Color-protecting detergents

Abstract

The aim of the invention is to improve the color protection properties of detergents when used to wash colored textiles. This is achieved essentially in that copolymers obtainable by radical polymerization of cyclic ketene acetals with acrylic and / or vinyl monomers and optionally further additional monomers are used.

Description

[0001] The present invention relates to the use of certain copolymers of ketene derivatives and monoethylene unsaturated comonomers as color transfer-inhibiting agents in the washing of textiles and detergents containing such agents.

[0002] In addition to essential ingredients for the washing process, such as surfactants and builders, detergents typically contain other components collectively known as laundry aids. These include diverse groups of active ingredients such as foam regulators, anti-graying agents, bleaching agents, bleach activators, and enzymes. These aids also include substances designed to prevent dyed textiles from appearing discolored after washing. This discoloration of washed, i.e., clean, textiles can occur either because dye is removed from the fabric during the washing process ("fading") or because dyes transferred from other colored textiles can transfer onto the fabric ("discoloration"). Discoloration can also be a concern with undyed items if they are washed together with colored items.To avoid these undesirable side effects of removing dirt from textiles by treating them with typically surfactant-containing aqueous systems, detergents, especially those intended as so-called color detergents for washing colored textiles, contain active ingredients that prevent dyes from being lifted from the fabric or at least prevent the deposition of detached dyes present in the wash water onto the textiles. Many of the polymers commonly used have such a high affinity for dyes that they attract them more readily from the dyed fiber, resulting in increased color loss.

[0003] Known color transfer inhibitors include polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine N-oxide, or copolymers thereof. The color transfer-inhibiting properties of certain triazine derivatives are known from international patent applications WO 2008 / 110469 A1 and WO 2007 / 019981 A1.

[0004] Surprisingly, it was found that copolymers of cyclic ketene acetals with acrylic or vinyl monomers have a positive effect on color transfer during the washing process and prevent the staining of undyed textiles.

[0005] The reaction of 2-methylene-4-phenyl-1,3-dioxolane with methacrylic esters is known from 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 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 WO 2011 / 112944 A1 discloses homopolymers, copolymers, or terpolymers of hydrophobic monomers as additives for detergents.

[0006] The invention relates to the use of copolymers obtainable by radical polymerization of cyclic ketene acetals with vinylimidazole and / or vinylpyrrolidone monomers to prevent the transfer of textile dyes from dyed textiles to undyed or differently colored textiles during their joint washing in aqueous solutions, in particular those containing surfactants.

[0007] In the radical polymerization of cyclic ketene acetals, the acetal ring opens, resulting in ester functionalities that improve the biodegradability of the resulting polymer. This improved biodegradability is considered a further advantage of the invention.

[0008] Preferably, the copolymers used according to the invention are 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 vinyl monomers or mixtures thereof with acrylic monomers, wherein the vinyl monomers consist at least partially, preferably entirely, of vinylimidazole and / or vinylpyrrolidone monomers. Apart from components originating from radical initiators or radical terminators, the copolymers preferably contain no components derived from monomers other than those mentioned. The copolymers preferably exist as a statistically determined structure, but can also contain a gradient or be structured as block copolymers.

[0009] 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.

[0010] The comonomer polymerizable with the ketene acetal is selected from vinylimidazole, vinylpyrrolidone, mixtures thereof, and mixtures of vinylimidazole and / or vinylpyrrolidone with preferably acrylic esters, acrylic amides, methacrylic esters, methacrylamides and mixtures thereof, wherein the alcohol component of the esters and the amine component of the amides are in particular 1-(3-hydroxypropyl)-1H-imidazole, 1-(3-hydroxypropyl)pyrrolidin-2-one, 1-(3-aminopropyl)imidazole, 1-(3-aminopropyl)-2-pyrrolidone or N,N-dimethylpropane-1,3-diamine and mixtures thereof.

[0011] The monomers mentioned can be polymerized according to the above-cited literature-based procedures or in analogy to them.

[0012] The active ingredients obtained in this way contribute to both of the aforementioned aspects of colorfastness; that is, they reduce both discoloration and fading, although the effect of preventing color transfer, particularly when washing white textiles, is most pronounced. A further object of the invention is therefore the use of such active ingredients to prevent changes in the color appearance of dyed textiles, preferably those made of or containing cotton, when washed in aqueous solutions, especially those containing surfactants. Changes in color appearance here do not refer to the difference between a soiled and a clean textile, but rather to the difference between a clean textile before and after the washing process.Another aspect of the invention is therefore a detergent containing a surfactant, other common detergent ingredients, and a copolymer as defined above in a color-transfer-inhibiting amount. A color-transfer-inhibiting amount is understood to be an amount that significantly reduces the transfer of dyes from dyed textiles to undyed or differently colored textiles when washed together, compared to otherwise identical conditions in the absence of the active ingredient. The aforementioned color-transfer-inhibiting active ingredients are preferably used in detergents in amounts of 0.01% to 5% by weight, and in particular from 0.05% to 0.5% by weight.

[0013] A further aspect of the invention is a method for washing white or dyed textiles in surfactant-containing aqueous solutions in the presence of differently colored textiles, characterized in that a surfactant-containing aqueous liquor containing a copolymer as defined above is used. In such a method, it is possible to wash white or undyed textiles together with the dyed textile without the white or undyed textile becoming stained. Preferably, 0.0003 g / l to 0.16 g / l, and in particular 0.0015 g / l to 0.015 g / l, of the copolymer as defined above is used in the aqueous liquor.

[0014] In addition to the aforementioned color transfer inhibitor, a detergent may contain other ingredients compatible with this component. For example, it may also contain another color transfer inhibitor, preferably in amounts of 0.1 wt.% to 2 wt.%, particularly 0.2 wt.% to 1 wt.%, which in a preferred embodiment is selected from the polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine N-oxide, or copolymers thereof.Suitable polyvinylpyrrolidones include those with molecular weights of 15,000 to 50,000, as well as those with higher molecular weights, for example, up to over 1,000,000, particularly from 1,500,000 to 4,000,000. Other suitable materials include N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers and carboxylic acid amides, polyesters and polyamides containing pyrrolidone groups, grafted polyamidoamines and polyethyleneimines, polyamine N-oxide polymers, polyvinyl alcohols, and copolymers based on acrylamidoalkenylsulfonic acids. Enzymatic systems comprising a peroxidase and hydrogen peroxide, or a substance that releases hydrogen peroxide in water, can also be used.The addition of a mediator compound for peroxidase, for example an acetosyringone, a phenol derivative, or a phenotiazine or phenoxazine, is preferred in this case, and the aforementioned polymeric color transfer inhibitors may also be used. For use in compositions according to the invention, polyvinylpyrrolidone preferably has an average (weight average) molar mass in the range of 10,000 to 60,000, particularly in the range of 25,000 to 50,000. Among the copolymers, those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5:1 to 1:1 with an average (weight average) molar mass in the range of 5,000 to 50,000, particularly 10,000 to 20,000, are preferred.

[0015] Detergents, which may be in the form of, in particular, powdered solids, compacted particles, homogeneous solutions, or suspensions, may contain, in principle, all known ingredients commonly used in such agents, in addition to the active ingredient employed according to the invention. The agents according to the invention may, in particular, contain builders, surfactants, bleaching agents based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestrants, electrolytes, pH regulators, and other auxiliary substances such as optical brighteners, anti-graying agents, foam regulators, as well as dyes and fragrances.

[0016] The products contain one or more surfactants, including in particular anionic surfactants, non-ionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

[0017] Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols, each with 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters, and fatty acid amides, which correspond to the aforementioned long-chain alcohol derivatives with respect to the alkyl moiety, as well as of alkylphenols with 5 to 12 carbon atoms in the alkyl group, are also suitable.

[0018] Preferably, alkoxylated, advantageously ethoxylated, and in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol are used as nonionic surfactants. The alcohol residue in these alcohols may be linear or, preferably, methyl-branched at the 2-position, or the mixture may contain both linear and methyl-branched residues, as is commonly found in oxo alcohol residues. However, alcohol ethoxylates with linear residues derived from native alcohols with 12 to 18 carbon atoms, e.g., from coconut, palm, tallow, or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol, are particularly preferred.Preferred ethoxylated alcohols include, for example, C12-C14 alcohols with 3 or 4 EO, C9-C11 alcohols with 7 EO, C13-C15 alcohols with 3, 5, 7, or 8 EO, C12-C18 alcohols with 3, 5, or 7 EO, and mixtures thereof, such as mixtures of C12-C14 alcohol with 3 EO and C12-C18 alcohol with 7 EO. The stated degrees of ethoxylation represent statistical averages, which may be whole numbers or fractions for a specific product. Preferred alcohol ethoxylates exhibit a narrow range of homologs (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. Particularly in agents for use in machine processes, extremely low-foaming compounds are typically used.These preferably include C12-C18 alkyl polyethylene glycol-polypropylene glycol ethers, each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule. However, other known low-foaming nonionic surfactants can also be used, such as C12-C18 alkyl polyethylene glycol-polybutylene glycol ethers, each containing up to 8 moles of ethylene oxide and butylene oxide units in the molecule, as well as end-capped alkyl polyalkylene glycol mixed ethers. Particularly preferred are alkoxylated alcohols containing hydroxyl groups, so-called hydroxy mixed ethers. Non-ionic surfactants also include alkyl glycosides of the general formula RO(G) x, in which R represents a primary straight-chain or methyl-branched, in particular 2-position methyl-branched aliphatic residue with 8 to 22, preferably 12 to 18 C atoms, and G represents a glucose unit with 5 or 6 C atoms, preferably glucose.The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number—which, as a quantity to be determined analytically, can also take on fractional values—between 1 and 10; preferably, x is between 1.2 and 1.4. Polyhydroxy fatty acid amides of formula IV are also suitable, in which R<1 CO represents an aliphatic acyl group with 6 to 22 carbon atoms, R<2 represents hydrogen, an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms, and [Z] represents a linear or branched polyhydroxyalkyl group with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

[0019] Preferably, polyhydroxy fatty acid amides are derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. Compounds of formula (V) also belong to the group of polyhydroxy fatty acid amides. where R3< represents a linear or branched alkyl or alkenyl group with 7 to 12 carbon atoms, R4< represents a linear, branched, or cyclic alkylene group or an arylene group with 2 to 8 carbon atoms, and R5< represents a linear, branched, or cyclic alkyl group or an aryl group or an oxy-alkyl group with 1 to 8 carbon atoms, wherein C1-C4 alkyl or phenyl groups are preferred, and [Z] represents a linear polyhydroxyalkyl group whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] is also preferably obtained by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose, or xylose.The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst. Another class of preferably used nonionic surfactants, which are employed either as the sole nonionic surfactant or in combination with other nonionic surfactants, particularly together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters. Nonionic surfactants of the amine oxide type, for example N-cocosalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides can also be suitable.The amount of these nonionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, and in particular no more than half of it. Other surfactants that can be considered are so-called gemini surfactants. These are generally understood to be compounds that possess two hydrophilic groups per molecule. These groups are usually separated from each other by a so-called "spacer." This spacer is typically a carbon chain that should be long enough to allow the hydrophilic groups sufficient distance to act independently. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to significantly reduce the surface tension of water. In exceptional cases, the term gemini surfactants is used to refer not only to such "dimeric" but also to correspondingly "trimeric" surfactants.Suitable gemini surfactants include, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer alcohol tris-sulfates and ether sulfates. End-capped dimer and trimer mixed ethers are particularly characterized by their bi- and multifunctionality. These end-capped surfactants possess good wetting properties and are low-foaming, making them especially suitable for use in machine washing or cleaning processes. Gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides can also be used.

[0020] Suitable anionic surfactants are, in particular, soaps and those containing sulfate or sulfonate groups. Sulfonate-type surfactants preferably include C9-C13 alkylbenzenesulfonates, olefin sulfonates (i.e., mixtures of alkene and hydroxyalkane sulfonates), and disulfonates, such as those obtained, for example, from C12-C18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Alkane sulfonates obtained from C12-C18 alkanes, for example, by sulfochlorination or sulfoxidation followed by hydrolysis or neutralization, are also suitable.Also suitable are esters of α-sulfofaticial acids (estersulfonates), for example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel, or tallow fatty acids, which are produced by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts. Preferably, these are the α-sulfonated esters of hydrogenated coconut, palm, palm kernel, or tallow fatty acids, whereby sulfonation products of unsaturated fatty acids, for example, oleic acid, may also be present in small amounts, preferably not exceeding about 2 to 3% by weight. In particular, α-sulfofaticial alkyl esters are preferred, which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example, methyl esters, ethyl esters, propyl esters, and butyl esters.Methyl esters of α-sulfofaticial acids (MES), as well as their saponified disalts, are particularly advantageous. Other suitable anionic surfactants include sulfated fatty acid glycerol esters, which represent mono-, di-, and triesters, as well as mixtures thereof, such as those obtained by esterification with a monoglycerol and 1 to 3 moles of fatty acid or by transesterification of triglycerides with 0.3 to 2 moles of glycerol. The alkali and, in particular, the sodium salts of the sulfuric acid half-esters of C12-C18 fatty alcohols, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or of C10-C20 oxo alcohols, and those half-esters of secondary alcohols of this chain length, are preferred as alk(en)yl sulfates.Alk(en)yl sulfates of the aforementioned chain length are also preferred, containing a synthetic, petrochemical-based, straight-chain alkyl group that exhibits analogous degradation behavior to the corresponding compounds based on fatty chemical raw materials. For detergent applications, C12-C16 alkyl sulfates, C12-C15 alkyl sulfates, and C14-C15 alkyl sulfates are particularly preferred. Also suitable are the sulfuric acid monoesters of straight-chain or branched C7-C21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-C11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 to 4 EO.Preferred anionic surfactants include the salts of alkylsulfosuccinic acid, also known as sulfosuccinates or sulfosuccinic acid esters, which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8 to C18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which are nonionic surfactants when considered individually. Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are especially preferred. It is also possible to use alk(en)yl succinic acid with preferably 8 to 18 carbon atoms in the alk(en)yl chain or its salts.Other suitable anionic surfactants include fatty acid derivatives of amino acids, such as N-methyltaurine (taurides) and / or N-methylglycine (sarcosides). Sarcosides and sarcosinates are particularly preferred, especially sarcosinates of higher and optionally mono- or polyunsaturated fatty acids, such as oleyl sarcosinate. Soaps are also suitable anionic surfactants. Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid, and behenic acid, as well as soap mixtures derived from natural fatty acids, for example, coconut, palm kernel, or tallow fatty acids, are particularly appropriate. Alkenyl succinic acid salts can also be used in combination with these soaps or as a substitute for soaps.

[0021] Anionic surfactants, including soaps, can be present in the form of their sodium, potassium, or ammonium salts, as well as soluble salts of organic bases such as mono-, di-, or triethanolamine. Preferably, anionic surfactants are present in the form of their sodium or potassium salts, particularly the sodium salts. Surfactants are typically present in detergents in proportions of 1% to 50% by weight, and particularly 5% to 30% by weight.

[0022] A detergent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. Water-soluble organic builders include polycarboxylic acids, in particular citric acid and sugar acids; monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid, as well as polyaspartic acid; polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), and 1-hydroxyethane-1,1-diphosphonic acid; polymeric hydroxy compounds such as dextrin; and polymeric (poly)carboxylic acids, in particular polycarboxylates accessible by the oxidation of polysaccharides or dextrins; polymeric acrylic acids; methacrylic acids; maleic acids; and copolymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality.The relative molecular mass of homopolymers of unsaturated carboxylic acids generally ranges from 3,000 g / mol to 200,000 g / mol, and that of copolymers from 2,000 g / mol to 200,000 g / mol, preferably from 30,000 g / mol to 120,000 g / mol, in each case based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular mass of 30,000 g / mol to 100,000 g / mol. Commercially available products include, for example, Sokalan® CP 5, CP 10, and PA 30 from BASF. 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% by weight.Water-soluble organic builder substances can also be terpolymers containing, as monomers, two unsaturated acids and / or their salts, and as a third monomer, vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate. The first acidic monomer or its salt is derived from a monoethylene-unsaturated C3-C8 carboxylic acid, 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, and / or a derivative of an allylsulfonic acid substituted at the 2-position with an alkyl or aryl group. Such polymers generally have a relative molecular mass between 1,000 g / mol and 200,000 g / mol. Other preferred copolymers are those containing acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.The organic building materials can be used, particularly for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50% by weight aqueous solutions. All the acids mentioned are generally used in the form of their water-soluble salts, especially their alkali salts.

[0023] Such organic builder substances can be present, if desired, in amounts up to 40 wt.%, in particular up to 25 wt.%, and preferably from 1 wt.% to 8 wt.%. Amounts close to the aforementioned upper limit are preferably used in paste-like or liquid, in particular aqueous, compositions according to the invention.

[0024] Suitable water-soluble inorganic builder materials include, in particular, alkali silicates, alkali carbonates, and alkali phosphates, which can be present in the form of their alkaline, neutral, or acidic sodium or potassium salts. Examples include trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, particularly 5 to 50, as well as the corresponding potassium salts or mixtures of sodium and potassium salts. Water-insoluble, water-dispersible inorganic builder materials include, in particular, crystalline or amorphous alkali aluminosilicates, in amounts of up to 50 wt%, preferably not exceeding 40 wt%, and in liquid form, in particular from 1 wt% to 5 wt%.Among these, crystalline sodium aluminosilicates of detergent quality, in particular zeolites A, P, and optionally X, alone or in mixtures, for example in the form of a co-crystallizate of zeolites A and X (Vegobond®<AX, a commercial product of Condea Augusta SpA), are preferred. Amounts close to the aforementioned upper limit are preferably used in solid, particulate agents. Suitable aluminosilicates, in particular, do not contain particles with a particle size greater than 30 µm and preferably consist of at least 80 wt% particles with a size less than 10 µm. Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.

[0025] 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 compositions according to the invention preferably have a molar ratio of alkali oxide to SiO₂ below 0.95, in particular from 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na₂O:SiO₂ of 1:2 to 1:2.8. The crystalline silicates, which can be present alone or in mixture with amorphous silicates, are preferably crystalline layered silicates of the general formula Na 2 Si x O 2x+1 · y H 2 O, in which x, the so-called modulus, is a number from 1.9 to 22, in particular 1.9 to 4 and y is a number from 0 to 33, and preferred values ​​for x are 2, 3 or 4.Preferred crystalline layered silicates are those in which x in the general formula mentioned above 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 general formula mentioned above, in which x represents a value from 1.9 to 2.1, prepared from amorphous alkali silicates, can also be used in compositions according to the invention. In a further preferred embodiment of compositions according to the invention, a crystalline sodium layered silicate with a modulus of 2 to 3 is used. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention. Crystalline layered silicates are commercially available, e.g.Na-SKS-1 (Na 2 Si 22 O 45 ·xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 ·xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 ·xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ·xH 2 O, makatite). Of these, Na-SKS-5 (α-Na₂Si₂O₅), Na-SKS-7 (β-Na₂Si₂O₅, natrosilite), Na-SKS-9 (NaHSi₂O₅·3H₂O), Na-SKS-10 (NaHSi₂O₅·3H₂O, kanemite), Na-SKS-11 (δ-Na₂Si₂O₅), and Na-SKS-13 (NaHSi₂O₅) are particularly suitable, but especially Na-SKS-6 (δ-Na₂Si₂O₅). In a preferred embodiment of the composition according to the invention, a granular compound of crystalline layered silicate and citrate, of crystalline layered silicate and the aforementioned (co-)polymeric polycarboxylic acid, or of alkali silicate and alkali carbonate is used, such as is commercially available under the name Nabion®< 15. Builder substances are normally present in amounts up to 75% by weight, especially 5% by weight to 50%.

[0026] Suitable peroxygen compounds for use in detergents include, in particular, organic peracids or pericy salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, or salts of diperdodecanedioic acid, hydrogen peroxide, and inorganic salts that release hydrogen peroxide under washing conditions, including perborate, percarbonate, persilicate, and / or persulfate such as caroate. If solid peroxygen compounds are to be used, they can be in the form of powders or granules, which may also be coated in a manner known in principle. If a composition according to the invention contains peroxygen compounds, these are present in amounts preferably up to 50% by weight, and in particular from 5% by weight to 30% by weight.The addition of small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates, as well as magnesium salts such as magnesium sulfate, may be useful.

[0027] Suitable bleaching activators include compounds that, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, particularly 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances bearing O- and / or N-acyl groups of the specified number of carbon atoms and / or optionally substituted benzoyl groups are suitable.Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, enol esters, as well as acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam.Hydrophilically substituted acylacetals and acyllactams are also preferred. Combinations of conventional bleach activators can also be used. Such bleach activators can be present in the usual quantity range, particularly in the presence of the aforementioned hydrogen peroxide-providing bleaching agents, preferably in amounts of 0.5 wt% to 10 wt%, and especially 1 wt% to 8 wt%, based on the total product. However, they are preferably omitted entirely when percarboxylic acid is used as the sole bleaching agent.

[0028] In addition to or instead of conventional bleach activators, sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes may also be included as so-called bleach catalysts.

[0029] Suitable enzymes for use in the agents include those from the classes of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases, and peroxidases, as well as mixtures thereof. Enzymatic agents obtained from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia, or Coprinus cinereus, are particularly suitable. The enzymes can be adsorbed onto carrier substances and / or embedded in coating substances to protect them against premature inactivation. They are preferably present in the detergents or cleaning agents according to the invention in amounts up to 5% by weight, and in particular from 0.2% by weight to 4% by weight. If the composition according to the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8,000 PE / g.If several enzymes are to be used in the composition according to the invention, this can be done by incorporating the two or more separate enzymes or enzymes prepared separately in a known manner, or by using two or more enzymes prepared together in a granulate.

[0030] Organic solvents that can be used in detergents, particularly when they are in liquid or paste form, in addition to water, include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol, and tert-butanol; diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol; mixtures thereof; and ethers derived from the aforementioned classes of compounds. Such water-miscible solvents are preferably present in the compositions according to the invention in amounts not exceeding 30% by weight, and particularly in amounts from 6% by weight to 20% by weight.

[0031] To adjust a desired pH value that is not achieved spontaneously through the mixing of the other components, the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali hydroxides. Such pH regulators are contained in the compositions according to the invention in amounts preferably not exceeding 20% ​​by weight, in particular from 1.2% by weight to 17% by weight.

[0032] Anti-graying agents serve to keep the dirt detached from the textile fibers suspended in the cleaning solution. Water-soluble colloids, mostly of organic origin, are suitable for this purpose, such as starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable. Furthermore, starch derivatives other than those mentioned above can be used, for example, aldehyde starches. Cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methyl carboxymethylcellulose, and mixtures thereof, are preferred, for example, in amounts of 0.1 to 5% by weight, based on the total amount of the agent.

[0033] Detergents can contain optical brighteners such as derivatives of diaminostilbene disulfonic acid or its alkali metal salts, although they are preferably free of optical brighteners for use as color detergents. Suitable examples include salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid or similarly structured compounds that, instead of the morpholino group, bear a diethanolamino group, a methylamino group, an anilino group, or a 2-methoxyethylamino group. Furthermore, optical brighteners of the substituted diphenylstyryl type may be present, for example, the alkali salts of 4,4'-bis(2-sulfostyryl)diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)diphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)diphenyl. Mixtures of the aforementioned optical brighteners may also be used.

[0034] Particularly when used in automated processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin that have a high proportion of C18-C24 fatty acids. Suitable non-surfactant foam inhibitors include, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes, and their mixtures with silanized silica or bis-fatty acid alkylenediamides. Mixtures of different foam inhibitors, such as those of silicones, paraffins, or waxes, are also advantageously used. Preferably, the foam inhibitors, especially silicone- and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance.In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

[0035] The production of solid agents presents no difficulties and can be carried out in known ways, for example by spray drying or granulation, whereby enzymes and any other thermally sensitive ingredients, such as bleaching agents, can be added separately at a later date. For the production of agents with an increased bulk density, particularly in the range of 650 g / l to 950 g / l, a process including an extrusion step is preferred.

[0036] To produce tablet-shaped products, which can be single-phase or multi-phase, single-color or multi-color, and in particular consist of one layer or several layers, especially two layers, the preferred method is to mix all components—optionally one layer each—in a mixer and compress the mixture using conventional tablet presses, for example, eccentric or rotary presses, with compression forces in the range of approximately 50 to 100 kN, preferably 60 to 70 kN. Particularly with multi-layer tablets, it can be advantageous to pre-compress at least one layer. This is preferably carried out with compression forces between 5 and 20 kN, particularly 10 to 15 kN. This method readily yields break-resistant tablets that are nevertheless sufficiently soluble under application conditions, with breaking and flexural strengths typically of 100 to 200 N, but preferably above 150 N.Preferably, a tablet produced in this way has a weight of 10 g to 50 g, particularly 15 g to 40 g. The shape of the tablets is arbitrary and can be round, oval, or rectangular, 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 rectangular or cuboid tablets, which are predominantly introduced via the dosing device of the washing machine, depends on the geometry and volume of this dosing device. Exemplary preferred embodiments have a base area of ​​(20 to 30 mm) x (34 to 40 mm), particularly 26 x 36 mm or 24 x 38 mm.

[0037] Liquid or pasty agents in the form of solutions containing common solvents are usually produced by simply mixing the ingredients, which can be placed in an automatic mixer in substance or as a solution. Examples 1: Preparation of a 2-methylene-1,3-dioxepane-vinylpyrrolidone copolymer (P1)

[0038] A solution of 2-methylene-1,3-dioxepane (MDO; 1 eq, 8 mmol) and azo-bis(isobutylonitrile) (AIBN; 1 mol%, 0.8 mmol) in 2 mL of dimethylformamide (DMF) was degassed by three freeze-vacuum-thaw cycles, kept under argon, and heated to 70°C. Vinylpyrrolidone (VP; 9 eq, 72 mmol) dissolved in 17 mL of DMF, which had been degassed in the same manner, was added via a syringe pump (4.9 mL h⁻¹) through a septum. After 5 hours of reaction time, the reaction mixture was poured into diethyl ether. The precipitated polymer was separated, dissolved in chloroform, reprecipitated by the addition of pentane, separated, and dried under reduced pressure at 60°C for 48 h. 4.6 g of copolymer P1 was obtained. M n : 13000 g / mol, M w : 30000 g / mol, D: 2.37 MDO was present to 8% in copolymer P1, determined by 1< H-NMR spectroscopy. Example 2: Preparation of a 2-methylene-1,3-dioxepane-vinylpyrrolidone copolymer (P2)

[0039] MDO (1 eq, 7 mmol) and AIBN (1 mol%, 0.7) were dissolved in 3.4 mL of DMF and degassed by a three-fold freeze-vacuum-thaw cycle, kept under argon, and heated to 70°C. VP (8 eq, 56 mmol) dissolved in 13 mL of DMF, which had been degassed in the same manner, was added through a septum using a syringe pump (2.4 mL h⁻¹). After 8 hours of reaction time, the reaction mixture was poured into diethyl ether. The precipitated polymer was separated, dissolved in chloroform, reprecipitated by the addition of pentane, separated, and dried under reduced pressure at 60°C for 48 h. 4.1 g of copolymer P2 were obtained. M n : 10000g / mol, M w : 21000g / mol, D: 2.08 MDO was present to 10% in the copolymer P2, determined by 1< H-NMR spectroscopy. Example 3: Preparation of a 2-methylene-1,3-dioxepane-vinylpyrrolidone copolymer (P3)

[0040] MDO (4.5 eq, 36 mmol) and AIBN (1 mol%, 0.8 mmol) were dissolved in 8.7 mL of DMF and degassed by a three-fold freeze-vacuum-thaw cycle, kept under argon, and heated to 70°C. VP (5.5 eq, 44 mmol) dissolved in 10.3 mL of DMF, which had been degassed in the same manner, was added through a septum using a syringe pump (0.83 mL h⁻¹). After 18 hours of reaction time, the reaction mixture was poured into diethyl ether. The precipitated polymer was separated, dissolved in chloroform, reprecipitated by the addition of pentane, separated, and dried under reduced pressure at 60°C for 48 h. 2.2 g of copolymer P3 were obtained. M n : 3100g / mol, M w : 4600g / mol, D:1,47 MDO was present to 33% in the copolymer P3, determined by 1< H-NMR spectroscopy. Example 4: Preparation of a 2-methylene-1,3-dioxepane-vinylpyrrolidone-vinylimidazole copolymer (P4)

[0041] MDO (3 eq, 24 mmol) and AIBN (1 mol%, 0.8 mmol) were dissolved in 5.8 mL of DMF and degassed by a three-fold freeze-vacuum-thaw cycle, kept under argon, and heated to 70°C. VP (3.5 eq, 28 mmol) and vinylimidazole (VI; 3.5 eq, 28 mmol), dissolved in 12.3 mL of DMF that had been degassed in the same manner, were added through a septum using a syringe pump (1.1 mL h⁻¹). After a reaction time of 2 hours, the reaction mixture was poured into diethyl ether. The precipitated polymer was separated, dissolved in chloroform, reprecipitated by the addition of pentane, separated, and dried under reduced pressure at 60°C for 48 h. 4.5 g of copolymer P4 were obtained. M n : 12000 g / mol, M w : 18000 g / mol, D: 1.47 MDO was present at 15% and VP and VI were each present at 42.5% in copolymer P4, determined by 1< H-NMR spectroscopy. Example 5: Preparation of a 2-methylene-1,3-dioxepane-vinylimidazole copolymer (P5)

[0042] MDO (1 eq, 6.6 mmol) and AIBN (1 mol%, 0.33 mmol) were dissolved in 0.65 ml of DMF and degassed by a three-fold freeze-vacuum-thaw cycle, kept under argon, and heated to 70°C. VI (4 eq, 26.4 mmol) dissolved in 2.1 ml of DMF, which had been degassed in the same manner, was added via a septum using a syringe pump (0.4 ml h⁻¹). After a reaction time of 2 hours, the reaction mixture was poured into diethyl ether. The precipitated polymer was separated, dissolved in chloroform, reprecipitated by the addition of pentane, separated, and dried under reduced pressure at 60°C for 48 h. 2.8 g of copolymer P5 were obtained. M n : 7500 g / mol, M w : 13000 g / mol, D: 1.78 MDO was present to 13% in the copolymer P5, determined by 1< H-NMR spectroscopy. Example 6: Color inhibition

[0043] The dyes listed in the following table (dyed textiles that readily release dye) were washed at 60°C for 30 minutes in the presence of white acceptor fabrics (6 cm x 16 cm) also listed in the table. The dyeing of the cotton textile was then determined spectrophotometrically and evaluated according to ISO 105 A04 (SSR scores on a scale of 1 to 5, 1 = strong dyeing, 5 = no dyeing). Washing liquors were used, each containing either a dye transfer inhibitor-free, water-based liquid detergent (F1 or F2; concentration 3.5 g / l) or the same amount of an otherwise identically composed detergent to which one of the polymers P1 to P5 prepared in Examples 1 to 5 had been added, with a reduction in the amount of water. The following SSR scores were obtained (mean of two determinations): Table 1: Results of the color inhibition Acceptor Color provider F1 F1 + P1 F1 + P2 F1 + P3 F1 + P4 F2 F2 + P5 Cotton Direct Black 22 3,7 4,2 4,2 n / a n / a n / a n / a Cotton Direct Orange 39 2,0 3,0 3,0 n / a 2,7 2.0 2,7 Cotton Direct Red 83:1, EMPA 2,9 3,6 3,6 3,5 4,9 3.0 4.9 polyamide Direct Black 22 3,5 4,1 4,2 n / a n / a 4.1 4.6 polyamide Direct Orange 39 2,4 4,0 4,0 3,3 3,8 2.5 4.1 na: Determination not carried out

[0044] It can be seen that, compared to the detergent without the addition of the essential copolymers, the white textiles were less strongly colored when washed with the addition of copolymer.

Claims

1. Use of copolymers obtainable by radical polymerisation of cyclic ketene acetals with vinylimidazole and / or vinylpyrrolidone monomers, to prevent the transfer of textile dyes from dyed textiles to undyed or differently coloured textiles when they are washed together, in particular in aqueous solutions containing surfactants.

2. Use of copolymers obtainable by radical polymerisation of cyclic ketene acetals with vinyl imidazole and / or vinyl pyrrolidone monomers to prevent changes in the colour impression of dyed textiles when they are washed, in particular in aqueous solutions containing surfactants.

3. Method for washing white or dyed textiles in aqueous solutions containing surfactants in the presence of textiles of a different colour, characterised in that an aqueous solution containing surfactants is used which contains a copolymer obtainable by radical polymerisation of cyclic ketene acetals with vinylimidazole and / or vinylpyrrolidone monomers.

4. Process according to claim 3, characterised in that 0.0003 g / l to 0.16 g / l, in particular 0.0015 g / l to 0.015 g / l of the copolymer is used in the aqueous liquor.

5. Detergent containing surfactant and other conventional detergent ingredients, characterised in that it contains a copolymer obtainable by radical polymerisation of cyclic ketene acetals with acrylic and / or vinyl monomers in a colour transfer-inhibiting amount.

6. Agent according to claim 5, characterised in that it contains the copolymer in amounts of 0.01 wt.% to 5 wt.%, in particular 0.05 wt.% to 0.5 wt.%.

7. Agent according to claim 5 or 6, characterised in that it additionally contains a further colour transfer inhibitor selected from polymers of vinyl pyrrolidone, vinyl imidazole, vinyl pyridine N-oxide or copolymers thereof.

8. Use according to claim 1 or 2, process according to claim 3 or 4, or agent according to one of claims 5 to 7, characterised 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%, vinyl monomers or mixtures thereof with acrylic monomers, wherein the vinyl monomers consist at least in part of vinyl imidazole and / or vinyl pyrrolidone monomers.

9. Use, process or agent according to any of the preceding claims, characterised in that the ketene acetal is selected from 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, 4-C1-12-alkyl-2-methylene-1,3-dioxane, 4,6-di-C1-12-alkyl-2-methylene-1,3-dioxolane and 5,6-benzo-2-methylene-1,3-dioxepane, 4-phenyl-2-methylene-1,3-dioxolane, 4,5-diphenyl-2-methylene-1,3-dioxolane, 4-phenyl-2-methylene-1,3-dioxane, 4,6-diphenyl-2-methylene-1,3-dioxolane, 4-phenyl-2-methylene-1,3-dioxepan, 4,7-diphenyl-2-methylene-1,3-dioxepan and mixtures thereof.

10. Use, process or agent according to any of the preceding claims, characterised in that the comonomer polymerisable with the ketene acetal is selected from vinylimidazole, vinylpyrrolidone, mixtures thereof, and mixtures of vinylimidazole and / or vinylpyrrolidone with acrylic acid esters, acrylic acid amides, methacrylic acid esters, methacrylic acid amides and mixtures thereof.

Images