EP3320073B1 - Detergent power-improving polymer active ingredients - Google Patents

Description

The present invention relates to the use of certain terpolymers for enhancing the primary washing power of detergents or cleaning agents when washing textiles or cleaning hard surfaces against, in particular, bleach-sensitive or enzyme-sensitive stains, and washing and cleaning agents which contain such polymers.

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 the presence of which increases the detergency of surfactants without, as a rule, themselves having to exhibit pronounced surfactant behavior. The same applies to cleaning agents for hard surfaces. Such substances are often referred to as detergency boosters.

The use of poly (N-vinylpyrrolidone) in detergents is known. For example, describes the international patent application WO 2011/001173 A1 Liquid detergents containing 0.01 to 5% by weight of cellulase and 0.01 to 5% by weight of poly (N-vinylpyrrolidone) and / or its salt with an average molecular weight of 20,000 g / mol to 60,000 g / mol .

From the international patent application WO 97/29139 A1 crosslinked polymers of 10 to 50% by weight of N-vinylcaprolactam and 50 to 90% by weight of N-vinylpyrrolidone are known, which in the presence of 0.5 to 7% by weight of a crosslinker, which also generates 1- Vinyl-3 (E) -ethylidenepyrrolidone can be produced. Such crosslinked polymers are suitable for filtering out polyphenols from beer.

The soil release effect of N-vinylcaprolactam homopolymers and copolymers with minor amounts of other monomers such as, for example, N-vinylpyrrolidone is from the European patent application EP 0 181 204 A2 known. From the European patent application EP 0 181 205 A2 it is known that such polymers can also be applied as coating materials to fibers, in particular made of polyester, in order to achieve the soil release effect.

From the US patent application US 2002/0177542 detergents are known which contain a soil release effect exhibiting and fabric softening amount of N-vinylcaprolactam homopolymer with a K value of at least 40.

The international patent application WO 2004/014326 A1 describes shampoos containing anionic surfactants, silicone derivatives containing amino and hydroxyl groups and water-soluble cationic polymers with an average molecular weight of 100,000 g / mol to 2,000,000 g / mol and charge densities of 0.6 to 4 meq / g, including N-vinylpyrrolidone / alkylaminoacrylate / N-vinylcaprolactam copolymers and which are used there because of their conditioning effect. From the patent application DE 10 2012 024 440 A1 is the use of polymerization of N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylsuccinimide, N-vinylglutarimide, N-vinyl acetamide, N-alkyl-N-vinyl acetamide, N-vinyl formamide, N-alkyl-N-vinyl formamide and / or mixtures of at least 2 of these monomers accessible polymers for enhancing the primary washing power of detergents or cleaning agents when washing textiles or when cleaning hard surfaces against soiling are known. The European patent application EP 1 570 037 A1 relates to detergents that contain polymers with a vinyl pyrrolidone backbone and C _4-20 alkyl side chains. From the international patent application WO 2013/034437 A1 it is known that poly (N, N-dimethylacrylamide) and / or by copolymerization of N, N-dimethylacrylamide with a comonomer selected from acrylamide, methacrylamide, N, N-disubstituted acrylamide, N, N-disubstituted methacrylamide, N ' , N'-Disubstituted aminoalkyl methacrylamide, N, N-disubstituted aminoalkylacrylamide, N-acryloylmorpholine, N-acryloylpyrrolidine, N-acryloylpyrrolidone, N-acryloylpiperidone, N-acryloylcaprolactam, N-acryloylpyrrolidone, N-acryloylpyridone, N-methloylpyridyrolacryidine, N-methloylpyridyrolacryidine, N-methloylpyridyrolacryidin, N-acryloylpyridyrolacryidin, N-acryloylmorpholine, N-acryloylmorpholine, N-methloylpyridyrol N-methacryloylcaprolactam and their mixtures, accessible polymers, increase the primary washing power of detergents or cleaning agents.

That by polymerizing N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylsuccinimide, N-vinylglutarimide, N-vinyl acetamide, N-alkyl-N-vinyl acetamide, N-vinyl formamide, N-alkyl-N-vinyl formamide and / or Mixtures of at least 2 of these monomers of accessible polymers contribute to the primary washing power of detergents and cleaning agents is from the international patent application WO 2013/034438 known.

Surprisingly, it has been found that certain terpolymers of N-vinylpyrrolidone, N-vinylcaprolactam and a further ethylenically unsaturated monomer have particularly good properties which increase the primary detergency.

The invention relates to the use of N-vinylpyrrolidone, N-vinylcaprolactam and a further ethylenically unsaturated compound selected from optionally alkoxylated C ₁ -C ₂₄ -alkyl (meth) acrylate, polyalkylene glycol (meth) acrylate, N- Alkyl-substituted (meth) acrylamide, acrylonitrile and mixtures thereof for enhancing the primary washing power of detergents or cleaning agents when washing textiles or when cleaning hard surfaces against, in particular, bleach-sensitive or enzyme-sensitive soiling.

Among the other ethylenically unsaturated compounds present in addition to N-vinylpyrrolidone and N-vinylcaprolactam, polyalkylene glycol methacrylates and, among them, polyethylene glycol methacrylates are preferred, the degrees of polymerization, which can assume whole or fractional numerical values, in these compounds preferably in the range from greater than 1 to 60, in particular 2 to 60, lie. C ₁ -C ₂₄ -alkyl (meth) acrylates, in which the alkyl group can be linear or branched, are preferably selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, Octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate and mixtures of at least two of these, the presence of butyl methacrylate being particularly preferred. The compounds mentioned here as being preferred can be used alone or in mixtures.

The copolymers used according to the invention are preferably not crosslinked and, with the exception of groups which may arise from customary free radical initiator and / or free radical chain termination compounds, do not have any components derived from monomers other than those mentioned. They are preferably obtainable by copolymerizing 60% by weight to 98% by weight N-vinylpyrrolidone, 1% by weight to 39% by weight N-vinylcaprolactam and 1% by weight to 20% by weight of the above further ethylenically unsaturated compound, the percentages by weight here referring to the total amount of monomers present in the copolymerization.

The polymeric active ingredient preferably has an average molecular weight (here and below for average molecular weights: numerical average) in the range from 1000 g / mol to 500,000 g / mol, in particular from 1100 g / mol to 150,000 g / mol.

Another object of the invention is a method for removing, in particular, bleach-sensitive or enzyme-sensitive soiling from textiles or hard surfaces, in which a washing or cleaning agent and a named polymeric active ingredient are used. This method can be carried out manually or by machine, for example with the aid of a household washing machine or dishwasher. It is possible here to use the particularly liquid agent and the active ingredient simultaneously or in succession. Simultaneous use can be carried out particularly advantageously through the use of an agent which contains the active ingredient. Bleach-sensitive or enzyme-sensitive stains are understood as meaning those which can usually be at least partially removed by bleaching agents or with the aid of enzymes, such as, for example, stains from red wine or chocolate mousse.

The active ingredients used according to the invention can be prepared in a simple way by radical polymerization of the ethylenically unsaturated monomers. The polymerization can be carried out as a block copolymerization or as a random copolymerization. Preferably it is carried out as a random copolymerization. Alternatively, it can be carried out as a block copolymerization, in which N-vinylpyrrolidone oligomer blocks are first produced and the other monomers are polymerized onto them. The use of the copolymers obtainable from the monomers mentioned leads to a significantly better detachment of, in particular, bleach-sensitive or enzyme-sensitive soiling on hard surfaces and on textiles, including those made of cotton or with a percentage of cotton, than when using compounds previously known for this purpose the case is. Alternatively, significant amounts of surfactants can be saved while maintaining the same dirt-releasing properties. A further advantage of the copolymers used in accordance with the invention is that they can easily be incorporated in a stable manner into liquid water-containing detergents and cleaning agents without this leading to phase separations. The invention therefore also relates to detergents and cleaning agents, in particular liquid, water-containing washing and cleaning agents which contain a named copolymer.

The use according to the invention can take place in the context of a washing or cleaning process in such a way that the active ingredient is added to a detergent or cleaning agent-containing liquor or, preferably, the active ingredient is introduced into the liquor as a component of a washing or cleaning agent, the concentration of active ingredient in the liquor preferably is in the range from 0.01 g / l to 0.5 g / l, in particular from 0.02 g / l to 0.2 g / l.

Detergents or cleaning agents which contain an active ingredient to be used according to the invention or are used together with this or are used in the method according to the invention can contain all the usual other constituents of such agents which do not interact in an undesirable manner with the active ingredient essential to the invention. An above-defined polymeric active ingredient is preferably incorporated into washing or cleaning agents in amounts of 0.1% by weight to 10% by weight, in particular 0.2% by weight to 5% by weight.

Surprisingly, it has been found that such active ingredients have a positive effect on the effect of certain other detergent and cleaning agent ingredients and that, conversely, the effect of the active ingredient is additionally intensified by certain other ingredients. These effects occur in particular with bleaching agents, with enzymatic active ingredients, especially proteases and lipases, with water-soluble inorganic and / or organic builders, in particular based on oxidized carbohydrates or polymeric polycarboxylates and with synthetic anionic surfactants of the sulfate and sulfonate type, which is why the use of at least one of the further ingredients mentioned together with 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 method according to the invention can preferably be peroxygen-based bleaching agents, in particular in amounts in the range of 5% by weight up to 70% by weight, and optionally bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight. The bleaching agents which 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 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 comprises 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 anurylamides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl phenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. The bleach activators can be coated with coating substances and / or granulated in a known manner in order to avoid interaction with the per compounds during storage, whereby with the help of carboxymethyl cellulose, granulated tetraacetylethylenediamine with mean 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, in each case based on the total detergent.

In a preferred embodiment, an agent according to the invention or used within the scope of the use according to the invention contains synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular alkylbenzenesulfonate, fatty alkyl sulfate, fatty alkyl ether sulfate, alkyl and / or dialkyl sulfosuccinate, sulfofatty acid esters and / or sulfofatty acid disalts, in particular in an amount equal to Range from 2 wt% to 25 wt%. The anionic surfactant is preferably selected from the alkylbenzenesulfonates, 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.

Another embodiment of such agents comprises the presence of 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 from 2% by weight to 25% 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, especially the ethoxylates, of primary alcohols with linear, especially 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 glycose 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 has values between 1 and 10, in the case of the glycosides preferably used below a value of 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 in agents which contain an active ingredient used according to the invention or are used in the context of the use according to the invention, preferably in Amounts from 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight, with amounts in the upper part of this range more likely to be found in liquid detergents and particulate detergents preferably rather smaller amounts of contain 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, including, for example, the aforementioned 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. Preferred anionic surfactants are also the salts of sulfosuccinic acid esters, which are also referred to as alkyl sulfosuccinates or dialkyl sulfosuccinates, and the monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol radicals or mixtures of these. Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol residue which, considered in itself, represents a nonionic surfactant. Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred.

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 in liquid agents which contain an active ingredient used according to the invention, however, higher amounts of soap of generally up to 20% by weight can also be included.

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.

In a further embodiment, the agent contains water-soluble and / or water-insoluble builders, in particular selected from alkali aluminosilicate, crystalline alkali 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 are also accessible 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. In this case, the third monomeric unit is formed by vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ carboxylic acids, with vinyl alcohol are particularly preferred. Preferred terpolymers here contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and also 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 (Meth) acrylic acid and / or (meth) acrylate to maleic acid and / 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. 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 and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, up to 10% by weight 30% by weight, preferably 15% by weight to 25% by weight methallylsulfonic acid and / or methallylsulfonate and, as the third monomer, 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight % of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. 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 2000 g / mol and 50,000 g / mol and in particular 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 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 have no particles with a particle size greater than 30 μm and preferably consist of at least 80% by weight of particles with a size less than 10 μm. Your calcium binding capacity, according to the information in the German patent DE 24 12 837 can be determined is in the range of 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal 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 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®. Those with a molar ratio of Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 are preferably added as a solid and not in the form of a solution in the course of production. 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 module, 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. Crystalline sheet silicates that come under this general formula are, for example, in the European patent application EP 0 164 514 described. Preferred crystalline sheet silicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both ß- and δ-sodium disitics (Na ₂ Si ₂ O _{5 ·} yH ₂ O) are preferred. Virtually anhydrous crystalline alkali silicates of the abovementioned general formula, in which x is a number from 1.9 to 2.1, prepared 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, as can be produced from sand and soda, is used. 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 content of alkali metal silicates 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 process according to the invention. In this connection, 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 or 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% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of substituted 4,4 ', are in agents which contain an active ingredient used according to the invention -Bis- (2,4,6-tri-amino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0.1% by weight to 2% by weight Complexing agents for 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.

In a further preferred embodiment, an agent according to the invention is liquid and contains 1% by weight to 90% by weight, in particular 10% by weight to 85% by weight, preferably 25% by weight to 75% by weight, and particularly preferably 35% by weight to 65% by weight of water, water-miscible solvent or a mixture of water and water-miscible solvent. Water-miscible solvents include, for example, monohydric alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols and triols with 2 to 4 carbon atoms, in particular ethylene glycol, propylene glycol and glycerol, and mixtures thereof and the ethers derived from the named classes of compounds. Such water-miscible solvents are preferably present in the agents according to the invention in amounts not exceeding 30% by weight, in particular from 2% by weight to 20% by weight. In such liquid agents, the active ingredients used according to the invention are generally dissolved or in suspended form.

The enzymes preferably present are selected in particular from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures of these. Protease obtained from microorganisms, such as bacteria or fungi, is primarily considered. 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 that 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®. Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.

The customary enzyme stabilizers that may be present, especially in liquid agents, include amino alcohols, for example mono-, di-, triethanol and propanolamine and mixtures thereof, lower carboxylic acids, boric acid, 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, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

The known polyester-active, soil-releasing polymers that can be used together with 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 preferred use of 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 called polymeric 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 with 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ^{11 is} hydrogen, an alkyl radical with 1 to 22 carbon atoms and their mixtures, a is a number from 2 to 6 and b is 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. In the polymer diol units, the degree of polymerization b 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 molecular weight distribution of preferred soil-releasing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000 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 metal or ammonium salt. Among these are the Sodium and potassium salts are particularly preferred. If desired, 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 soil-releasing polyester instead of the HOOC-Ph-COOH monomer. 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, eloic acidic acid, petroselic acid, linoleumic acid, arsenicic 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 having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, 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 can thus be present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, that is to say 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 made from ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used in combination with an active ingredient essential to the invention.

The soil-releasing 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, 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.

The production of solid agents according to the invention does not present any difficulties and can be carried out in a known manner, for example by spray drying or granulation, enzymes and any other thermally sensitive ingredients such as bleaching agents being added later if necessary. For the production of agents according to the invention with increased bulk density, in particular in the range from 650 g / l to 950 g / l, a method having an extrusion step is preferred.

To produce agents according to the invention in tablet form, which can be single-phase or multi-phase, single-colored or multi-colored and in particular consist of one layer or several, in particular two layers, the procedure is preferably such that all constituents - optionally one layer each - are in one Mixers are mixed with one another and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing forces in the range from about 50 to 100 kN, preferably at 60 to 70 kN. In the case of multilayer tablets in particular, it can be advantageous if at least one layer is pre-pressed. This is preferably carried out at press forces between 5 and 20 kN, in particular at 10 to 15 kN. In this way, unbreakable tablets which dissolve sufficiently quickly under the conditions of use and have breaking and flexural strengths of normally 100 to 200 N, but preferably more than 150 N, are obtained without any problems up to 40 g. The three-dimensional shape of the tablets is arbitrary and can be round, oval or angular, with intermediate shapes also being possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of angular or cuboid tablets, which are introduced predominantly via the dosing device, for example the dishwasher, depends on the geometry and the volume of this dosing device. Exemplary preferred embodiments have a base area of (20 to 30 mm) × (34 to 40 mm), in particular of 26 × 36 mm or of 24 × 38 mm.

Liquid or pasty agents according to the invention in the form of solutions containing customary solvents, in particular water, are generally produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

In a 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 15% by weight, in particular 2% by weight to 10% by weight nonionic surfactant, 2% by weight. -% to 30 wt .-%, in particular 5 wt .-% to 20 wt .-% synthetic anionic surfactant, up to 15 wt .-%, in particular 2 wt .-% to 12.5 wt .-% 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 up 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.

In a further 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 of bleach, in particular alkali percarbonate, up to 15% by weight %, in particular 1% by weight to 10% by weight bleach activator, 20% by weight to 55% by weight inorganic builder, up to 10% by weight, in particular 2% by weight to 8% by weight. -% water-soluble organic builder, 10 wt .-% to 25 wt .-% synthetic anionic surfactant, 1 wt .-% to 5 wt .-% nonionic surfactant and up to 25 wt .-%, in particular 0.1 wt .-% up to 25% by weight of inorganic salts, in particular alkali metal carbonate and / or hydrogen carbonate.

Examples Example 1: Production of Polymers A: Production of the terpolymer NVP / NVCap / PEGMA (85: 5: 10) (polymer A)

382 mg of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (AAPH) and 18.55 g of N-vinylpyrrolidone (NVP) were dissolved in 167 ml of water. The solution was degassed and heated to 70 ° C. in a nitrogen atmosphere with stirring. After 30 minutes, a mixture of 3.44 g of AAPH, 37.8 g of NVP, 4.09 g of N-vinylcaprolactam (NVCap) and 17.7 g of polyethylene glycol methacrylate (300 g / mol, PEGMA) in 185 ml of water was inside of 1 hour was added and the reaction mixture was stirred at 70 ° C. for a further 3 hours. The terpolymer formed was precipitated by adding tetrahydrofuran (THF). 75 g of polymer A were obtained (M _w 73760 g / mol, measured by GPC using the Ready-Cal Kit® polystyrene standards; the polydispersity index (PDI) with PDI = M _w / M _n , M _{w being} the weight-average molecular weight and M _{n being} the number average molecular weight was 2.2).

B: Production of the terpolymer NVP / NVCap / PEGMA (90: 5: 5) (polymer B)

382 mg of AAPH and 21.32 g of NVP were dissolved in 167 ml of water. The solution was degassed and heated to 70 ° C. in a nitrogen atmosphere with stirring. After 30 minutes, a mixture of 3.44 g of AAPH, 43.28 g of NVP, 4.28 g of NVCap and 9.2 g of PEGMA in 185 ml of water was added over the course of 1 hour and the reaction mixture was kept at 70 ° C. for 3 hours further stirred. The terpolymer formed was precipitated by adding THF. 75 g of polymer B were obtained (M _w 53189 g / mol, PDI 2.2).

C: Production of the terpolymer NVP / NVCap / BuMA (90: 5: 5) (polymer C)

1.53 g of 2,2'-azobis (2-methylpropionitrile) (AIBN), 7.23 g of NVP, 510 mg of NVCap and 521 mg of butyl methacrylate (BuMA) were dissolved in 23 ml of 1-methoxy-2-propanol (MPG) . The solution was degassed, placed under a nitrogen atmosphere and the temperature was increased to 75 ° C. A mixture of 1.53 g of AIBN, 65.05 g of NVP, 4.58 g of NVCap and 4.69 g of BuMA in 208 ml of MPG was then added over the course of 2 hours and the reaction mixture was kept at 75 ° C. for a further 3 hours touched. The terpolymer formed was precipitated by adding tert-butyl methyl ether (TBME). 83 g of polymer C were obtained (M _w 31982 g / mol, PDI 1.7).

D: Production of the terpolymer NVP / NVCap / BuMA (85: 5: 10) (polymer D)

1.54 g AIBN, 6.83 g NVP, 509 mg NVCap and 1.04 g BuMA were dissolved in 217 ml MPG. The solution was degassed, placed under a nitrogen atmosphere and the temperature was increased to 75 ° C. Then a mixture of 1.54 g of AIBN, 61.43 g of NVP, 4.58 g of NVCap and 9.32 g of BuMA in 217 ml of MPG was added over the course of 2 hours and the reaction mixture was kept at 75 ° C. for a further 3 hours touched. The terpolymer formed was precipitated by adding TBME. 83 g of polymer D were obtained (M _w 38352 g / mol, PDI 1.9).

Example 2: washing trials

The performance of the polymers produced in Example 1 was tested in washing tests at a washing temperature of 20 ° C. under European conditions (16 ° dH) in Miele washing machines. The polymers were each incorporated in amounts of 2% by weight, based on the detergent, into a commercially available liquid detergent and this was then used in the washing of textiles provided with 111 standardized soils. For comparison, the liquid detergent free of the respective polymers was also used under the same conditions. The agent with polymer A showed a significantly better washing performance on 14 of the soils compared to the liquid detergent free from the polymer, the agent with polymer B on 23 soils, the agent with polymer C on 22 soils, and the agent with polymer C on 21 Soiling.

Claims (10)

1. The use of polymers obtained by copolymerization of N-vinylpyrrolidone, N-vinylcaprolactam and an additional ethylenically unsaturated compound selected from optionally alkoxylated C₁-C₂₄ alkyl (meth)acrylate, polyalkylene glycol (meth)acrylate, N-alkyl-substituted (meth)acrylamide, acrylonitrile and mixtures thereof for enhancing the primary detergency of washing or cleaning agents when washing textiles or when cleaning hard surfaces of stains.
2. The use according to claim 1, characterized in that the stains are bleach-sensitive or enzyme-sensitive stains.
3. The use according to claim 1 or 2, characterized in that the additional ethylenically unsaturated compound is selected from polyalkylene glycol methacrylates, in particular polyethylene glycol methacrylates, C₁-C₂₄ alkyl (meth)acrylates, in which the alkyl group can be linear or branched, in particular methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, alone or in mixtures.
4. The use according to one of claims 1 to 3, characterized in that the polymer can be obtained by copolymerization of from 60 wt.% to 98 wt.% N-vinylpyrrolidone, from 1 wt.% to 39 wt.% N-vinylcaprolactam and from 1 wt.% to 20 wt.% of the additional ethylenically unsaturated compound, the percentages by weight relating to the total amount of monomers present in the copolymerization.
5. The use according to one of claims 1 to 4, characterized in that the polymer has an average molecular weight in the range of from 1000 g/mol to 500,000 g/mol, in particular from 1100 g/mol to 150,000 g/mol.
6. The use according to one of claims 1 to 5, characterized in that the polymer is added to a liquor containing a washing or cleaning agent or is introduced into the liquor as a component of a washing or cleaning agent.
7. A method for removing in particular bleach-sensitive or enzyme-sensitive stains from textiles or hard surfaces, in which method a washing or cleaning agent and a polymer, which can be obtained by copolymerization of N-vinylpyrrolidone, N-vinylcaprolactam and an additional ethylenically unsaturated compound, selected from optionally alkoxylated C₁-C₂₄ alkyl (meth)acrylate, polyalkylene glycol (meth)acrylate, N-alkyl-substituted (meth)acrylamide, acrylonitrile and mixtures thereof, are used.
8. A washing or cleaning agent containing a polymer which can be obtained by copolymerization of N-vinylpyrrolidone, N-vinylcaprolactam and an additional ethylenically unsaturated compound, selected from optionally alkoxylated C₁-C₂₄ alkyl (meth)acrylate, polyalkylene glycol (meth)acrylate, N-alkyl-substituted (meth)acrylamide, acrylonitrile and mixtures thereof.
9. The agent according to claim 8, characterized in that it contains the polymer in amounts of from 0.1 wt.% to 10 wt.%, in particular from 0.2 wt.% to 5 wt.%.
10. The agent according to claim 8 or 9, characterized in that it is liquid and contains from 1 wt.% to 90 wt.%, in particular from 10 wt.% to 85 wt.%, water, water-miscible solvent, or a mixture of water and water-miscible solvent.