EP3848441A1 - Carboxymethylated poly(2-vinylpyridins) as dirt loosening agents - Google Patents

Abstract

The cleaning performance of detergents when washing textiles should be improved. This was mainly achieved through the use of carboxymethylated poly (2-vinylpyridines).

Description

The present invention relates to the use of certain soil-releasing active ingredients for enhancing the cleaning performance of detergents when washing textiles.

In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents usually contain other components that can be summarized under the term washing auxiliaries and that include such different groups of active ingredients as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors. Such auxiliaries also include substances which give the laundry fiber dirt-repellent properties and which, if present during the washing process, support the dirt-releasing ability of the other detergent constituents. The same applies accordingly to cleaning agents for hard surfaces. Such dirt-releasing substances are often referred to as “soil release” active ingredients or, because of their ability to make the treated surface, for example the fiber, dirt-repellent, they are referred to as “soil repellents”. For example, from the US patent U.S. 4,136,038 the dirt-releasing effect of methyl cellulose is known. 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 US patent U.S. 4,000,093 discloses detergents which contain 0.1% by weight to 3% by weight alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and also 5% by weight to 50% by weight surfactant, the surfactant component essentially consists of C ₁₀ - to C ₁₃ -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 ₁₅ and higher.

Because of their chemical similarity to polyester fibers in textiles made of this material, particularly effective soil-releasing agents are copolyesters that contain dicarboxylic acid units such as terephthalic acid or sulfoisophthalic acid, alkylene glycol units such as ethylene glycol or propylene glycol and polyalkylene glycol units such as polyethylene glycol. Soil-releasing copolyesters of the type mentioned, as well as their use in detergents, have been known for a long time.

The polymers known from the prior art have the disadvantage that they have no or only inadequate effectiveness, particularly in the case of textiles which do not or at least not predominantly consist of polyester. A large part of today's textiles consists of cotton or cotton-polyester blends, so there is a need for in particular greasy soiling on textiles of this type, in particular, is more effective soil-releasing active ingredients.

It has surprisingly been found that this object can be achieved by using certain carboxymethylated poly (2-vinylpyridines).

zur Verstärkung der Reinigungsleistung von Waschmitteln beim Waschen von Textilien.The invention relates to the use of 2-vinylpyridine polymers which contain units of the general formula I,

to increase the cleaning performance of detergents when washing textiles.

Polymers of the general formula I can be obtained by reacting haloacetic esters, for example ethyl bromoacetate, with poly (2-vinylpyridine) and subsequent hydrolysis of the ester groups, for example from Billing, M., Elter, JK and Schacher, FH, in Polymer 2016, 104, 40-48 described. Poly (2-vinylpyridine) can be obtained by radical polymerization of 2-vinylpyridine. The polymer used according to the invention contains no units other than those shown in formula I apart from the radical initiator and / or radical terminator compounds present in the polymerization. The ratio of the relative proportions of the two units, n: m, is preferably in the range from 60:40 to 10:90, in particular from 50:50 to 20:80. The said ratio can easily be controlled by the amount of haloacetic acid ester used per pyridine N atom; As a result of the production process, the carboxymethylpyridinium units and the pyridinium units are generally randomly distributed in the polymer used according to the invention. The number-average molecular weight of the polymers used according to the invention is preferably in the range from 5,000 g / mol to 100,000 g / mol, in particular from 10,000 g / mol to 50,000 g / mol.

Another object of the invention is a method for washing textiles in which a detergent and a soil-releasing agent in the form of a polymer defined above are used. These methods can be carried out manually or, if necessary, with the aid of a conventional household washing machine. It is possible to use the detergent and the soil-releasing agent at the same time or one after the other. The simultaneous Application can be carried out particularly advantageously through the use of a detergent which contains the soil-releasing active ingredient. The method essentially consists in bringing a textile in need of cleaning or at least the soiled part of its surface into contact with an aqueous preparation that contains the polymer defined above, the aqueous preparation for a certain time on the textile or at least the soiled part of it Allow the surface to act and remove the aqueous preparation, for example by rinsing the textile with water.

The effect of the active ingredient to be used according to the invention is particularly pronounced when used repeatedly, that is to say in particular to remove soiling from textiles that had already been washed and / or aftertreated in the presence of the active ingredient before they were provided with the soiling. In connection with the aftertreatment, it should be pointed out that the described positive aspect can also be achieved by a washing process in which the textile is free after the actual washing process, which with the help of a detergent, which can contain a named active ingredient, but in this case also from this, is carried out, is brought into contact with an aftertreatment agent, for example as part of a fabric softener step, which contains an active ingredient to be used according to the invention, in the presence of water. With this procedure, too, the washing performance-enhancing effect of the active ingredients to be used according to the invention occurs in the next washing process, even if, if desired, a detergent without an active ingredient to be used according to the invention is used again. This is significantly higher than the one resulting from the use of a conventional soil release agent. In a particularly preferred embodiment, the active ingredient essential to the invention is added in the fabric softener cycle, in particular for machine laundry.

The active ingredient used according to the invention leads to a significantly better removal of, in particular, grease and cosmetic soiling on textiles, in particular those made of cotton or cotton-containing fabric, than is the case when using compounds previously known for this purpose. Alternatively, significant amounts of surfactants can be saved while maintaining the same fat removal capacity.

The uses according to the invention can be carried out in the context of a washing process in such a way that the soil-releasing active ingredient is added to a detergent-containing liquor or, preferably, the active ingredient is introduced into the liquor as a component of a detergent that contains the object to be cleaned or that is brought into contact with it. Further objects of the invention are therefore detergents which contain polymers defined above.

The use according to the invention in the context of a laundry aftertreatment process can accordingly take place in such a way that the soil-releasing active ingredient of the washing liquor is removed is added separately, which is used after the wash cycle carried out using a detergent, or it is incorporated as a component of the laundry aftertreatment agent, in particular a fabric softener. In this aspect of the invention, the detergent used before the laundry aftertreatment agent can also contain an active ingredient to be used according to the invention, but can also be free of this.

The washing process is preferably carried out at a temperature of 15 ° C to 60 ° C, particularly preferably at a temperature of 20 ° C to 40 ° C. The washing process is also preferably carried out at a pH of 6 to 11, particularly preferably at a pH of 7.5 to 9.5. The concentration of the polymer used in the wash liquor is preferably 0.0001 g / l to 1 g / l, in particular 0.001 g / l to 0.2 g / l.

Agents that contain an active ingredient to be used according to the invention in the form of the named polymer or are used together with this or are used in the method according to the invention can contain all the usual other components of such agents that do not interact in an undesirable manner with the active ingredient according to the invention, in particular surfactant. The agent preferably contains the active ingredient defined above in amounts from 0.01% by weight to 5% by weight, particularly preferably from 0.02% by weight to 3% by weight, this and the following amounts being based on each other refer to the entire remedy unless otherwise stated.

Surprisingly, it has been found that the active ingredient used according to the invention has a positive effect on the effect of certain other detergent ingredients and that, conversely, the effect of the soil release active ingredient is additionally reinforced by certain other detergent ingredients. These effects occur in particular with bleaching agents, with enzymatic active ingredients, 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 sulfate and sulfonate type, and with color transfer inhibitors, for example vinylpyrrolidone , Vinylpyridine or vinylimidazole polymers or copolymers or corresponding polybetaines, which is why the use of at least one of the further ingredients mentioned together with the active ingredient to be used according to the invention is preferred.

An agent which contains an active ingredient to be used according to the invention or is used together with it or is used in the process according to the invention preferably contains peroxygen-based bleaching agents, in particular in amounts in the range from 5% by weight to 70% by weight, and optionally However, in another preferred embodiment, bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight, can also be free from bleaching agent and bleach activator. The bleaching agents that can be considered are preferably the peroxygen compounds usually used in detergents, such as percarboxylic acids, for example dodecanediperic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, Alkali perborate, which can be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are usually present as alkali salts, in particular as sodium salts. Such bleaches are in detergents which contain an active ingredient used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight, in each case on the entire medium, with percarbonate in particular being used. The optionally present component of the bleach activators includes the commonly used N- or O-acyl compounds, for example poly-acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines and carboxylic acid anuryl amides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. To avoid interaction with the peroxygen compounds during storage, the bleach activators may have been coated or granulated with coating substances in a known manner, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine with weight-average particle sizes of 0.01 mm to 0.8 mm, granulated 1.5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or trialkylammonium acetonitrile made up in particulate form 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 detergent.

In a preferred embodiment, an agent used according to the invention or used in the process according to the invention contains 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 acids / or fatty acid amides and mixtures thereof, in particular in an amount in the range from 2% by weight to 25% by weight.

Another embodiment of such agents comprises the presence of synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty 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 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 proportion of compounds with longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight.

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 usable alkoxylates. 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 moiety can also be used. The ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and fatty acid polyhydroxyamides are also suitable. So-called alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) _n -OR ¹² , in which R ^{12 is} an alkyl or alkenyl radical having 8 to 22 carbon atoms, G is a monosaccharide unit and n is a number between 1 and 10 mean. The glycoside component (G) _n is oligo- or polymers from naturally occurring aldose or ketose monomers, to which in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxosis. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugars they contain but also by their number, the so-called degree of oligomerization. The degree of oligomerization n generally assumes fractional numerical values as a variable to be determined analytically; it is between 1 and 10, and in the case of the glycosides preferably used, it is below 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its ready availability. The alkyl or alkenyl part R ^{12 of} the glycosides is preferably also derived 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, that is to say mixtures with essentially R ¹² = dodecyl and R ¹² = tetradecyl.

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

Instead or in addition, the agents can contain further 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. %, each based on the total agent. Particularly suitable synthetic anionic surfactants for use in such agents are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as a counter cation. The derivatives of fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived 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, derived sulfonation products, as well as the sulfo fatty acids resulting from these by formal saponification.

Other optional surfactant ingredients are soaps, 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, being suitable. In particular, preference is given to soap mixtures which are composed of 50% by weight to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. In particular, however, liquid agents which contain a polymer used according to the invention can also contain higher amounts of soap, generally up to 20% by weight.

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

In a further embodiment, the agent contains water-soluble and / or water-insoluble builders, in particular selected from alkali metal alumosilicate, crystalline alkali metal silicate with a module greater than 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range from 2.5% by weight to 60 Wt%.

The agent 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 polycarboxylic acids, in particular citric acid and sugar acids, and polymeric (poly) carboxylic acids, in particular the polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which can also be obtained by oxidation of polysaccharides may contain small amounts of polymerizable substances without carboxylic acid functionality polymerized. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, that of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid . A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 g / mol to 100,000 g / mol. 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 acid makes up 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 a third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C 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. The third monomeric unit is formed in this case by vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, vinyl alcohol derivatives are preferred which represent an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate as well 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, vinyl alcohol and / or vinyl acetate. 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, are very particularly preferred. 5: 1. 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 40% by weight to 60% by weight, in particular 45 to 55% by weight (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 methallyl sulfonic acid or methallyl sulfonate 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, with Mono-, di- or oligosaccharides are preferred, sucrose is particularly preferred. By using the third monomer, predetermined breaking points are presumably built into the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative molecular weight between 1000 g / mol and 200,000 g / mol, preferably between 3000 g / mol and 10,000 g / mol. In particular for the production of liquid agents, they can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

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

The water-insoluble, water-dispersible inorganic builder materials used are in particular 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, used. Among these, the crystalline aluminosilicates in detergent quality, in particular zeolite NaA and optionally NaX, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular do not have any particles with a particle size of more than 30 μm and preferably consist of at least 80% by weight of particles with a size of less than 10 μm. Their calcium binding capacity is in the range from 100 to 200 mg CaO per gram.Suitable substitutes or partial substitutes for said aluminosilicate 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 agents 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, in particular the amorphous sodium silicates, with a molar ratio 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®. In the course of production, they are preferably added as a solid and not in the form of a solution. The crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline _{sheet silicates of the general formula Na 2} Si _x O _{2x + 1} · yH ₂ O, in which x, the so-called modulus, is a number of 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline sheet silicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both β- and δ-sodium _{disilicates (Na 2} Si ₂ O ₅ · yH ₂ O) are preferred. Virtually anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali silicates can also be used in agents which contain an active ingredient to be used according to the invention. In a further preferred embodiment of agents according to the invention a crystalline layered sodium silicate with a module of 2 to 3 is used, as can be produced 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 which contain an active ingredient 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 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 agents which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

In addition to the inorganic builder mentioned, further water-soluble or water-insoluble inorganic substances can be contained in the agents which contain an active ingredient to be used according to the invention, used together with this or used in the method according to the invention. In this context, the alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal sulfates and mixtures thereof are suitable. Such additional inorganic material can be present in amounts up to 70% by weight.

In addition, the agents can contain other constituents that are customary in detergents and cleaning agents. These optional components 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, up to 1 wt .-%, in particular 0.01 wt .-% to 0.5 wt .-% optical brighteners, in particular compounds from the class of the substituted 4,4 'are in agents which contain an active ingredient used according to the invention -Bis- (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for Contain heavy metals, in particular aminoalkylenephosphonic acids and their salts, and up to 2% by weight, in particular 0.1% by weight to 1% by weight, foam inhibitors, the stated proportions by weight referring to the total agent.

Solvents that can be used in particular with liquid agents are, in addition to water, preferably those that are water-miscible. These include the lower alcohols, for example ethanol, propanol, iso-propanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the cited classes of compounds. The active ingredients used according to the invention are generally dissolved or in suspended form in such liquid agents.

Any enzymes present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures of these. Primarily protease obtained from microorganisms such as bacteria or fungi comes into question. It can be obtained in a known manner from suitable microorganisms by fermentation processes. 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 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 of 6 to 9.5. Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®.

The customary enzyme stabilizers optionally present, 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, in particular behen soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which can also contain microfine, optionally silanized or otherwise hydrophobized silica. For use in particulate agents, foam inhibitors of this type are preferably bound to granular, water-soluble carrier substances.

In a preferred embodiment, an agent into which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight 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% by weight, in particular 2% by weight to 8% by weight % water-soluble organic builder, 10% by weight to 25% by weight synthetic anionic surfactant, 1% by weight to 5% by weight 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 hydrogen carbonate.

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 1% by weight to 25% by weight, in particular 5% by weight to 15% by weight nonionic surfactant, up to 10% by weight, in particular 0.5% by weight to 8% by weight synthetic anionic surfactant, 3% by weight to 15% by weight , in particular 5% by weight to 10% by weight soap, 0.5% by weight to 5% by weight, in particular 1% by weight to 4% by weight organic builder, in particular polycarboxylate such as citrate, up to 1.5% by weight, in particular 0.1% by weight to 1% by weight complexing agent for heavy metals, such as phosphonate, and in addition to any enzyme, enzyme stabilizer, color and / or fragrance contained, water and / or water-miscible solvent .

It is also possible to use a combination of a soil-releasing active ingredient, which is essential to the invention, with a soil-releasing polymer composed of a dicarboxylic acid and an optionally polymeric diol to enhance the cleaning performance of detergents when washing textiles. Such combinations with a particularly polyester-active soil-releasing polymer are also possible within the scope of the agents according to the invention and the method according to the invention.

The known polyester-active soil-releasing polymers that can be used in addition to the active ingredients 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 preferably used dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR ¹¹ -) _a OH, which is also known as a polymer Diol H- (O- (CHR ¹¹ -) _a ) _b OH may be present. Ph therein denotes 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. The polyesters obtainable from these preferably contain 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 in the polymer diol units is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil-releasing polyesters is in the range from 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol. The acid on which the remainder Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferred. If desired, instead of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be contained 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 has the value 2 and R ¹¹ is hydrogen and the alkyl radicals with 1 to 10, in particular 1 to 3 carbon atoms is selected. Among the last-mentioned 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 molar mass in the range from 1000 g / mol to 6000 g / mol.

If desired, these polyesters composed as described above can also be end-group-capped, with possible end groups being alkyl groups with 1 to 22 carbon atoms and esters of monocarboxylic acids. The end groups bonded via ester bonds 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, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, linroselic acid, eloearic acid, petroselic acid, linroselic acid, aresolic acid, petroselic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid . The end groups can also be based on hydroxymonocarboxylic acids with 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids can for their part be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, that is, their degree of oligomerization, is preferably in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used in combination with a combination with an active ingredient essential to the invention.

The polyester-active soil-releasing polymers are preferably water-soluble, the term "water-soluble" having 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 a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.

Preferred laundry aftertreatment agents which contain an active ingredient to be used according to the invention have a so-called esterquat, that is to say a quaternized ester of carboxylic acid and amino alcohol, as the fabric softening active ingredient. These are known substances that can be obtained by the relevant methods of preparative organic chemistry, for example by partially esterifying triethanolamine with fatty acids in the presence of hypophosphorous acid, 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 der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² und R³ unabhängig voneinander für Wasserstoff oder R¹CO, R⁴ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- beziehungsweise Palmfettsäuren sowie elaidinsäure-reiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin in der Regel im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugt eingesetzten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18-Talg-bzw. Palmfettsäure (lodzahl 0 bis 40) ab. Quaternierte Fettsäuretriethanolaminestersalze der Formel (IV), 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 preferred in the agents are quaternized fatty acid triethanolamine ester salts which follow the formula (IV),

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 esterquats that can be used for the purposes 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 arise, for example, from the pressure splitting of natural fats and oils. Technical C _12/18 coconut fatty acids and in particular partially hydrogenated C _16/18 tallow or palm fatty acids and elaidic acid-rich C _{16/18 fatty acid cuts 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 esterquats, a use ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The esterquats used with preference are technical mixtures of mono-, di- and triesters with one 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 (IV) in which R ^{1 is} 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 has been found to be particularly advantageous.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴ und R⁵ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized carboxylic acid triethanolamine ester salts, quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (V) are also suitable as 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 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, a further group of suitable ester quats are the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyldialkylamines of the formula (VI),

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 is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimum degree of esterification, the exemplary details given for (IV) also apply mutatis mutandis to the esterquats of the formulas (V) and (VI). The esterquats are usually sold in the form of 50 to 90 percent strength by weight alcoholic solutions, which can also be diluted with water without any problems, with ethanol, propanol and isopropanol being the usual alcoholic solvents.

Esterquats are preferably used in amounts of 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. If desired, the laundry aftertreatment agents used according to the invention can additionally contain the detergent ingredients listed above, provided they do not interact negatively with the ester quat in an unreasonable manner. It is preferably a liquid, water-containing agent.

Examples Example 1: Preparation of carboxymethylated poly (2-vinylpyridines)

To prepare the carboxymethylated poly (2-vinylpyridine) s, poly (2-vinylpyridine) was first prepared by means of free radical polymerization. To this end, 2 g of 4,4'-azobis (4-cyanovaleric acid) (V-501) were added to a solution of 100 g of freshly distilled 2-vinylpyridine in 100 ml of distilled ethanol and the reaction mixture was stirred at 70 ° C. for 26 hours. The solvent and excess monomer were then removed under reduced pressure and then dried at 70 ° C. in a high vacuum.

The intermediate product subsequently reacted had a number-weighted average molar mass of 23,700 g / mol, a dispersity of 1.9 (SEC, H ₂ O / 0.1% TFA / 0.1M NaCl, P2VP calibration) and a residual monomer content of eight Percent by weight.

For functionalization, the required amount of ethyl bromoacetate was added by syringe to solutions each of 20 g of the poly (2-vinylpyridine) synthesized as described in 200 ml of ethanol and the reaction mixtures were stirred at 50 ° C. for three days. When calculating the required amounts, it was assumed that the residual monomer had completely converted, which is why the amounts of ethyl bromoacetate used were above the desired degree of functionalization compared to the amount of polymer used. The following amounts of ethyl bromoacetate were used: P1: 5.40 ml; P2: 6.38 ml; P3: 9.32 ml; P4: 12.76 ml.

The solvent was then removed under reduced pressure and the polymers were then dried using a high vacuum pump.

In a last step, the ethyl functionality of the ester was removed by stirring a solution of the polymer obtained in each case in 200 ml to 250 ml concentrated hydrochloric acid for six days at 50.degree. The solvent was then removed under reduced pressure and the polymers obtained were dried in a high vacuum. The polymers were then dissolved in distilled water and dialyzed against water to remove impurities, salts and functionalized monomer; for this purpose, the aqueous solutions of the polymers were adjusted to a pH of approximately 6 in order to avoid damage to the membranes.

The polymers obtained had degrees of functionalization of 14% (P1), 25% (P2), 40% (P3) and 49% (P4).

Example 2: Medium

Table 1 shows the composition (ingredients in percent by weight, in each case based on the total agent) of the detergents M1, M2 and M3 according to the invention and of the agent V1 free of a corresponding active ingredient: Table 1: Compositions V1 V2 M1 M2 M3 M4 C _9-13 alkyl benzene sulfonic acid 8.3 8.3 8.3 8.3 8.3 8.3 Lauryl ether sulfate with 2 EO 3 3 3 3 3 3 C _12-18 fatty alcohol with 7 EO 6.3 6.3 6.3 6.3 6.3 6.3 C _12-18 fatty acid 1.5 1.5 1.5 1.5 1.5 1.5 NaOH 0.5 0.5 0.5 0.5 0.5 0.5 Monoethanolamine 3.3 3.3 3.3 3.3 3.3 3.3 Active ingredient P1 ^a) - - 1 - - - Active ingredient P2 ^a) - - - 1 - - Active ingredient P3 ^a) - - - - 1 - Active ingredient P4 ^a) - - - - - 1 Polymer ^b) - 1 - - - - Citric acid 2 2 2 2 2 2 Enzymes 1.5 1.5 1.5 1.5 1.5 1.5 water to 100 a) From example 1
b) Polymer of methacrylic acid trimethylammonium ethyl ester chloride and methacrylic acid methoxyoligoethoxyethyl ester, for comparison

Example 3: Soil release effect

Clean textiles made of cotton (for soiling A to C), polyester / cotton blends (for soiling D) or polyester (for soiling E and F) were washed in a Miele® W 1514 washing machine at 40 ° C with 17 l of water of 16 ° dH per wash cycle with the detergent V1 or V2 specified in Example 2 or with the detergents also specified there M1, M2, M3 or M5 in a dose of 50 ml each per wash cycle washed 3 times and then air-dried. This was followed by the application of standardized soiling (A: salad dressing; B: garden soil; C: blood; D: frying fat; E: lipstick; F: make-up; on the test textiles and aging of the soiling over 7 days. The textiles prepared in this way were underneath the above-mentioned conditions with a load of 3.5 kg (clean filling laundry plus test textiles) washed again with the respective detergent. The evaluation was carried out colorimetrically; Table 2 shows the mean values of the differences in the brightness values before and after washing from 5-fold Provisions specified. Table 2: Differences in brightness values Soiling / medium V1 V2 M1 M2 M3 M4 A. nb 64.6 69.9 70.4 67.1 68.6 B. nb 52.6 51.5 52.1 52.2 53.7 C. nb 31.2 31.4 32.7 32.2 32.1 D. 58.3 61.7 63.6 62.8 58.6 60.5 E. 22.2 29.2 28.9 27.1 23.4 25.1 F. 29.3 38.3 38.8 37.2 31.5 34.7 nb: not determined

Claims (10)

Use of 2-vinylpyridine polymers which contain units of the general formula I,

to strengthen the cleaning performance against soiling from detergents when washing textiles. Use according to Claim 1, characterized in that the textiles were washed and / or aftertreated in the presence of the active ingredient before they were provided with the soiling. Process for washing textiles, in which a detergent and a 2-vinylpyridine polymer which contains units of the general formula I,

come into use. Process according to Claim 3, characterized in that the concentration of the 2-vinylpyridine polymer used in the wash liquor is 0.0001 g / l to 1 g / l, in particular 0.001 g / l to 0.2 g / l. Process according to Claim 3 or 4, characterized in that it is carried out using a detergent containing the 2-vinylpyridine polymer. Process for washing textiles according to one of Claims 3 to 5, characterized in that it is carried out using a laundry aftertreatment agent, in particular fabric softener, containing the 2-vinylpyridine polymer. Detergent containing a 2-vinylpyridine polymer which contains units of the general formula I,

Agent according to Claim 7, characterized in that it contains the 2-vinylpyridine polymer in amounts of 0.01% by weight to 5% by weight, particularly preferably 0.02% by weight to 3% by weight . Use according to one of claims 1 to 2, method according to one of claims 3 to 6, or means according to claim 7 or 8, characterized in that in the 2-vinylpyridine polymer the ratio of the relative proportions of the two units, n: m, im The range is from 60:40 to 10:90, in particular from 50:50 to 20:80. Use, method or agent according to one of the preceding claims, characterized in that the number-average molecular weight of the 2-vinylpyridine polymer is in the range from 5,000 g / mol to 100,000 g / mol, in particular from 10,000 g / mol to 50,000 g / mol lies.