Polymeric soil release agents

Abstract

The aim of the invention is to improve the cleaning performance of detergents during the laundering of textiles. This is achieved essentially by the use of copolymers obtainable by radical polymerisation of cyclic ketene acetals with acrylic and / or vinyl monomers which are at least proportionately ammonium-substituted.

Description

[0001] The present invention relates to the use of certain copolymers of ketene derivatives and monoethylene unsaturated comonomers to enhance the cleaning performance of detergents when washing textiles.

[0002] In addition to essential ingredients for the washing process, such as surfactants and builders, detergents typically contain other components collectively known as washing aids. These include diverse groups of active ingredients such as foam regulators, anti-graying agents, bleaching agents, bleach activators, and color transfer inhibitors. Such aids also include substances that impart dirt-repellent properties to the fabric fibers and, if present during the washing process, enhance the dirt-removing capacity of the other detergent components. The same principle applies to cleaning agents for hard surfaces. These dirt-removing substances are often referred to as "soil release" agents or, because of their ability to make the treated surface, such as the fiber, dirt-repellent, as "soil repellents."For example, the dirt-removing effect of methylcellulose is known from US patent US 4,136,038. European patent application EP 0 213 729 discloses the reduced redeposition when using detergents containing a combination of soap and a nonionic surfactant with alkyl hydroxyalkyl cellulose. European patent application EP 0 213 730 discloses textile treatment agents containing cationic surfactants and nonionic cellulose ethers with HLB values ​​of 3.1 to 3.8. US patent 4,000,093 discloses detergents containing 0.1 wt.% to 3 wt.% alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and 5 wt.% to 50 wt.% surfactant, wherein the surfactant component consists substantially of C 10 to C 13 alkyl sulfate and includes up to 5 wt.% C 14 alkyl sulfate and less than 5 wt.% alkyl sulfate with alkyl groups of C 15 and higher.However, it has been observed in individual cases that the effect of such cellulose derivatives in water-based liquid detergents may diminish, especially after prolonged storage under unfavorable conditions.

[0003] Due to their chemical similarity to polyester fibers, copolyesters containing 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 are particularly effective dirt-removing agents in textiles made from this material. Dirt-removing copolyesters of this type, as well as their use in detergents, have been known for a long time. The reaction of 2-methylene-4-phenyl-1,3-dioxolane with methacrylic acid esters is described in V. Delplace, E. Guégain, S. Harrisson, D. Gigmes, Y. Guillaneuf, J. Nicolas, Chem. Commun., 2015, 51, 12847-12850. Patent application WO 2012 / 120138 A1 discloses polymers cross-linked by bioresorbable cross-linkers from α,β-unsaturated carboxylic acid esters or amides and cyclic ketene acetals. Copolymers of vinylpyrrolidone and 2-methylene-1,3-dioxepane are known from patent US 5,912,312.Patent applications DE 10 2008 018 905 A1 and DE 10 2008 028 146 A1 disclose copolymers of cyclic ketene acetals and up to two different methacrylic acid derivatives. Patent application DE 39 27 811 A1 discloses copolymers of at least 12 wt.% mono- or polyunsaturated carboxylic anhydrides and radically ring-opening cyclic ketene derivatives.

[0004] Surprisingly, polymers accessible from ketene derivatives and monoethylene unsaturated comonomers bearing an ammonium substituent were found to have a dirt-removing effect.

[0005] The invention relates to the use of copolymers obtainable by radical polymerization of cyclic ketene acetals with acrylic and / or vinyl monomers, which are at least partially ammonium-substituted, to enhance the cleaning performance of detergents when washing textiles.

[0006] In the radical polymerization of cyclic ketene acetals, the acetal ring opens, giving rise to ester functionalities that can improve the biodegradability of the resulting polymer. This improved biodegradability is considered a further advantage of the invention.

[0007] Preferably, the copolymers used according to the invention are composed of 5 mol% to 50 mol%, in particular 35 mol% to 15 mol%, of at least one cyclic ketene acetal monomer and 50 mol% to 95 mol%, in particular 65 mol% to 85 mol%, of at least one acrylic or vinyl monomer, which bears at least a portion of an ammonium substituent. Apart from components originating from radical initiators or radical terminators, the copolymers preferably contain no components derived from other monomers. The copolymers preferably exist as a statistically determined structure, but can also contain a gradient or be structured as block copolymers.

[0008] The ketene acetal is preferably selected from 2-methylene-1,3-dioxolane, 2-methylene-1,3-dioxane, 2-methylene-1,3-dioxepane, which may optionally be substituted in the acetal ring, such as 4,5,-Di-C 1-12-alkyl-2-methylene-1,3-dioxolane, 4-C 1-12-alkyl-2-methylene-1,3-dioxolane, 5-C 1-12-alkyl-2-methylene-1,3-dioxepane, 5,6-Di-C 1-12-alkyl-2-methylene-1,3-dioxepane, 4-C 1-12-alkyl-2-methylene-1,3-dioxane, 4,6-Di-C 1-12-alkyl-2-methylene-1,3-dioxolane and 5,6-Benzo-2-methylene-1,3-dioxepane, 4-Phenyl-2-methylene-1,3-dioxolane, 4,5-Di-phenyl-2-methylene-1,3-dioxolane, 4-Phenyl-2-methylene-1,3-dioxane, 4,6-Di-phenyl-2-methylene-1,3-dioxolane, 4-Phenyl-2-methylene-1,3-dioxepane, 4,7-Di-phenyl-2-methylene-1,3-dioxepane and their mixtures.

[0009] The acrylic or vinyl monomer is preferably selected from acrylic esters, acrylic amides, methacrylic esters, methacrylamides, vinylimidazole, vinylpyrolidone, and mixtures thereof, with 2-(dimethylamino)alkyl methacrylate, polypropylene glycol methacrylate, alkyl methacrylate, methacrylamide, N-methyl methacrylamide, and mixtures thereof being particularly suitable. It is especially selected from 2-(dimethylamino)ethyl methacrylate (DMAEMA) and methyl polyethylene glycol methacrylate (MPEGMA) and mixtures thereof. The required proportion of ammonium-substituted acrylic monomers can be achieved, for example, by using trialkylammonium alkyl (meth)acrylates.

[0010] The monomers mentioned can be polymerized according to the above-cited literature-based procedures or in analogy to them.

[0011] Another aspect of the invention is a method for washing textiles, in which a detergent and a soil-removing agent in the form of a copolymer as defined above are used. This process can be carried out manually or, optionally, with the aid of a conventional household washing machine. It is possible to apply the detergent and the soil-removing agent simultaneously or sequentially. Simultaneous application is particularly advantageous when using a detergent that contains the soil-removing agent.The process essentially consists of bringing a textile in need of cleaning, or at least the soiled part of its surface, into contact with an aqueous preparation containing the copolymer defined above, allowing the aqueous preparation to act on the textile, or at least the soiled part of its surface, for a certain period of time, and removing the aqueous preparation, for example by rinsing the textile with water.

[0012] The effect of the active ingredient used according to the invention is particularly pronounced with repeated application, that is, especially for removing soiling from textiles that had already been washed and / or post-treated in the presence of the active ingredient before becoming soiled. In connection with post-treatment, it should be noted that the aforementioned positive aspect can also be achieved through a washing process in which, after the actual washing process, which is carried out using a detergent that may contain the aforementioned active ingredient but in this case may also be free of it, the textile is brought into contact with a post-treatment agent, for example, as part of a fabric softener step, which contains the active ingredient used according to the invention, in the presence of water.Even with this procedure, the washing-performance-enhancing effect of the active ingredients used according to the invention occurs in the next washing process, even if, if desired, a detergent without an active ingredient used according to the invention is used again. This effect is significantly higher than that resulting from the use of a conventional soil-release active ingredient. In a particularly preferred embodiment, the active ingredient essential to the invention is added during the fabric softening cycle of the textile washing process, particularly in machine washing.

[0013] The active ingredient used according to the invention leads to a significantly better removal of, in particular, grease and cosmetic soiling from textiles, especially those made of cotton or cotton-containing fabrics, than is the case when using compounds previously known for this purpose. Alternatively, significant quantities of surfactants can be saved while maintaining the same grease-removing capacity.

[0014] Furthermore, it was observed that in the presence of the copolymers essential to the invention during the washing process, less dirt already removed from the textile is redeposited onto the cleaned textile, so that textiles washed in the presence of a copolymer essential to the invention gray significantly less than those washed in its absence. A further object of the invention is therefore the use of the copolymers defined above to reduce the graying of textiles, in particular textiles made of or containing cotton, during washing.

[0015] The uses according to the invention can be carried out in the context of a washing process by adding the dirt-removing active ingredient to a liquor containing detergent or preferably by introducing the active ingredient as a component of a detergent into the liquor that contains the object to be cleaned or that is brought into contact with it.

[0016] The use according to the invention within the framework of a laundry after-treatment process can be carried out by adding the soil-removing active ingredient separately to the rinsing solution, which is used after the washing cycle with the application of a detergent, or by introducing it as a component of the laundry after-treatment agent, in particular a fabric softener. In this aspect of the invention, the detergent used before the laundry after-treatment agent can also contain an active ingredient to be used according to the invention, but can also be free of it.

[0017] Further objects of the invention are therefore detergents and laundry after-treatment agents containing copolymers defined above and a surfactant.

[0018] 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 further preferably carried out at a pH value of 6 to 11, particularly preferably at a pH value of 7.5 to 9.5. The concentration of the copolymer in the washing liquor is preferably 0.0001 g / l to 1 g / l, particularly 0.001 g / l to 0.2 g / l.

[0019] Detergents containing, or used in conjunction with, an active ingredient according to the invention in the form of the copolymer mentioned above, or employed in processes according to the invention, may contain all other usual components of such agents that do not interact undesirably with the active ingredient essential to the invention, but must contain at least one surfactant. Preferably, the active ingredient defined above is used in amounts of 0.01 wt.% to 10 wt.%, particularly preferably from 0.1 wt.% to 3 wt.%, wherein these and the following quantities refer to the entire agent unless otherwise specified. Preferably, an agent according to the invention, or used in the process according to the invention, or used within the scope of the use according to the invention, is aqueous and liquid; it contains, in particular, 2 wt.% to 92 wt.%, and more preferably, 3 wt.% to 85 wt.% water.

[0020] Surprisingly, it was found that the active ingredient used according to the invention positively influences the effect of certain other detergent ingredients and that, conversely, the effect of the soil release active ingredient is further enhanced by certain other detergent ingredients. These effects occur particularly with bleaching agents, enzymatic active ingredients, especially proteases and lipases, water-soluble inorganic and / or organic builders, especially those based on oxidized carbohydrates or polymeric polycarboxylates, synthetic anionic surfactants of the sulfate and sulfonate type, and dye transfer inhibitors, for example, vinylpyrrolidone, vinylpyridine, or vinylimidazole polymers or copolymers, or corresponding polybetaines. Therefore, the use of at least one of the aforementioned additional ingredients together with the active ingredient used according to the invention is preferred.

[0021] An agent containing, or used in conjunction with, an active ingredient according to the invention, or employed in the process according to the invention, preferably contains peroxygen-based bleaching agents, particularly in amounts ranging from 3% to 70% by weight, and optionally bleach activator, particularly in amounts ranging from 0.5% to 10% by weight. However, in another preferred embodiment, it may also be free of bleaching agents and bleach activator. The bleaching agents considered are preferably peroxygen compounds typically used in detergents, such as percarboxylic acids, for example, dodecanediperic acid or phthaloylaminoperoxicapronic acid, hydrogen peroxide, alkali perborate (which may be present as a tetrahydrate or monohydrate), percarbonate, perpyrophosphate, and persilicate, which are typically present as alkali salts, particularly sodium salts.Such bleaching agents are present in detergents containing an active ingredient used according to the invention, preferably in amounts up to 25 wt.%, particularly up to 15 wt.%, and most preferably from 3 wt.% to 15 wt.%, in each case based on the total product, with percarbonate being particularly used. The optionally present component of the bleaching activators comprises the commonly used N- or O-acyl compounds, for example, multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, and cyanurates, as well as carboxylic anhydrides, in particular phthalic anhydride, carboxylic esters, in particular sodium isononanoylphenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts.To prevent interaction with peroxygen compounds during storage, the bleaching activators can be coated or granulated in a known manner, with tetraacetylethylenediamine granulated with carboxymethylcellulose, 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 in particle form being particularly preferred. Such bleaching activators are preferably present in detergents in amounts up to 8 wt.%, and in particular from 0.5 wt.% to 6 wt.%, based on the total product.

[0022] In a preferred embodiment, an agent used in the invention or employed in the process according to the invention contains a non-ionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides, as well as mixtures thereof, in particular in an amount in the range of 2 wt.% to 25 wt.%.

[0023] 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, sulfofatty acid esters, and / or sulfofatty acid disalts, especially in an amount in the range of 2 wt.% to 25 wt.%. Preferably, the anionic surfactant is 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 single substances, but rather cuts or mixtures. Among these, those whose proportion of compounds with longer-chain residues in the range of 16 to 18 carbon atoms exceeds 20 wt.% are preferred.

[0024] Suitable nonionic surfactants include alkoxylates, in particular ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols with 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. Derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, especially so-called oxo alcohols, can also be used to produce usable alkoxylates. Accordingly, alkoxylates, especially ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl, or octadecyl, residues, as well as mixtures thereof, are suitable.Furthermore, corresponding alkoxylation products of alkylamines, vicinal diols, and carboxylic acid amides, which correspond to the aforementioned alcohols with respect to the alkyl moiety, can be used. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and fatty acid polyhydroxyamides are suitable. Suitable alkyl polyglycosides for incorporation into the compositions according to the invention are compounds of the general formula (G) n -OR 12< , in which R 12< represents an alkyl or alkenyl group with 8 to 22 carbon atoms, G a glucose unit, and n a number between 1 and 10. The glycoside component (G) n consists of oligo- or polymers of naturally occurring aldose or ketose monomers, including in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose and lyxose.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, as a quantity to be determined analytically, generally takes on fractional values; it lies between 1 and 10, and for the preferably used glycosides, below a value of 1.5, particularly between 1.2 and 1.4. Glucose is the preferred monomer building block due to its good availability. The alkyl or alkenyl moiety R12 of the glycosides is preferably also derived from readily available derivatives of renewable raw materials, especially fatty alcohols, although their branched-chain isomers, particularly so-called oxo alcohols, can also be used to produce usable glycosides.Suitable, therefore, are in particular the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl, or octadecyl groups, as well as mixtures thereof. Particularly preferred alkyl glycosides contain a coconut fatty acid alkyl group, that is, mixtures with essentially R12 = dodecyl and R12 = tetradecyl.

[0025] Non-ionic surfactant is used in compositions containing a soil release agent used according to the invention, or is used in the process according to the invention, preferably in amounts of 1 wt.% to 30 wt.%, in particular from 1 wt.% to 25 wt.%, wherein amounts in the upper part of this range are more likely to be found in liquid detergents and particulate detergents preferably contain lower amounts of up to 5 wt.%.

[0026] The compositions may contain, instead of or in addition to, further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as alkylbenzenesulfonates, in amounts preferably not exceeding 20% ​​by weight, and in particular from 0.1% by weight to 18% by weight, in each case based on the total composition. Particularly suitable synthetic anionic surfactants for use in such compositions are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms, which bear an alkali, ammonium, or alkyl or hydroxyalkyl-substituted ammonium ion as a countercation. Derivatives of fatty alcohols with, in particular, 12 to 18 carbon atoms and their branched-chain analogues, the so-called oxo alcohols, are preferred.Alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium, or alkyl / hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the aforementioned alcohols, so-called ether sulfates. Preferably, such ether sulfates 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 the sulfonation products derived from fatty acids with 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols with 1 to 6 C atoms, preferably 1 to 4 C atoms, as well as the sulfofatty acids obtained from these by formal saponification.

[0027] Soaps are also considered as optional surfactant ingredients, including saturated fatty acid soaps such as the salts of lauric, myristic, palmitic, or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example, coconut, palm kernel, or tallow fatty acids. Soap mixtures are particularly preferred that consist of 50 wt.% to 100 wt.% saturated C12-C18 fatty acid soaps and up to 50 wt.% oleic acid soap. Preferably, soap is present in amounts of 0.1 wt.% to 5 wt.%. However, especially in liquid compositions containing a polymer used according to the invention, higher amounts of soap, generally up to 20 wt.%, may also be present.

[0028] Optionally, the composition may also contain betaines and / or cationic surfactants, which – if present – ​​are preferably used in amounts of 0.5 wt.% to 7 wt.%. Among these, the esterquats discussed below are particularly preferred.

[0029] In a further embodiment, the agent contains water-soluble and / or water-insoluble builder, in particular selected from alkali aluminosilicate, crystalline alkali silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range of 2.5 wt.% to 60 wt.%.

[0030] The composition preferably contains 20 wt.% to 55 wt.% 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, especially citric acid and sugar acids, as well as polymeric (poly)carboxylic acids, especially polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids, and copolymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, and 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 free acid.A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular mass of 50,000 g / mol to 100,000 g / mol. Suitable, though 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 content is at least 50 wt.%. Terpolymers containing two carboxylic acids and / or their salts as monomers, and a 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 monoethylene-unsaturated C3-C8 carboxylic acid and preferably from a C3-C4 monocarboxylic acid, in particular (meth)acrylic acid.The second acidic monomer or its salt can be a derivative of a C4-C8 dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case by vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives are particularly preferred, which are esters of short-chain carboxylic acids, for example, of C1-C4 carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60 wt.% to 95 wt.%, in particular 70 wt.% to 90 wt.% (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate, as well as 5 wt.% to 40 wt.%, preferably 10 wt.% to 30 wt.% vinyl alcohol and / or vinyl acetate.Particularly preferred are 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 especially between 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 substituted at the 2-position with an alkyl group, preferably a C1-C4 alkyl group, or an aromatic group, preferably derived from benzene or benzene derivatives. Preferred terpolymers contain 40 wt.% to 60 wt.%, in particular 45 wt.% to 55 wt.% (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, 10 wt.% to 30 wt.%, preferably 15 wt.% to 25 wt.% methallylsulfonic acid or methallylsulfonate and as a third monomer 15 wt.% to 40 wt.%.-%, preferably 20 wt.% to 40 wt.% of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo-, or polysaccharide, with mono-, di-, or oligosaccharides being preferred, and sucrose being particularly preferred. The use of the third monomer presumably introduces predetermined breaking points into the polymer, which are responsible for the polymer's good biodegradability. These terpolymers generally have a relative molecular mass between 1000 g / mol and 200,000 g / mol, preferably between 3000 g / mol and 10,000 g / mol. They can be used, particularly for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 wt.% aqueous solutions. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, especially their alkali salts.

[0031] Such organic builder substances are preferably present in amounts up to 40 wt.%, particularly up to 25 wt.%, and most preferably from 1 wt.% to 5 wt.%. Amounts close to the aforementioned upper limit are preferably used in paste-like or liquid, particularly aqueous, agents.

[0032] Water-insoluble, water-dispersible inorganic builder materials, particularly crystalline or amorphous alkali aluminosilicates, are used in amounts of up to 50 wt.%, preferably not exceeding 40 wt.%, and in liquid form, particularly from 1 wt.% to 5 wt.%. Among these, crystalline aluminosilicates of detergent quality, especially zeolite NaA and optionally NaX, are preferred. Amounts close to the aforementioned upper limit are preferably used in solid, particulate form. Suitable aluminosilicates, in particular, do not contain particles with a grain size exceeding 30 mm and preferably consist of at least 80 wt.% of particles with a size of less than 10 mm. Their calcium binding capacity, which can be determined according to the specifications of German patent DE 24 12 837, is in the range of 100 to 200 mg CaO per gram.Suitable substitutes or partial substitutes for the aforementioned aluminosilicate are crystalline alkali silicates, which can be present alone or in mixtures with amorphous silicates. The alkali silicates suitable as framework materials in the composition preferably have a molar ratio of alkali oxide to SiO₂ below 0.95, particularly from 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are sodium silicates, especially amorphous sodium silicates, with a molar ratio of Na₂O:SiO₂ of 1:2 to 1:2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. During production, they are preferably added as a solid rather than in solution.As crystalline silicates, which can be present alone or in a mixture with amorphous silicates, preferably crystalline layered silicates of the general formula Na₂Si₆XO₆2x+1·yH₂O are used, where x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20, with preferred values ​​for x being 2, 3, or 4. Preferred crystalline layered silicates are those in which x in the aforementioned general formula takes the values ​​2 or 3. In particular, both β- and δ-sodium disilicates (Na₂Si₂O₅·yH₂O) are preferred. Practically anhydrous crystalline alkali silicates of the above-mentioned general formula, in which x is a number from 1.9 to 2.1, prepared from amorphous alkali silicates, can also be used in compositions containing an active ingredient to be used according to the invention.In a further preferred embodiment of the composition according to the invention, a crystalline sodium layered silicate with a modulus of 2 to 3 is used, such as can be produced from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention. Their alkali silicate content is preferably 1 wt.% to 50 wt.% and particularly 5 wt.% to 35 wt.%, based on anhydrous active substance. If alkali aluminosilicate, in particular zeolite, is also present as an additional building block, the alkali silicate content is preferably 1 wt.% to 15 wt.% and particularly 2 wt.% to 9 wt.%, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4:1 to 10:1.In compositions containing 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 particularly 1:1 to 2:1.

[0033] In addition to the aforementioned inorganic builder, further water-soluble or water-insoluble inorganic substances may be contained in the compositions, used together with an active ingredient according to the invention, or employed in processes according to the invention. Suitable substances in this context are alkali carbonates, alkali hydrogen carbonates, and alkali sulfates, as well as mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.

[0034] In addition, the products may contain other ingredients commonly found in detergents and cleaning agents. These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals (e.g., aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids), foam inhibitors (e.g., organopolysiloxanes or paraffins), solvents, and optical brighteners (e.g., stilbene disulfonic acid derivatives). Preferably, compositions containing an active ingredient used according to the invention contain up to 1 wt.%, in particular 0.01 wt.% to 0.5 wt.% optical brighteners, in particular compounds from the class of substituted 4,4'-bis-(2,4,6-triamino-s-triazinyl)-stilbene-2,2'-disulfonic acids, up to 5 wt.%, in particular 0.1 wt.% to 2 wt.% complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts, and up to 2 wt.%, in particular 0.1 wt.% to 1 wt.%, are present.-% contain foam inhibitors, with the stated weight percentages referring to the entire product.

[0035] Solvents that can be used, particularly with liquid preparations, are preferably those that are water-miscible, in addition to water. These include lower alcohols, for example ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers derived from the aforementioned classes of compounds. In such liquid preparations, the active ingredients used according to the invention are generally present in dissolved or suspended form.

[0036] Any enzymes present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, or mixtures thereof. Protease derived from microorganisms such as bacteria or fungi is the primary candidate. It can be obtained from suitable microorganisms through fermentation processes using known methods. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym®, or Maxapem®. The lipase used can be obtained, for example, from Humicola lanuginosa, Bacillus species, Pseudomonas species, Fusarium species, Rhizopus species, or Aspergillus species. Suitable lipases are commercially available under names such as Lipolase ®< , Lipozym ®< , Lipomax ®< , Lipex ®< , Amano ®< -Lipase, Toyo-Jozo ®< -Lipase, Meito ®< -Lipase and Diosynth ®< -Lipase.Suitable amylases are commercially available under names such as Maxamyl®, Termamyl®, Duramyl®, and Purafect® OxAm. The cellulase used can be an enzyme derived from bacteria or fungi, exhibiting an optimum pH preferably in the slightly acidic to slightly alkaline range of 6 to 9.5. Such cellulases are commercially available under names such as Celluzyme®, Carezyme®, and Ecostone®.

[0037] Common enzyme stabilizers that may be present, particularly in liquid products, include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and their mixtures, lower carboxylic acids, boric acid or alkali borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example calcium-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.

[0038] Suitable foam inhibitors include long-chain soaps, in particular behen soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may also contain microfine, optionally silanized or otherwise hydrophobized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

[0039] In a preferred embodiment, a means into which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25 wt.%, in particular 4 wt.% to 20 wt.% bleaching agent, in particular alkali percarbonate, up to 15 wt.%, in particular 1 wt.% to 10 wt.% bleaching activator, 20 wt.% to 55 wt.% inorganic builder, up to 10 wt.%, in particular 2 wt.% to 8 wt.% water-soluble organic builder, 10 wt.% to 25 wt.% synthetic anionic surfactant, 1 wt.% to 5 wt.% non-ionic surfactant and up to 25 wt.%, in particular 0.1 wt.% to 25 wt.% inorganic salts, in particular alkali carbonate and / or hydrogen carbonate.

[0040] In a further preferred embodiment, a composition in which the active ingredient to be used according to the invention is incorporated is liquid and contains 1 wt.% to 25 wt.%, in particular 5 wt.% to 15 wt.% non-ionic surfactant, up to 10 wt.%, in particular 0.5 wt.% to 8 wt.% synthetic anionic surfactant, 3 wt.% to 15 wt.%, in particular 5 wt.% to 10 wt.% soap, 0.5 wt.% to 5 wt.%, in particular 1 wt.% to 4 wt.% organic builder, in particular polycarboxylate such as citrate, up to 1.5 wt.%, in particular 0.1 wt.% to 1 wt.% complexing agent for heavy metals, such as phosphonate, and, in addition to optionally contained enzyme, enzyme stabilizer, color and / or fragrance, water and / or water-miscible solvent.

[0041] It is also possible to use a combination of an essential dirt-removing active ingredient of the invention with a dirt-removing polymer consisting of a dicarboxylic acid and an optionally polymeric diol to enhance the cleaning performance of detergents when washing textiles. Such combinations with a dirt-removing polymer, particularly one active in polyesters, are also possible within the scope of the inventive composition and the inventive method.

[0042] Among the known polyester-active, dirt-removing polymers that can be used in addition to the active ingredients of the invention are copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid, or terephthalic acid; diols, for example ethylene glycol or propylene glycol; and polydiols, for example polyethylene glycol or polypropylene glycol. Preferred dirt-removing polyesters include compounds that are formally accessible by esterification of two monomers, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO-(CHR 11< -) a OH, which can also exist as the polymeric diol H-(O-(CHR 11< -) a ) b OH.In this, Ph represents an o-, m-, or p-phenylene residue, which may bear 1 to 4 substituents selected from alkyl groups with 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups, and mixtures thereof; R11 represents hydrogen, an alkyl group with 1 to 22 carbon atoms, and mixtures thereof; a represents a number from 2 to 6; and b represents a number from 1 to 300. Preferably, the polyesters obtainable from these contain both monomerdiol units -O-(CHR11 -)aO- and polymerdiol units -(O-(CHR11 -)a)bO-. The molar ratio of monomerdiol units to polymerdiol units is preferably 100:1 to 1:100, and particularly 10:1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range of 4 to 200, in particular from 12 to 140.The molecular weight, or the mean molecular weight or the maximum of the molecular weight distribution, of preferred dirt-removing polyesters is in the range of 250 g / mol to 100,000 g / mol, particularly from 500 g / mol to 50,000 g / mol. The acid underlying the term Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, melithic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid, and sulfoteterephthalic acid, as well as mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably present in salt form, particularly as alkali or ammonium salts. Among these, the sodium and potassium salts are particularly preferred.If desired, instead of the HOOC-Ph-COOH monomer, small proportions, in particular not more than 10 mol% based on the proportion of Ph with the meaning given above, of other acids having at least two carboxyl groups may be contained in the dirt-removing 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, cortic acid, azelaic acid, and sebacic acid. 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 selected from hydrogen and the alkyl groups with 1 to 10, in particular 1 to 3, carbon atoms. Among the latter diols, those of the formula HO-CH 2 -CHR 11< -OH, in which R 11< has the above-mentioned 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. Polyethylene glycol, with an average molar mass in the range of 1000 g / mol to 6000 g / mol, is particularly preferred among the polymeric diols.

[0043] If desired, these polyesters, composed as described above, can also be end-capped, with suitable end groups being alkyl groups with 1 to 22 carbon atoms and esters of monocarboxylic acids. The end groups linked via ester bonds can be based on alkyl, alkenyl, and aryl monocarboxylic acids with 5 to 32 carbon atoms, particularly 5 to 18 carbon atoms.These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which can bear 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, its hydrogenation product hydroxystearic acid, as well as o-, m- and p-hydroxybenzoic acid.The hydroxymonocarboxylic acids can themselves be linked to one another via their hydroxyl and carboxyl groups and thus be present multiple times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, i.e., their degree of oligomerization, is in the range of 1 to 50, particularly 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, are used in combination with an active ingredient essential to the invention.

[0044] The polyester-active, dirt-removing polymers are preferably water-soluble, where "water-soluble" is 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, the polymers preferably used exhibit a solubility of at least 1 g per liter, and in particular at least 10 g per liter, under these conditions.

[0045] Preferred laundry treatment agents containing an active ingredient used according to the invention have as their fabric softening agent a so-called esterquat, that is, a quaternized ester of carboxylic acid and amino alcohol. These are known substances that can be obtained using the relevant methods of preparative organic chemistry, for example, by partially esterifying triethanolamine with fatty acids in the presence of hypophosphoric acid, passing air through the mixture, and then quaternizing it with dimethyl sulfate or ethylene oxide. The preparation of solid esterquats is also known, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.

[0046] The preferred ester quats in the agents are quaternized fatty acid triethanolamine ester salts, which follow formula (IV), in which R1<CO represents an acyl group with 6 to 22 carbon atoms, R2< and R3< independently represent hydrogen or R1<CO, R4< represent an alkyl group with 1 to 4 carbon atoms or a (CH2CH2O)q hydrogen group, m, n, and p collectively represent 0 or numbers from 1 to 12, q represents numbers from 1 to 12, and X represents a charge-balancing anion such as a halide, alkyl sulfate, or alkyl phosphate. Typical examples of esterquats that can be used in accordance with the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid, and erucic acid, as well as their technical mixtures, such as those obtained, for example, during the pressure cracking of natural fats and oils.Preferably, technical-grade C12 / 18 coconut fatty acids and, in particular, partially hydrogenated C16 / 18 tallow or palm fatty acids, as well as C16 / 18 fatty acid fractions rich in elaidic acid, are used. For the production of the quaternary 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-related properties of the ester quats, a ratio of 1.2:1 to 2.2:1, preferably 1.5:1 to 1.9:1, has proven particularly advantageous. The preferably used ester quats represent technical mixtures of mono-, di-, and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical-grade C16 / 18 tallow or palm fatty acids (iodine value 0 to 40).Quaternated fatty acid triethanolamine ester salts of formula (IV), in which R 1< CO stands for an acyl group with 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 O and X for methyl sulfate, have proven to be particularly advantageous.

[0047] In addition to the quaternated triethanolamine ester salts of carboxylic acids, quaternated ester salts of carboxylic acids with diethanolalkylamines of formula (V) are also suitable as ester quats. in which R 1< CO stands for an acyl group with 6 to 22 carbon atoms, R 2< for hydrogen or R 1< CO, R 4< and R 5< independently of each other for alkyl groups with 1 to 4 carbon atoms, m and n together for 0 or numbers from 1 to 12 and X for a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

[0048] Finally, another group of suitable ester quats includes the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyldialkylamines of formula (VI), in which R 1< CO stands for an acyl group with 6 to 22 carbon atoms, R 2< for hydrogen or R 1< CO, R 4< , R 6< and R 7< independently of each other for alkyl groups with 1 to 4 carbon atoms, m and n together for 0 or numbers from 1 to 12 and X for a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

[0049] Regarding the selection of preferred fatty acids and the optimal degree of esterification, the exemplary specifications given for (IV) also apply mutatis mutandis to the ester quats of formulas (V) and (VI). Ester quats are usually commercially available as 50 to 90 wt% alcoholic solutions, which can also be easily diluted with water, with ethanol, propanol, and isopropanol being the usual alcoholic solvents.

[0050] Esterquats are preferably used in amounts of 5% to 25% by weight, particularly 8% to 20% by weight, based on the total laundry after-treatment agent. Optionally, the laundry after-treatment agents used according to the invention may additionally contain the detergent ingredients listed above, provided they do not interact negatively with the esterquat in an unacceptably negative manner. Preferably, the agent is a liquid, aqueous agent. Examples Example 1: Synthesis of poly(MDO-co-DMAEMA-co-MPEGMA) (P1)

[0051] To a degassed solution of 2.74 g of 2-methylene-1,3-dioxepane (MDO; 24 mmol) and 98.5 mg of azo-bis-(isobutylonitrile) (AIBN; 0.6 mmol) in 8.25 ml of anisole under argon, a similarly degassed solution of 2.92 g of 2-(dimethylamino)ethyl methacrylate (DMAEMA; 20.4 mmol) and 4.68 g of methyl polyethylene glycol methacrylate (MPEGMA; 15.6 mmol) in 22.9 ml of dimethylformamide was added using a syringe pump (1.9 ml / h). The reaction mixture was stirred for 16 h at a temperature of 70°C. Methyl iodide was then added to the DMAEMA side chains in a 2:1 molar ratio for quaternization. The reaction mixture was stirred for 16 h at room temperature. The pale yellow precipitate was filtered off, washed with pentane, dissolved in chloroform, reprecipitated by adding pentane, filtered again, and dried under vacuum at 40 °C for 48 h. 6.8 g of copolymer P1 (66% of theory) were obtained. GPC in water: Mw 31,000 g / mol and Mn 14,000 g / mol (D = 2.24). MDO is present to 30% in copolymer P1, determined by 1< H-NMR spectroscopy. Example 2: Stain removal

[0052] Table 1 shows the composition (ingredients in weight percent, each based on the total product) of the detergent M1 according to the invention and of the product V1 free of a corresponding active ingredient: Table 1: Composition V1 M1 C 9 - 13 alkyl benzene sulfonate, Na salt 9 9 Sodium lauryl ether sulfate with 2 EO 3 3 C 12-14 fatty alcohol with 7 EO 7 7 C12-18 fatty acid, sodium salt 2 2 NaOH 0,5 0,5 Citric acid 2 2 1-Hydroxyethane-1,1-diphosphonate, sodium salt 0,6 0,6 Other enzymes, dye, optical brighteners, alcohols, boric acid, solvents, dyes 14 14 P1 - 1 Water per 100

[0053] Washing tests were conducted using either V1 or M1 in a Miele softtronic® < W 1935 washing machine (cotton short wash program with increased water volume, 40 °C; water hardness 16 °dH; dosage 53 g of the respective product per wash cycle). In addition to a 3.5 kg load of laundry, eight 20 x 40 cm polyester textiles were used. The laundry loads were washed three times with the respective detergent and dried after each wash. After the three pre-washes, the textiles were soiled as specified in Table 2 below and then aged for seven days. Afterward, the soiled fabrics were stapled onto towels and washed under the conditions described above using the same detergent as before. The fabrics were dried, and their brightness, also specified in Table 2, was measured using a Mach 5 colorimeter (Colour Consult). Table 2: Washing results for polymer 1 Soiling Y values ​​for V1 Y values ​​for W1 Mascara 56,2 61,7 frying fat 63,1 67,7 shoe polish 33,0 39,3 Engine oil 54,9 65,8 lipstick 36,6 48,8

[0054] It can be seen that, compared to the detergent without the addition of the essential copolymer, the textiles are less soiled when using the detergent with the copolymer additive.

Claims

1. Use of copolymers obtainable by radical polymerization of cyclic ketene acetals with acrylic and / or vinyl monomers, which are at least partially ammonium-substituted, to enhance the cleaning performance of detergents against soiling when washing textiles.

2. Use according to claim 1, characterized in that the textiles were washed and / or post-treated in the presence of the copolymer before being contaminated.

3. Use of copolymers obtainable by radical polymerization of cyclic ketene acetals with acrylic and / or vinyl monomers, which are at least partially ammonium-substituted, to reduce the greying of textiles during washing.

4. Method for washing textiles, in which a detergent and a copolymer obtainable by radical polymerization of cyclic ketene acetals with acrylic and / or vinyl monomers, which are at least partially ammonium-substituted, are used.

5. Method according to claim 4, characterized in that the concentration of the copolymer used in the washing liquor is 0.0001 g / l to 1 g / l, in particular 0.001 g / l to 0.2 g / l.

6. Process according to claim 4 or 5, characterized in that it is carried out using a detergent containing the copolymer.

7. Method for washing textiles according to one of claims 4 to 6, characterized in that it is carried out using a laundry after-treatment agent, in particular a fabric softener, containing the copolymer.

8. Washing or laundry after-treatment agent containing a copolymer obtainable by radical polymerization of cyclic ketene acetals with acrylic and / or vinyl monomers which are at least partially ammonium-substituted, and a surfactant.

9. Agent according to claim 8, characterized in that it contains the copolymer in amounts of 0.01 wt% to 10 wt%, in particular 0.1 wt% to 3 wt%.

10. Use according to any one of claims 1 to 3, process according to any one of claims 4 to 7, or agent according to claim 8 or 9, characterized in that the copolymer is composed of 5 mol% to 50 mol%, in particular 15 mol% to 35 mol%, of at least one cyclic ketene acetal monomer and 50 mol% to 95 mol%, in particular 65 mol% to 85 mol%, of at least one acrylic or vinyl monomer which is at least partially ammonium-substituted; and / or that the ketene acetal is selected from 2-methylene-1,3-dioxolane, 2-methylene-1,3-dioxane, 2-methylene-1,3-dioxepane, which may optionally be substituted in the acetal ring, such as 4,5-di-C1-12-alkyl-2-methylene-1,3-dioxolane, 4-C1-12-alkyl-2-methylene-1,3-dioxolane, 5-C1-12-alkyl-2-methylene-1,3-dioxepane, 5,6-di-C1-12-alkyl-2-methylene-1,3-dioxepane and 5,6-benzo-2-methylene-1,3-dioxepane, and mixtures thereof; and / or that the acrylic or vinyl monomer is selected from acrylic acid esters, acrylic acid amides, methacrylic acid esters, methacrylic acid amides, vinylimidazole, vinylpyrrolidone and mixtures thereof, which are at least partially ammonium-substituted.

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