EP2917319B1 - Polymers comprising polar groups as stain removing agents - Google Patents

Description

The present invention relates to the use of certain soil release polymer active agents to enhance the cleaning performance of detergents in the washing of textiles, and more particularly to liquid laundry detergents and cleaners containing such soil release agents, and to a process for washing textiles using such polymeric active ingredients.
Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builder materials usually further ingredients that can be summarized by the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and dye transfer inhibitors. Such adjuvants also include substances which impart soil repellency properties to the laundry fiber and, if present during the wash, aid the soil release properties of the remaining detergent ingredients. The same applies mutatis mutandis to cleaners for hard surfaces. Such soil release agents are often referred to as "soil release" agents or because of their ability to impart soil repellency to the treated surface, such as the fiber, as "soil repellents". For example, the soil release-enhancing effect of alkyl hydroxyalkyl celluloses and alkyl celluloses such as methyl cellulose is known.
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.
Surprisingly, it has been found that certain graft copolymers which are structurally different from such esters have a soil release-capable action, in particular in the case of textiles which consist of polyester or contain a polyester fraction.
The invention relates to the use of a soil release agent selected from graft copolymers as defined in the claims which have a polar group for enhancing the cleaning performance of detergents in the washing of textiles.

Preferred are water-soluble polymers obtainable by graft copolymerization. Suitable grafting bases are polyalkylene glycols, in particular polyethylene glycols, having an average (number average) molecular weight of, for example, 50 g / mol to 50,000 g / mol, in particular 1000 g / mol to 10,000 g / mol. To prepare the graft branches, 2-propene-1-sulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyldimethyl-3-methacrylamidopropylammonium salt, 1-allyloxy-2-hydroxypropylsulfonic acid, salts, in particular alkali metal salts, of these acids, and mixtures thereof are used. From these, for example, graft copolymers can be obtained which have a graft base content of from 10% by weight to 90% by weight and a content of grafted branches of from 90% by weight to 10% by weight, based in each case on the polymer , The ratio of grafting to grafting is preferably chosen so that the graft copolymers are water-soluble, the water solubility at 20 ° C and pH 7 at least about 1 g / l, but preferably more, for example at least 2 g / l, 5 g / l or 10 g / l.
The proportion of polar groups in the polymer is preferably 5% by weight to 90% by weight, in particular 40% by weight to 70% by weight, in each case based on the polymer.

Another object of the invention is a process for washing textiles, in which a detergent and a said soil release agent are used. In this case, the detergent and soil-release agent, especially in the presence of water, are brought into contact with a textile in need of cleaning. The method can be carried out manually or preferably by means of a conventional household washing machine. It is possible to apply the particular liquid detergent and soil release agent simultaneously or sequentially. The simultaneous application can be particularly advantageous by the use of a detergent containing the soil release agent, perform. The process is preferably carried out at temperatures of the washing solution in the range from 15 ° C to 60 ° C, in particular from 20 ° C to 40 ° C.
Particularly pronounced is the washing performance-enhancing effect of the active ingredients to be used according to the invention in the case of multiple applications, that is to say in particular for the removal of The active ingredients in multiple applications, that is, in particular for the removal of soiling of corresponding textiles, which had already been washed in the presence of the active ingredient and / or post-treated before they were provided with the soiling. In connection with the aftertreatment it should be pointed out that the designated positive aspect can also be realized by a washing process in which the textile after the actual washing process, with the help of a detergent which may contain a named active ingredient, but in this case also free may be carried out by this, with an aftertreatment agent, for example in the context of a fabric softening step, which contains an active substance to be used according to the invention is brought into contact. In this procedure as well, if desired again a detergent without an active ingredient to be used according to the invention is used in the next washing process, the washing performance-enhancing effect of the active ingredients to be used according to the invention occurs. This is significantly higher than that resulting from the use of a conventional SRP active ingredient.

The active ingredients used in the invention are as described easily produced and ecologically and toxicologically harmless. They lead to a significantly better detachment of particular grease and cosmetics stains on textiles, including those made of cotton or cotton-containing fabric, as is the case when using previously known for this purpose compounds. 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 in such a way that the active ingredient is added to a detergent-containing, in particular aqueous, liquor or, preferably, the active ingredient is introduced into the liquor as a constituent of a washing agent. Another object of the invention is therefore a detergent containing an active ingredient described above. Such an agent, especially if it is liquid, optionally after dissolving in or diluted with water, applied in the sense of a pre-treatment measure on a soiled textile as a whole or preferably on its soiled parts and after the exposure, which can be done under the influence of mechanical force, if desired to be washed out.

The use according to the invention in the context of a laundry aftertreatment process can be carried out in such a way that the active ingredient of the rinsing liquor is added separately, which is used after the wash cycle, in particular using a bleach-containing detergent, or it is incorporated as a component of a laundry aftertreatment agent, in particular a softener. In this aspect of the invention, said detergent may also contain, but may be free of, an active ingredient to be used according to the invention.

Detergents containing an active ingredient 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 do not interact in an undesired manner with the active ingredient essential to the invention. The active substance defined above is preferably incorporated in detergents in amounts of from 0.01% by weight to 5% by weight, in particular from 0.1% by weight to 2% by weight. The detergents are preferably liquid and hydrous and have a pH in the range of 6 to 11, preferably 7.5 to 9.5.

Surprisingly, it has been found that such active ingredients positively affect the action of certain other detergent ingredients and that, conversely, the effect of the soil-release agent is further enhanced by certain other detergent ingredients. These effects occur in particular with bleaches, with enzymatic active substances, in particular proteases and lipases, with water-soluble inorganic and / or organic builders, in particular based on oxidized carbohydrates or polymeric polycarboxylates, with synthetic anionic surfactants of the sulphate and sulphonate type, and with color transfer inhibitors, for example vinylpyrrolidone , Vinylpyridin- or vinylimidazole polymers or copolymers or corresponding Polybetainen on, which is why the use of at least one of said further ingredients together with the invention to be used drug is preferred.

An agent which contains an active substance to be used according to the invention or is used together or is used in the process according to the invention preferably contains peroxygen-based bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally Bleach activator, especially in amounts ranging from 2% to 10% by weight. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic 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 containing an active ingredient 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 .-%, each based 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 anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, and also cationic nitrile derivatives such as trimethylammonium acetonitrile salts. The bleach activators can to avoid interaction with the peroxygen compounds during storage in a known manner coated with coating substances or granulated, wherein granulated tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2 with the aid of carboxymethylcellulose , 4-dioxohexahydro-1,3,5-triazine, and / or particulate form trialkylammonium acetonitrile is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.

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 and Fettsäurepolyhydroxyamide into consideration. For incorporation into the invention Agents suitable so-called alkylpolyglycosides 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. 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 which contain a soil-release agent used according to the invention, or used in the process according to the invention, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 Wt .-%, with amounts in the upper part of this range are more likely to be found in liquid detergents and particulate detergents preferably contain rather lower amounts of up to 5 wt .-%.

The agents may instead or additionally contain other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as, for example, alkylbenzenesulfonates, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight. %, in each case based on total resources. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of 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. To the usable surfactants Sulfate type also includes the sulfated alkoxylation of said alcohols, so-called 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% 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 polycarboxylic acids, in particular citric acid and sugar acids, as well as the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which also small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized. 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. Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may 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, 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 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, according to the information of the 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 are described, 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 .beta.- and δ-Natriumdisitikate (Na ₂ Si ₂ O ₅ · yH ₂ O) are preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1.9 to 2.1, can be used in agents which contain an active ingredient to be used 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 can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention. their Content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In agents containing both amorphous and crystalline alkali metal 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 to 2: 1.

In addition to the said inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the compositions which contain an active substance to be used according to the invention together with it or used in the process 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 customary in detergents and cleaners. These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably, in agents which contain an active substance 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 active compounds 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, it comes from microorganisms, such as bacteria or fungi Protease in question. It can be obtained in a known manner by fermentation processes from suitable microorganisms. 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, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species. 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 commercially available under the names Celluzyme®, Carezyme® and Ecostone®.

The customary enzyme stabilizers present, if appropriate, in particular in liquid agents include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid or alkali borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.

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.

In a preferred embodiment, an agent to which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular from 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 into which the active ingredient to be used according to the invention is incorporated 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 fragrance water and / or water-miscible solvent.

It is also possible to use a combination of a soil release agent according to the invention with a soil release polymer of a dicarboxylic acid and an optionally polymeric diol to enhance the cleaning performance of detergents in the washing of textiles. Also within the scope of the inventive composition and the method according to the invention, such combinations are possible with a particular polyester-active soil release polymer.

The known polyester-active soil release polymers which can be used in addition to the active compounds 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 radical 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. To this 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, these polyesters composed 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 bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid , The end groups may also be based on hydroxymonocarboxylic acids having from 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which includes hydroxystearic acid and o-, m-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 a combination with an essential ingredient of the invention.

The soil release-bearing additional 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 which comprise an active substance 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 which can be obtained by the relevant methods of preparative organic chemistry, for example by partially esterifying triethanolamine in the presence of hypophosphorous acid with fatty acids, passing air through and then quaternizing with dimethyl sulfate or ethylene oxide. 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.

in denen R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² und R³ unabhängig voneinander für Wasserstoff oder R¹CO, R⁴, R⁵ und R⁶ unabhängig voneinander für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Formel (IV) oder m und n in Formeln (V) und (VI) 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 (lodzahl 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. Esterquats werden vorzugsweise in Mengen von 5 Gew.-% bis 25 Gew.-%, insbesondere 8 Gew.-% bis 20 Gew.-%, jeweils bezogen auf gesamtes Wäschenachbehandlungsmittel, eingesetzt. Gewünschtenfalls können die erfindungsgemäß verwendeten Wäschenachbehandlungsmittel zusätzlich oben aufgeführte Waschmittelinhaltsstoffe enthalten, sofern sie nicht in unzumutbarer Weise negativ mit dem Esterquat wechselwirken. Bevorzugt handelt es sich um ein flüssiges, wasserhaltiges Mittel. Referenzbeispiel Waschgerät: Miele W 918 Novotronic® Waschprogramm: Einlaugenverfahren Koch-Bunt Programm Waschtemperatur: 40°C oder 20 °C Flottenvolumen: 17 l Wasserhärte: 16°dH Füllwäsche: 3,5kg saubere Wäsche(Kopfkissen, Trikot, Geschirr-, Gerstenkornhandtücher) inkl. Testtextilien Testtextilien aus Polyester wurden mit einem Waschmittel E1, welches einen der oben beschriebenen Wirkstoffe enthielt, mit dem Waschmittel V1, dem dieser Wirkstoff fehlte, oder mit dem Waschmittel V2, das stattdessen ein anderes Polymer enthielt, unter den oben angegebenen Bedingungen 3x gewaschen und nach der Wäsche luftgetrocknet. Danach erfolgte die Applizierung standardisierter fett/pigmenthaltiger Anschmutzungen (A: Motoröl; B: Lippenstift: C: Hautfett) sowie eine Alterung der Anschmutzungen von 7 Tagen. Die so vorbereiteten Textilien wurden unter den oben genannten Bedingungen erneut mit dem Waschmittel gewaschen. Die Auswertung erfolgte colorimetrisch; in Tabelle 2 sind die Mittelwerte (Helligkeit, Y-Werte) aus 5-fach-Bestimmungen angegeben. Tabelle 1: Waschmittelzusammensetzung [Gew.-%]: V1 E1 V2 C_12-14-Fettalkohol mit 7 EO 7 7 7 C_12-18-Fettsäure, Na-Salz 10 10 10 Borsäure 4 4 4 Zitronensäure 2 2 2 Propandiol 6 6 6 NaOH 3 3 3 Protease 0,6 0,6 0,6 Amylase 0,1 0,1 0,1 Wirkstoff - 1 - Polymer²⁾ - - 1 Wasser auf 100 ¹⁾ Propfcopolymer aus Polyethylenoxid mit Vinylacetat
²⁾ Mit durchschnittlich 40 EO ethoxyliertes Polyethylenimin 600 Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow formulas (IV), (V) or (VI),

in which R ^{1 is} 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 , R ⁵ and R ^{6 are} independently an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H group, m, n and p in formula (IV) or m and n in formulas (V) and (VI) in sum for 0 or numbers from 1 to 12, q for 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, arachic acid, behenic acid and erucic acid as well as their technical mixtures, as obtained for example in the pressure splitting of natural fats and oils. Preferably, technical C _12/18 coconut _fatty acids and, in particular, partially hydrogenated C _16/18 tallow or palm oil fatty acids and also elaidic acid-rich C _16/18 fatty acid cuts are 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 having 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 number 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. 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. reference example Washer: Miele W 918 Novotronic® Wash program: Single-leach cooking-colorful program Washing temperature: 40 ° C or 20 ° C Fleet size: 17 l Water hardness: 16 ° dH filling laundry: 3.5kg clean linen (pillows, jersey, crockery, barley grain towels) including test textiles Polyester test fabrics were washed with a detergent E1 containing one of the above-described active ingredients, with the detergent V1, which lacked this active ingredient, or with the detergent V2, which instead contained another polymer, under the conditions indicated above 3 times and after Laundry air dried. This was followed by the application of standardized grease / pigment soiling (A: motor oil, B: lipstick: C: skin fat) and an aging of soiling of 7 days. The textiles thus prepared were washed again with the detergent under the conditions mentioned above. The evaluation was carried out colorimetrically; Table 2 shows the mean values (brightness, Y values) from 5-fold determinations. V1 E1 V2 C _12-14 fatty alcohol with 7 EO 7 7 7 C _12-18 fatty acid, Na salt 10 10 10 boric acid 4 4 4 citric acid 2 2 2 propanediol 6 6 6 NaOH 3 3 3 protease 0.6 0.6 0.6 amylase 0.1 0.1 0.1 active substance - 1 - Polymer ²⁾ - - 1 water on 100 ¹⁾ graft copolymer of polyethylene oxide with vinyl acetate
²⁾ With an average of 40 EO ethoxylated polyethyleneimine 600

The detergent with an active ingredient to be used according to the invention showed a significantly better washing performance than the otherwise equal composition which it lacked: Table 2: Wash results Soiling \ Central V1 E1 A; 40 ° C 48.4 54.1 B; 40 ° C 57.6 60.7 C; 40 ° C 50.5 55.7 A; 20 ° C 51.0 52.1 C; 20 ° C 51.5 54.7

Claims (10)

1. The use of an active ingredient which allows the removal of dirt and is selected from graft copolymers which contain a polyalkylene glycol graft base and, as a grafted branch, polymerized compounds comprising at least one olefinically unsaturated double bond and a polar group, selected from 2-propene-1-sulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyl dimethyl-3-methacrylamido propyl ammonium salt, 1-allyloxy-2-hydroxypropyl sulfonic acid, salts, in particular alkali metal salts, of said acids, and mixtures thereof, for increasing the cleaning performance of washing agents when washing textiles.
2. The use of a combination of an active ingredient which allows the removal of dirt and is selected from graft copolymers which contain a polyalkylene glycol graft base and, as a grafted branch, polymerized compounds comprising at least one olefinically unsaturated double bond and a polar group, selected from 2-propene-1-sulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyl dimethyl-3-methacrylamido propyl ammonium salt, 1-allyloxy-2-hydroxypropyl sulfonic acid, salts, in particular alkali metal salts, of said acids, and mixtures thereof, and a dicarboxylic acid and an optionally polymeric diol, for increasing the cleaning performance of washing agents when washing textiles.
3. The use according to claim 1 or 2 when washing textiles, which had already been washed and/or post-treated in the presence of the active ingredient which allows the removal of dirt before they were soiled.
4. A method for washing textiles, wherein a washing agent and an active ingredient are used, which active ingredient allows the removal of dirt and is selected from graft copolymers which contain a polyalkylene glycol graft base and, as a grafted branch, polymerized compounds comprising at least one olefinically unsaturated double bond and a polar group, selected from 2-propene-1-sulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyl dimethyl-3-methacrylamido propyl ammonium salt, 1-allyloxy-2-hydroxypropyl sulfonic acid, salts, in particular alkali metal salts, of said acids, and mixtures thereof.
5. The method according to claim 4, characterized in that said method is carried out at temperatures of the washing solution in the range of from 15 °C to 60 °C, in particular from 20 °C to 40 °C.
6. The method according to claim 4 or 5, characterized in that, after the actual washing process, which is carried out using a washing agent which in particular contains a bleaching agent, the textile is brought into contact with a post-treatment agent, which contains the active ingredient or which contains the active ingredient which allows the removal of dirt and esterquat.
7. The method according to one of claims 4 to 6, characterized in that the agent contains the active ingredient which allows the removal of dirt in amounts of from 0.01 wt.% to 5 wt.%, in particular from 0.1 wt.% to 2 wt.%.
8. The use or method according to one of the preceding claims, characterized in that the active ingredient which allows the removal of dirt is a water-soluble polymer which can be obtained by means of graft copolymerization.
9. The use or the method according to claim 8, characterized in that the graft base is a polyalkylene glycol, in particular polyethylene glycol, having an average (number average) molecular weight of from 50 g/mol to 50000 g/mol, in particular from 1000 g/mol to 10000 g/mol.
10. The use or method according to claim 8 or 9, characterized in that the graft copolymer has a graft base content of from 10 wt.% to 90 wt.% and a grafted branch content of from 90 wt.% to 10 wt.%, in each case based on the polymer, and/or the proportion of polar groups in the polymer is from 5 wt.% to 90 wt.%, in particular from 40 wt.% to 70 wt.%, in each case based on the polymer.