose derivatives used according to the invention are easy to manufacture and ecological as described as well as toxicologically harmless. They lead to a significantly better one Replacement of especially grease and cosmetic stains on cotton respectively cotton-containing fabrics than has been used for this so far The purpose of known connections is the case. Alternatively, at constant fat loss ability significant Amounts of surfactants can be saved.

The use according to the invention can be within the scope a washing process in such a way that a bleach and adding the cellulose derivative to a detergent-containing liquor that Cellulose derivative of a fleet containing bleach and detergent separately adds or preferably the cellulose derivative as part of a introduces detergent containing bleach into the fleet. Another The invention therefore relates to a detergent containing bleach, which contains a cellulose derivative described above.

The use according to the invention in the context of a Laundry aftertreatment process can accordingly be carried out in such a way that the cellulose derivative the washing liquor separately adds that after using a bleach Detergent used wash cycle is used, or as Part of the laundry treatment agent, especially a fabric softener, brings. In this aspect of the invention, said bleach-containing can Detergent also a cellulose derivative to be used according to the invention included, but can also be free of this. Conversely, can the laundry after-treatment agent mentioned also contain a bleach, but can also be free of it his.

An agent which contains a cellulose derivative to be used according to the invention or is used together with it or is used in the method according to the invention contains bleaching agents, preferably based on peroxygen, in particular in amounts in the range from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali perborate, which can be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, as a rule as alkali salts, in particular as sodium salts. Bleaching agents of this type are obtained in detergents which contain a cellulose derivative used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight on the entire medium, with percarbonate in particular being used. The optional component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines and sulfurate amides, sulfuryl amides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl phenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose, and also cationic nitrile derivatives such as trimethylammonium acetonitrile salts. The bleach activators can be coated or granulated with coating substances in a known manner in order to avoid the interaction with the per-compounds during storage, with tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm granulated with the aid of carboxymethyl cellulose, as described, for example, by in the European patent specification EP 37 026 described method can be prepared, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as described in the German patent DD 255 884 described processes can be prepared, and / or according to the processes described in the international patent applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927 particulate trialkylammonium acetonitrile is particularly preferred. In detergents such are bleach activators preferably in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the total agent.

Detergents containing bleach, which is to be used according to the invention Cellulose derivative contain or used together with this or in the method according to the invention can be used all usual other ingredients of such funds that are not included in undesirable Interact with the cellulose derivative essential to the invention. The cellulose derivative is preferably used in amounts of 0.1% by weight. up to 5 wt .-%, in particular 0.5 wt .-% to 2.5 wt .-% in bleach-containing Detergent incorporated.

Surprisingly it has been found that such Cellulose derivatives with the above properties have the effect certain other detergent ingredients are positive influence and that vice versa the effect of the cotton-active soil-release cellulose derivative certain other detergent ingredients are additionally reinforced. These effects occur particularly with enzymatic active substances, especially proteases and lipases in water-soluble organic builders, in particular based on oxidized carbohydrates or polymeric polycarboxylates, for synthetic anionic surfactants of the sulfate and sulfonate type Color transfer inhibitors, for example vinylpyrrolidone, vinylpyridine or vinylimidazole polymers or copolymers or corresponding polybetaines, and in the case of graying inhibitors, for example other, especially anionic cellulose ethers like carboxymethyl cellulose, which is why the use at least one of the other ingredients mentioned together with those to be used according to the invention Cellulose derivatives is preferred.

In a preferred embodiment contains an inventive, used according to the invention or in the method according to the invention agent used 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 as well as their mixtures, in particular in an amount in the range of 2% to 25% by weight.

Another embodiment of such means comprises the presence of synthetic anionic surfactant from sulfate and / or Sulfonate type, especially fatty alkyl sulfate, fatty alkyl ether sulfate, Sulfofatty acid esters and / or sulfo fatty acid disalts, in particular in an amount in the range from 2% by weight to 25% by weight. The anionic surfactant from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates selected, in which the alkyl or alkenyl group 8 to 22, in particular 12th has up to 18 carbon atoms. These are usually not about individual substances, but about cuts or mixtures. Among them, those are preferred whose proportion of compounds with relatively long Residues in the range of 16 to 18 carbon atoms is over 20 wt .-%.

The nonionic surfactants in question 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 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the alkoxylates, in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used. Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used. In addition, there are the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as in accordance with the processes in the US patents US 1 985 424 . US 2,016,962 and US 2 703 798 and the international patent application WO 92/06984 can be considered. So-called alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) _n -OR ^{1 2} , in which R ^{1 2 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. Such compounds and their preparation are described, for example, in European patent applications EP 92 355 . EP 301 298 . EP 357 969 and EP 362 671 or the U.S. patent US 3,547,828 described. The glycoside component (G) _n is an oligomer or polymer from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Xylose and Lyxose belong to. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization. The degree of oligomerization n generally takes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl part R ^{12 of} the glycosides preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl glycosides contain a coconut fatty alkyl radical, ie mixtures with essentially R ¹² = dodecyl and R ¹² = tetradecyl.

Nonionic surfactant is in which used one according to the invention Contain soil release active ingredient, used according to the invention or in the method according to the invention are used, preferably in amounts of 1% by weight to 30% by weight, contain in particular from 1% by weight to 25% by weight, with amounts found in liquid detergents in the upper part of this area are and particulate detergent preferably contain smaller amounts of up to 5 wt .-%.

The funds can be used instead or in addition Surfactants, preferably synthetic anionic surfactants of sulfate or Sulphonate type such as alkyl benzene sulphonates in quantities from preferably not over 20% by weight, in particular from 0.1% by weight to 18% by weight, in each case based on total means included. As for use in such Synthetic anionic surfactants which are particularly suitable are the alkyl and / or Alkenyl sulfates with 8 to 22 carbon atoms, which are an alkali, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ion wear as a counter cation.

The derivatives of fatty alcohols are preferred with in particular 12 to 18 carbon atoms and their branched chains Analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can in a known manner by reaction of the corresponding alcohol component with a usual Sulfating agent, especially sulfur trioxide or chlorosulfonic acid, and subsequent Neutralization with alkali, ammonium or alkyl or hydroxyalkyl substituted Ammonium bases are made. The surfactants from Belong to sulfate type also the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, especially 4 to 10 ethylene glycol groups per molecule. To the Suitable anionic surfactants of the sulfonate type include those by reacting Fettsäureestern α-sulfoesters obtainable with sulfur trioxide and subsequent neutralization, especially those differing from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 up to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation products, and the sulfofatty acids resulting from these by formal saponification.

Soaps are possible as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable. Soap mixtures are preferred, to 50 wt .-% to 100 wt .-% of saturated C ₁ -C _{2 1 8} fatty acid soaps and set to 50 wt .-% to oleic acid soap. Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. However, in particular in liquid compositions which contain a polymer used according to the invention, higher amounts of soap, as a rule up to 20% by weight, can also be present.

If desired, the Agents also contain betaines and / or cationic surfactants, which - if present - are preferred be used in amounts of 0.5 wt .-% to 7 wt .-%. Under these the ester quats discussed below are particularly preferred.

In another embodiment contains the medium water-soluble and / or water-insoluble builders, selected in particular made of alkali alumosilicate, crystalline alkali silicate with modulus over 1, monomeric Polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5% to 60% by weight.

The composition preferably contains 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110 accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances copolymerized without carboxylic acid functionality. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as monomers can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ carboxylic acids, with vinyl alcohol are particularly preferred. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight of vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2, are very particularly preferred. 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which, in the 2-position, has an alkyl radical, preferably a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is substituted. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight. %, preferably 15% by weight to 25% by weight of methallylsulfonic acid or methallylsulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate. This carbohydrate can 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 creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers can be produced in particular by methods described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are described, and generally have a relative molecular mass between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. They can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the 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 in amounts up to 40 wt .-%, in particular up to Contain 25 wt .-% and particularly preferably from 1 wt .-% to 5 wt .-%. Amounts close to the above limit are preferably in paste or liquid, in particular water-containing agents used.

As water-insoluble, water-dispersible inorganic builder materials become especially crystalline or amorphous alkali alumosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid Averages in particular of 1% by weight up to 5% by weight. Among these are the crystalline aluminosilicates in detergent quality, in particular zeolite NaA and optionally NaX, preferred.

Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size of more than 30 mm and preferably consist of at least 80% by weight of particles with a size of less than 10 mm. Your calcium binding capacity, which according to the information in the German patent specification DE 24 12 837 can be determined, is in the range of 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the alumosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in the compositions preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, especially the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a Na ₂ O: SiO ₂ molar ratio of 1: 1.9 to 1: 2.8 can be prepared by the process of the European patent application EP 0 425 427 getting produced. They are preferably added as a solid and not in the form of a solution during production. 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} · _y H are used ₂ O, in which x, known as the modulus, an integer 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 that fall under this general formula are described, for example, in the European patent application EP 0 164 514 described. Preferred crystalline layered silicates are those in which x in the general formula mentioned 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. δ-sodium silicates with egg nem module between 1.9 and 3.2 can according to the Japanese patent applications JP 04/238 809 or JP 04/260 610 getting produced. Also practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can be produced from amorphous alkali silicates, as in the European patent applications EP 0 548 599 . EP 0 502 325 and EP 0 425 428 described, can be used in agents containing a polymer according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as is the case with the method of the European patent application EP 0 436 835 can be made from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as they are based on 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 according to the invention. Their alkali silicate content is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on the anhydrous active substance. If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is then preferably 4: 1 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

In addition to the inorganic Builders can more water soluble or water-insoluble inorganic substances in the compositions which are used according to the invention Contain cellulose derivative, used together with this or in processes according to the invention are used to be included. Are suitable in this context the alkali carbonates, alkali hydrogen carbonates and alkali sulfates and their mixtures. Such additional inorganic material can be present in amounts up to 70% by weight his.

In addition, the funds can be further in Washing and cleaning agents usual Components included. These optional components include in particular Enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic, polyphosphonic and / or aminopolyphosphonic acids, Foam inhibitors, for example organopolysiloxanes or paraffins, solvent and optical brighteners, for example stilbene disulfonic acid derivatives. Before are preferably in means, which is used according to the invention Cellulose derivative contain up to 1% by weight, in particular 0.01% by weight up to 0.5% by weight of optical brighteners, in particular compounds the class of substituted 4,4'-bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, bis 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for heavy metals, in particular aminoalkylenephosphonic and their salts and up to 2% by weight, in particular 0.1% by weight to 1 wt .-% foam inhibitors contain, the weight percentages mentioned refer to the entire average.

Solvent, which in particular with liquid Funds can be used in addition to water are preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, isopropanol, and the isomeric butanols, glycerin, lower glycols, for example Ethylene and propylene glycol, and those from the classes of compounds mentioned derivable ether. The liquid used in the present invention lies in such liquid media Cellulose derivatives usually dissolved or in suspended form in front.

Enzymes which may be present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof. Protease obtained from microorganisms such as bacteria or fungi is primarily suitable. It can be obtained in a known manner by fermentation processes from suitable microorganisms, for example in the German published documents DE 19 40 488 . DE 20 44 161 . DE 21 01 803 and DE 21 21 397 , the U.S. patents US 3,623,957 and US 4,264,738 , the European patent application EP 006 638 and the international patent application WO 91/02792. Proteases are commercially available, for example, under the names BLAP ^® , Savinase ^® , Esperase ^® , Maxatase ^® , Optimase ^® , Alcalase ^® , Durazym ^® or Maxapem ^® . The lipase that can be used can be from Humicola lanuginosa, such as 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 patent application WO 90/10695, from Fusarium species, such as, for example, 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 described, won. Suitable lipases are for example available under the names Lipolase ^®, Lipozym ^®, Lipomax® ^®, Lipex ^{®, ®} Amano lipase, Toyo Jozo ^® lipase, Meito ^® lipase and Diosynth lipase ^® commercially. geeigne te amylases are commercially available for example under the name Maxamyl ^®, Termamyl ^®, Duramyl ^® and Purafect ^® OxAm. The cellulase which can be used can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5. Such cellulases are, for example, from the German published documents 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 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 ^® .

The usual enzyme stabilizers which may be present, in particular in liquid agents, include amino alcohols, for example mono-, di-, triethanol- and propanolamine and mixtures thereof, and lower carboxylic acids, for example from European patent applications EP 376 705 and EP 378 261 known, 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 those 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, in particular beef soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may also contain microfine, optionally silanized or otherwise hydrophobized silica. For use in particulate compositions, such foam inhibitors are preferably bound to granular, water-soluble carrier substances, as is the case, for example, in the German patent application 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 is an agent in the cellulose derivative to be used according to the invention is incorporated, particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight, of bleach, in particular alkali percarbonate, up to 15% by weight, in particular 1 % By weight to 10% by weight bleach activator, 20% by weight to 55% by weight inorganic Builder, up to 10 wt .-%, in particular 2 wt .-% to 8 wt .-% water-soluble organic builder, 10% to 25% by weight synthetic anionic surfactant, 1% by weight to 5% by weight of nonionic surfactant and up to 25% by weight, in particular 0.1% by weight to 25% by weight of inorganic salts, in particular Alkali carbonate and / or bicarbonate.

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

Possible is also the use of a combination of the cotton active dirt-releasing cellulose derivative with a polyester-active dirt-releasing polymer from a dicarboxylic acid and an optionally polymeric diol to enhance cleaning performance of detergents containing bleach when washing textiles. Also within the scope of agents according to the invention and the method according to the invention are such combinations of the cotton-active dirt-releasing cellulose derivative mentioned possible with a polyester-active dirt-releasing polymer.

The known polyester-active dirt-releasing polymers which can be used in addition to the cellulose 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. The preferred dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-OOOH and the second monomer being a diol HO- (CHR ¹¹ -) _a OH, which is also used as a polymer Diol H- (O- (CHR ₁₁ -) _a ) _b OH may be present. Therein, Ph represents an o-, m- or p-phenylene radical, which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ^{11 is} hydrogen, an alkyl radical having 1 to 22 carbon atoms and their mixtures, a a number from 2 to 6 and b a number from 1 to 300. Preferably, both monomer diol units -O- (CHR ₁₁ -) _a O- and polymer diol units - ( O- (CHR ¹¹ -) _a ) _b O- before. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. The degree of polymerization b is preferably in the polymer diol units in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred dirt-releasing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000. The acid on which the rest Ph is based becomes preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among them, the sodium and potassium salts are particularly preferred. If desired, instead of the HOOC-Ph-OOOH monomer, small amounts, in particular not more than 10 mol%, based on the amount of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the dirt-releasing polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, 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 carbon 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 with an average molecular weight in the range from 1000 to 6000.

If desired, the as described above, polyester also end-capped be, the end groups being alkyl groups having 1 to 22 carbon atoms and Esters of monocarboxylic acids come into question. The over End groups bonded to ester bonds can be alkyl, alkenyl and aryl monocarboxylic acids 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, are based. These include Valeric acid, Caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linololic acid, linostolic acid Behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotinic acid, melissic acid, benzoic acid, the 1 to 5 substituents with a total of up to 25 carbon atoms, in particular Can carry 1 to 12 carbon atoms, for example tert-butylbenzoic acid. The End groups can also hydroxymonocarboxylic acids with 5 to 22 carbon atoms on which, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their Hydrogenation product include hydroxystearic acid and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic can in turn over its hydroxyl group and its carboxyl group may be linked to one another and thus exist more than once in an end group. Preferably lies the number of hydroxymonocarboxylic acid units per end group, this means their degree of oligomerization, 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 from 750 to Have 5000 and the molar ratio from ethylene terephthalate to polyethylene oxide terephthalate 50:50 to Is 90:10, used in combination with the cellulose derivatives.

The soil release polymers are preferred water soluble, where under the term "water-soluble" 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 should be understood. However, polymers used with preference have under these conditions a solubility of at least 1 g per liter, in particular at least 10 g per liter on.

Preferred laundry aftertreatment compositions which contain a cellulose derivative to be used according to the invention have a so-called ester quat as the softening active ingredient, that is to say a quaternized ester of carboxylic acid and amino alcohol. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this context, reference is made to the 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. From the German patent specification DE 43 08 794 a process for the production of solid ester quats is also known, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Overviews on this topic have been published, 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) appeared.

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 elaidinsäurereiche 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 the formula (I)

in which R ¹ CO stands for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats that 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, arachic 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. Technical C _12/18 coconut _fatty acids and in particular partially hardened C _16/18 tallow or palm fatty acids as well as C _16/18 fatty acid _cuts rich in elaidic acid are preferably 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. With regard to the application properties of the ester quats, an application 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 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 fatty acid (iodine number 0 to 40) , Quaternized fatty acid triethanolamine ester salts of the formula (I) in which R ¹ CO for an acyl radical having 16 to 18 carbon atoms, R ² for R ¹ CO, R ³ for hydrogen, R ⁴ for a methyl group, m, n and p for 0 and X for Methyl sulfate is 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 which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X stands for 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-dihydroxypropyldialkylamines of the formula (III) should be mentioned as a further group of suitable ester quats,

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimum degree of esterification apply to those mentioned for (I) exemplary information analogously also for the esterquats of the formulas (II) and (III). Usually the esterquats arrive in the form of 50 to 90 weight percent alcoholic solutions on the market, which can also be easily diluted with water can, ethanol, propanol and isopropanol being the usual alcoholic solvents are.

Ester quats are preferably in Amounts from 5% by weight to 25% by weight, in particular 8% by weight to 20 % By weight, based in each case on the total laundry aftertreatment agent, used. If desired, the used according to the invention Fabric conditioners additionally Detergent ingredients listed above included, unless they are unreasonably negative with the Interacting with Esterquat. It is preferably a liquid, hydrated agent.

Examples

Example 1: Containing a detergent (V1) 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 5 parts by weight Tinopal ^® DMS-X 0.2 parts by weight
2 parts by weight of methyl-hydroxyethyl cellulose, average molecular weight 95,000 (W1) or 2 parts by weight of methyl-hydroxypropyl cellulose, average molecular weight 50,000 (W2) were added. For comparison, a detergent V2 was also prepared from V1 by adding 2 parts by weight of polyethylene terephthalate-polyoxyethylene glycol copolymer (Repel-O- ^Tex® ). Pure cotton, finished cotton, and polyester / cotton blended fabrics 50/50 were treated as follows: Washer: Miele W 918 Novotronic ^® Primary washing power: Soak-in procedure normal program Washing temperature: 40 ° C Determination: 5 times Fleet size: 18 1 Water hardness: 16 ° dH filling laundry: 3.5 kg of clean laundry

The fabrics were washed uncontaminated three times with the detergent to be tested under the conditions specified above and dried after each wash. After prewashing three times, the fabrics were soiled with the following standardized soiling by hand:
0.10 g lipstick
0.10 g black shoe polish
0.10 g dust / skin fat

The soiled tissues were measured with a Minolta CR 200 and then aged at RT for 7 days. The soiled tissues were then stapled onto towels and washed under the conditions specified above.

Tabelle 2: Baumwolle veredelt

Tabelle 3: Baumwolle / Polyester

The tissues were dried and measured again with a Minolta CR 200. The washing results (dde values) were as follows: Table 1: Cotton pure

Table 2: Cotton refined

Table 3: Cotton / polyester

It can be seen that the detergents with those to be used according to the invention Cellulose derivative (W1 and W2) has a significantly better washing performance show as the means that lacks this (V1), or that in its place contains a polyester (V2).

Example 2:

As described in Example 1 Washing tests carried out, the tissues being soiled three times with detergent V1, but additionally with cellulose derivative-containing softener S1 (15% by weight ester quat and 2% by weight of the methyl-hydroxyethyl cellulose used in Example 1 in water) or with the same softener as the cellulose derivative was missing (SO) rinsed and after every wash were dried. Subsequently the tissues were soiled with the standardized soiling, the soiled tissues were measured with a Minolta CR 200, Aged 7 days at RT, then stapled on towels and under the conditions given in Example 1 washed with V1 and with S1 or SO flushed.

Tabelle 5: Baumwolle veredelt

Tabelle 6: Baumwolle / Polyester

The tissues were dried and measured again with a Minolta CR 200. The following washing results (dde values) resulted: Table 4: Cotton pure

Table 5: Cotton refined

Table 6: Cotton / polyester

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

Tabelle 8: Baumwolle veredelt

Tabelle 9: Baumwolle / Polyester

Example 3 Containing a detergent (V3) 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 2 parts by weight enzyme 1.5 parts by weight
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 and V4, the detergents V5 and W3 were prepared from these. As described in Example 1, washing tests were carried out with these agents. The following washing results (dde values) resulted: Table 7: Cotton pure

Table 8: Cotton refined

Table 9: Cotton / polyester

It can be seen that the detergents with the cellulose derivative (V5 and W3) better results in most cases show as the corresponding means, which lack this (V3 and V4), but that that agents containing bleach with the cellulose derivative used according to the invention (W3) gives the best performance.

Claims (14)

Use of dirt-releasing cellulose derivatives that available are by alkylation and hydroxyalkylation of cellulose reinforcement the cleaning performance of detergents containing bleach Washing of textiles consisting in particular of cotton or Cotton included. Use of dirt-releasing cellulose derivatives that available are by alkylation and hydroxyalkylation of cellulose reinforcement the cleaning performance of detergents containing bleach Washing of textiles consisting in particular of cotton or Contain cotton, and already in the presence of the cellulose derivative washed and / or after-treated before using the Soiling were provided. Use of a combination of dirt-releasing cellulose derivative, that available is by alkylation and hydroxyalkylation of cellulose, and a polyester active dirt release polymer from a dicarboxylic acid and an optionally polymeric diol to enhance cleaning performance of detergents containing bleach when washing textiles. Use according to one of claims 1 to 3, characterized in that the cellulose derivative is alkylated with C ₁ to C ₁₀ groups, in particular C ₁ to C ₃ groups, and in addition C ₂ to C ₁₀ hydroxyalkyl groups, in particular C ₂ - C ₃ hydroxyalkyl groups. Use according to one of claims 1 to 4, characterized in that that in Cellulose derivative averaged 0.5 to 2.5, especially 1 to 2 alkyl groups and 0.02 to 0.5, especially 0.05 to 0.3, hydroxyalkyl groups are contained per anhydroglycosomer monomer unit. Use according to one of claims 1 to 5, characterized in that that the average molecular weight of the cellulose derivative in the range of 10,000 D. up to 150,000 D, in particular from 40,000 D to 120,000 D and especially is preferably in the range from 80,000 D to 110,000 D. Use according to one of claims 1 to 6, characterized in that that in the bleach-containing detergent 5 wt .-% to 70 wt .-% bleach and optionally bleach activator, especially in amounts in Range of 2 wt .-% to 10 wt .-% is included. Process for washing textiles, in which a detergent containing bleach and a dirt-releasing cellulose derivative, that available is by alkylation and hydroxyalkylation of cellulose, to Come into play. A method according to claim 8, characterized in that this Textile after the actual washing process, which is done with the help of a bleach Running detergent with a post-treatment agent which is a cellulose derivative contains that available is in contact by alkylation and hydroxyalkylation of cellulose brought. A method according to claim 9, characterized in that he uses a laundry after-treatment agent, which is a dirt-releasing cellulose derivative, that available is by alkylation and hydroxyalkylation of cellulose, and Contains ester quat. A method according to claim 10, characterized in that this Agent ester quat in amounts of 5% by weight to 25% by weight, in particular Contains 8 wt .-% to 20 wt .-%. Method according to one of claims 8 to 11, characterized in that that this Agent cellulose derivative in amounts of 0.1 wt.% To 5 wt.%, In particular Contains 0.5 wt.% To 2.5 wt.%. Method according to one of claims 8 to 12, characterized in that that in the bleach-containing detergent 5 wt .-% to 70 wt .-% bleach and optionally bleach activator, especially in amounts in Range of 2 wt .-% to 10 wt .-% is included. Detergent containing bleach, containing a dirt-releasing cellulose derivative, that available is by alkylation and hydroxyalkylation of cellulose.