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 aim is essentially achieved by using polyester-based comb polymers that are obtained by aza-Michael addition of primary monoamines or primary or secondary diamines on diesters from unsaturated monocarboxylic acids and diols.

Description

[0001] The present invention relates to the use of certain polyester-based comb polymers as color transfer inhibiting agents in the washing of textiles and to detergents containing such agents.

[0002] In addition to the ingredients essential for the washing process, such as surfactants and builder materials, detergents generally contain other components that can be summarized under the term "washing aids" and include such diverse groups of active ingredients as foam regulators, graying inhibitors, bleaching agents, bleach activators, and enzymes. Such aids also include substances designed to prevent dyed textiles from changing their color appearance after washing. This change in the color appearance of washed, i.e., clean, textiles can be due, on the one hand, to dye components being removed from the textile during the washing process ("fading"), and, on the other hand, to dyes detached from other-colored textiles depositing on the textile ("discoloration"). This discoloration aspect can also play a role in undyed laundry when washed together with colored items.To avoid these undesirable side effects of removing dirt from textiles by treating them with aqueous systems that typically contain surfactants, detergents, especially those intended for washing colored textiles, contain active ingredients that prevent dyes from detaching from the textile or at least prevent the deposition of detached dyes in the wash liquor on textiles. Many of the polymers commonly used have such a high affinity for dyes that they attract them more strongly from the dyed fibers, resulting in increased color loss.

[0003] Known dye transfer inhibitors include, for example, polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine N-oxide, or copolymers thereof. The dye transfer inhibiting properties of certain triazine derivatives are known from international patent applications WO 2008 / 110469 A1 and WO 2007 / 019981 A1. Boardman Saskia J. et al., "Polymers for dye transfer inhibition in laundry applications," Journal of Applied Polymer Science, Vol. 138, No. 1, July 9, 2020, page 49632, disclose polyester-based dye transfer inhibitors for detergents, including a polyester of terephthalic acid and 2-amino-2-methyl-1,3-propanediol.

[0004] Surprisingly, it was found that aza-Michael addition products of S-substituted primary aminothiols to oligoesters of unsaturated dicarboxylic acids and diols have a positive effect on dye transfer in the washing process and prevent staining of undyed textiles.

[0005] The aza-Michael addition is known from D.M. Lynn, R. Langer, J. Am. Chem. Soc. 2000, 122, 10761-10768; D.M. Lynn, D.G. Anderson, D. Putnam, R. Langer, J. Am. Chem. Soc. 2001, 123, 8155-8156; J. Shen, S.-W. Huang, M. Liu, R.-X. Zhou, Polymer 48 (2007) 675-681; V.V. Filipovic, B.D. Nedeljkovic, M. Vukomanivic, S. Lj. Tomic, Polymer Testing 68 (2018) 270-278; and from patent US 9 458 299 B1. Its application to unsaturated dicarboxylic acids is described in G.J. Noordzij, C.R.M.

[0006] Wilsens, Frontiers in Chemistry, November 2019, Volume 7, Article 729. Michael additions to polyesters of unsaturated polycarboxylic acids are described in TJ Farmer, JH Clark, DJ Macquarrie, JK Ogunjobi, and RL Castle, Polym. Chem., 2016, 7, 1650–1658.

[0007] The invention relates to the use of polyester-based comb polymers, obtainable by aza-Michael addition of S-substituted primary aminothiols to oligoesters of mono- or diethylenically unsaturated dicarboxylic acids and diols, for preventing the transfer of textile dyes from dyed textiles to undyed or differently colored textiles when they are washed together in aqueous solutions, in particular those containing surfactants.

[0008] S-substituted primary aminothiols are particularly those of the general formula selected in which R stands for a straight-chain or branched hydrocarbon radical having 2 to 12 C atoms or -(CR 3< R 4< -CR 3< R 4< -O) y -CR 3< R 4< -CR 3< R 4< -, in which independently of one another R 3< and R 4< stand for H or a C 1 -C 3 alkyl radical, R 1< stands for a heterocycle, in particular an N-containing heterocycle, y stands for a number from 1 to 12, in particular for a number 1 to 4, and x stands for a number from 0 to 30, in particular for a number 5 to 20, where y and x can also have non-integer values. R 1< is preferably a pyrrolidone, imidazole or pyridine N-oxide radical. Such compounds can, as can be seen in principle from SPS Koo, MM Stamenovic, RA Prasath, AJ Inglis, FE du Prez, C. Barner-Kowollik, W. van Kamp, T. Junkers, Journal of Polymer Science: Part A: Polymer Chemistry, 48, 2010, 1690-1713; AK Sinha, D. Equbal, Asian J. Org. Chem. 2019, 8, 32-47; and Y. Li, Y. Zhang, Q. Li, H. Li, S. Zheng, Y.Hu, Macromol. Chem. Phys. 2015, 216, 569-581, are known to be prepared by radical addition of compounds H 2 NR-SH to compounds R 1< -CH=CH 2 , whereby the latter can oligomerize or polymerize to form compounds of the given formula with x greater than 1.

[0009] In unsaturated dicarboxylic acids, the double bonds can be in the E or Z configuration. Preferred mono- or diethylenically unsaturated dicarboxylic acids are maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, muconic acid, and mixtures thereof. Monoethylenically unsaturated dicarboxylic acids are preferably used.

[0010] Preferred diols are selected from those of the general formula HO-CHR'-A-CHR'-OH, in which A stands for -(CR 1< R 2< ) m - or -((CR 5< R 6< ) p -O-(CR 5< R 6< ) q ) n -, in which, independently of one another, R 1< and R 2< are H or a C 1 -C 12 alkyl radical, R 5< and R 6< are H or a C 1 -C 3 alkyl radical, R' is H or a methyl radical, m is a number from 0 to 10, n is a number from 0 to 30 and, independently of one another, p and q are numbers from 1 to 3, where m, n, p and q can also have non-integer values ​​when using diol mixtures. R 1< and / or R 2< and / or R 5< and / or R 6< is preferably H or an alkyl radical having 1 to 3 carbon atoms. R' is preferably H. Preferably, m is a number in the range from 1 to 4, and / or n is a number in the range from 2 to 4.

[0011] The dicarboxylic acids and diols mentioned can be esterified with one another by known processes, preferably using equimolar amounts of dicarboxylic acid and diol, so that the resulting oligoester has, on average, the same number of carboxylic acid end groups as hydroxyl end groups. However, it is also possible to use more than equimolar amounts of dicarboxylic acid or diol, so that the average proportion of carboxylic acid end groups or hydroxyl end groups in the resulting oligoester increases and, in extreme cases, reaches 100%. The degree of oligomerization z in the oligoesters is preferably in the range from 1 to 30, particularly preferably from 2 to 30, and even more preferably from 5 to 15, and, as a quantity to be determined analytically, can also assume non-integer values.

[0012] The S-substituted primary aminothiols mentioned can be added to the esters according to the literature procedures cited above or based on these. When using itaconic acid (R 2< = CH 2 ) or maleic acid (R 2< = direct bond), for example, polyester-based comb polymers of the formula where R, R 1< , R', A, x, and z have the meanings given above. By simultaneously using various S-substituted primary aminothiols, for example, aminoalkylpyrrolidone and aminoalkylimidazole compounds, in the 1,4-addition, target compounds can be obtained in which the substitution units, for example, the aminoalkylpyrrolidone and aminoalkylimidazole residues, are present in a statistical distribution.

[0013] The active ingredients thus obtainable contribute to both of the previously mentioned aspects of color constancy, i.e., they reduce both discoloration and fading, although the effect of preventing staining is most pronounced, particularly when washing white textiles. The invention therefore further relates to the use of active ingredients thus obtainable to prevent changes in the color appearance of dyed textiles, preferably those made of cotton or containing cotton, when they are washed in aqueous solutions, particularly those containing surfactants. The change in the color appearance is not to be understood as the difference between soiled and clean textiles, but rather as the difference between clean textiles before and after the washing process.The invention therefore further provides a detergent containing surfactant and other common detergent ingredients, as well as a polyester-based comb polymer as defined above, in a dye-transfer-inhibiting amount. A dye-transfer-inhibiting amount is understood to mean an amount that significantly reduces the transfer of dyes from dyed textiles to undyed or differently colored textiles when they are washed together, compared to otherwise identical conditions in the absence of the active ingredient. The dye-transfer-inhibiting active ingredients mentioned are used in detergents in amounts of 0.01 wt.% to 5 wt.%, in particular 0.05 wt.% to 1 wt.%.

[0014] The invention further provides a process for washing white or dyed textiles in surfactant-containing aqueous solutions in the presence of textiles of a different color, which process is characterized in that a surfactant-containing aqueous liquor containing a polyester-based comb polymer as defined above is used. In such a process, it is possible to wash white or undyed textiles together with the dyed textile without the white or undyed textile becoming dyed. Preferably, 0.0003 g / l to 0.16 g / l, in particular 0.0015 g / l to 0.03 g / l, of the polyester-based comb polymer as defined above is used in the aqueous liquor.

[0015] In addition to the dye transfer inhibitor mentioned, a detergent may contain conventional ingredients compatible with this component. For example, it may additionally contain another dye transfer inhibitor, preferably in amounts of 0.1 wt.% to 2 wt.%, in particular 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 have molecular weights of 15,000 to 50,000, as well as polyvinylpyrrolidones with higher molecular weights, for example, up to over 1,000,000, in particular from 1,500,000 to 4,000,000, 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 yields hydrogen peroxide in water can also be used.The addition of a mediator compound for the peroxidase, for example, an acetosyringone, a phenol derivative, or a phenotiazine or phenoxazine, is preferred in this case, although the above-mentioned polymeric dye transfer inhibitor active ingredients can also be used additionally. For use in the compositions according to the invention, polyvinylpyrrolidone preferably has an average (weight-average) molecular weight in the range of 10,000 to 60,000, in particular 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) molecular weight in the range of 5,000 to 50,000, in particular 10,000 to 20,000, are preferred.

[0016] Detergents, which can be in the form of powdered solids, in compacted particle form, as homogeneous solutions or suspensions, can, in principle, contain all known ingredients commonly used in such detergents, in addition to the active ingredient used according to the invention. The detergents according to the invention contain ingredients selected from builders, surface-active surfactants, bleaching agents based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, and other auxiliaries, such as optical brighteners, graying inhibitors, foam regulators, as well as dyes and fragrances.

[0017] The agents according to the invention contain one or more surfactants, particularly anionic surfactants, non-ionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

[0018] Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols, each containing 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 regard to the alkyl moiety, as well as of alkylphenols with 5 to 12 carbon atoms in the alkyl radical, are also suitable.

[0019] Nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially 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. The alcohol radical can be linear or, preferably, methyl-branched in the 2-position, or can contain linear and methyl-branched radicals in a mixture, as is usually the case in oxo alcohol radicals. However, alcohol ethoxylates with linear radicals from alcohols of native origin 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, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO, or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO, or 7 EO, and mixtures thereof, such as mixtures of C 12 -C 14 alcohols with 3 EO and C 12 -C 18 alcohols with 7 EO. The stated degrees of ethoxylation represent statistical averages, which can be a whole or fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO, or 40 EO. Extremely low-foaming compounds are commonly used, especially in detergents for use in mechanical processes.These preferably include C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers, each containing up to 8 mol of ethylene oxide and propylene oxide units per molecule. However, other known low-foam nonionic surfactants can also be used, such as C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ethers, each containing up to 8 mol of ethylene oxide and butylene oxide units per molecule, as well as end-capped alkyl polyalkylene glycol mixed ethers. Hydroxyl-containing alkoxylated alcohols, so-called hydroxy mixed ethers, are also particularly preferred. The non-ionic surfactants also include alkyl glycosides of the general formula RO(G) x, in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is a glycose unit having 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 assume fractional values ​​- between 1 and 10; preferably, x is between 1.2 and 1.4. Also suitable are polyhydroxy fatty acid amides of the formula IV in which R 1< CO stands for an aliphatic acyl radical having 6 to 22 carbon atoms, R 2< stands for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] stands for a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups: . The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of formula (V), in which R 3< represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4< represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5< represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1 -C 4 alkyl or phenyl radicals being preferred, and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also preferably obtained here 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 used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated, or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides, may also be suitable.The amount of these nonionic surfactants preferably does not exceed that of the ethoxylated fatty alcohols, in particular not more than half of that. Other surfactants considered are so-called gemini surfactants. These generally refer to compounds that possess two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer." This spacer is usually a carbon chain long enough to allow the hydrophilic groups to act independently of each other. 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 refers not only to such "dimeric" surfactants, but also to corresponding "trimeric" surfactants.Suitable gemini surfactants include 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 particularly 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 include, in particular, soaps and those containing sulfate or sulfonate groups. Sulfonate-type surfactants are preferably C 9 -C 13 alkylbenzenesulfonates, olefinsulfonates, i.e., mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide followed by alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C 12 -C 18 alkanes, for example, by sulfochlorination or sulfoxidation followed by hydrolysis or neutralization.Also suitable are the esters of α-sulfofatty acids (ester sulfonates), 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 C atoms in the fatty acid molecule and subsequent neutralization to water-soluble monosalts. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel, or tallow fatty acids, although sulfonation products of unsaturated fatty acids, for example oleic acid, may also be present in small amounts, preferably in amounts not exceeding about 2 to 3 wt.%. Particularly preferred are α-sulfofatty acid alkyl esters which have an alkyl chain with no more than 4 C atoms in the ester group, for example methyl esters, ethyl esters, propyl esters, and butyl esters.The methyl esters of α-sulfofatty acids (MES), as well as their saponified disalts, are used with particular advantage. Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di-, and triesters, as well as mixtures thereof, as obtained by esterification of a monoglycerol with 1 to 3 mol of fatty acid or by transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred alk(en)yl sulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid monoesters of C 12 -C 18 fatty alcohols, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or of C 10 -C 20 oxo alcohols, and those monoesters of secondary alcohols of this chain length.Also preferred are alk(en)yl sulfates of the stated chain length, which contain a synthetic, petrochemically produced, straight-chain alkyl radical, which exhibit degradation behavior similar to that of the corresponding compounds based on oleochemical raw materials. For washing purposes, C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates, as well as C 14 -C 15 alkyl sulfates, are particularly preferred. Also suitable are the sulfuric acid monoesters of straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 -C 18 fatty alcohols with 1 to 4 EO.Preferred anionic surfactants also include the salts of alkyl sulfosuccinic acid, also known as sulfosuccinates or sulfosuccinic acid esters, and the 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, considered individually, are nonionic surfactants. Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk(en)ylsuccinic acid, preferably with 8 to 18 carbon atoms in the alk(en)yl chain, or salts thereof.Other suitable anionic surfactants include fatty acid derivatives of amino acids, for example 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. Other suitable anionic surfactants include, in particular, soaps. Particularly suitable are 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. The well-known alkenylsuccinic acid salts can also be used together with these soaps or as soap substitutes.

[0021] The 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. The anionic surfactants are preferably present in the form of their sodium or potassium salts, especially in the form of the sodium salts. Surfactants are present in detergents in amounts of normally 1% to 50% by weight, especially 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 builder substances include polycarboxylic acids, in particular citric acid and sugar acids; monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic 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 the polycarboxylates obtainable by oxidation of polysaccharides or dextrins; 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 homopolymers of unsaturated carboxylic acids is generally between 3,000 g / mol and 200,000 g / mol, and that of copolymers between 2,000 g / mol and 200,000 g / mol, preferably between 30,000 g / mol and 120,000 g / mol, in each case based on the 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 Sokalan® CP 5, CP 10, and PA 30 from BASF. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene, and styrene, in which the acid content is at least 50% by weight.Terpolymers containing two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer can also be used as water-soluble organic builders. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid, preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth)acrylic acid. The second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid substituted in the 2-position by an alkyl or aryl radical. Such polymers generally have a relative molecular mass of between 1,000 g / mol and 200,000 g / mol. Further preferred copolymers are those which have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.The organic builders can be used, particularly for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, especially their alkali metal salts.

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

[0024] Suitable water-soluble inorganic builder materials include, in particular, alkali silicates, alkali carbonates, and alkali phosphates, which may 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, in particular 5 to 50, as well as the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali aluminosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in particular in amounts of up to 50 wt.%, preferably not more than 40 wt.%, and in liquid compositions, in particular from 1 wt.% to 5 wt.%.Among these, crystalline sodium aluminosilicates of detergent quality, especially zeolite A, P, and optionally X, are preferred, 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). Amounts close to the stated upper limit are preferably used in solid, particulate agents. Suitable aluminosilicates, in particular, contain no particles with a grain size larger than 30 µm and preferably consist of at least 80 wt.% particles with a size smaller 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 aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates usable as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 of less than 0.95, in particular from 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are sodium silicates, in particular amorphous sodium silicates, with a molar Na 2 O:SiO 2 ratio of 1:2 to 1:2.8. As crystalline silicates, which can be present alone or in a mixture with amorphous silicates, crystalline layered silicates of the general formula Na 2 Si x O 2x+1 · y H 2 O are preferably used, 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 phyllosilicates are those in which x in the general formula mentioned assumes the values ​​2 or 3. In particular, both β and δ-sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred. Virtually anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali silicates, can also be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline sodium phyllosilicate with a modulus of 2 to 3 is used. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention. Crystalline phyllosilicates 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-Na 2 Si 2 O 5 ), Na-SKS-7 (ß-Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 ·3H 2 O), Na-SKS-10 (NaHSi 2 O 5 ·3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but in particular Na-SKS-6 (δ-Na 2 Si 2 O 5 ) are particularly suitable. In a preferred embodiment of the agents according to the invention, a granular compound of crystalline layered silicate and citrate, of crystalline layered silicate and the above-mentioned (co-)polymeric polycarboxylic acid, or of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion ®< 15. Builder substances are normally present in amounts up to 75% by weight, especially 5% to 50% by weight.

[0026] Peroxygen compounds suitable for use in detergents include, in particular, organic peracids or peracidic 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 used in the form of powders or granules, which can also be coated in a manner known in principle. If a detergent according to the invention contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, 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] Bleach activators that can be used are compounds that, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those that carry O- and / or N-acyl groups with the stated number of carbon atoms and / or optionally substituted benzoyl groups.Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxo-xahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, enol esters and 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 acyl acetals and acyl lactams are also preferred. Combinations of conventional bleach activators can also be used. Such bleach activators can be present, particularly in the presence of the above-mentioned hydrogen peroxide-providing bleaching agents, in the usual amount range, preferably in amounts of 0.5 wt.% to 10 wt.%, in particular 1 wt.% to 8 wt.%, based on the total composition. However, they are preferably completely absent when percarboxylic acid is used as the sole bleaching agent.

[0028] In addition to the conventional bleach activators or instead of them, 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 detergents include those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases, and peroxidases, as well as mixtures thereof. Enzymatic active ingredients 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 carriers 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 of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the agent 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 agent according to the invention, this can be done by incorporating two or more separate enzymes or enzymes prepared separately in a known manner or by two or more enzymes prepared together in one granulate.

[0030] The organic solvents that can be used in addition to water in the detergents, especially when they are in liquid or pasty form, 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; and mixtures thereof and the ethers derived from the aforementioned classes of compounds. Such water-miscible solvents are preferably present in the detergents according to the invention in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.

[0031] To adjust a desired pH value that does not arise automatically from the mixing of the other components, the agents 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 agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

[0032] The purpose of graying inhibitors is to keep the dirt detached from the textile fibers suspended in the liquor. Suitable for this purpose are water-soluble colloids, usually of an organic nature, 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 for this purpose. Starch derivatives other than those mentioned above can also be used, for example, aldehyde starches. Preference is given to cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the agent.

[0033] Detergents can contain, for example, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts as optical brighteners, 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 carry a diethanolamino group, a methylamino group, an anilino group, or a 2-methoxyethylamino group instead of the morpholino group. Furthermore, brighteners of the substituted diphenylstyryl type may be present, for example, the alkali metal 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 can also be used.

[0034] Particularly when used in mechanical 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 contain a high proportion of C 18 -C 24 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 bisfatty acid alkylenediamides. Mixtures of different foam inhibitors, for example, those made of silicones, paraffins, or waxes, are also advantageously used. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or water-dispersible carrier substance.In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

[0035] The production of solid formulations presents no difficulties and can be carried out in a known manner, for example, by spray drying or granulation, with enzymes and any other thermally sensitive ingredients, such as bleaching agents, being added separately later if necessary. For the production of formulations with 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 tablets, which may be single-phase or multi-phase, single-colored or multi-colored, and in particular consist of one or more layers, in particular two layers, the preferred procedure is to mix all the components—optionally one layer each—in a mixer and compress the mixture using conventional tablet presses, for example eccentric presses or rotary presses, with compression forces in the range of approximately 50 to 100 kN, preferably 60 to 70 kN. Particularly in the case of multi-layer tablets, it can be advantageous if at least one layer is pre-compressed. This is preferably carried out at compression forces between 5 and 20 kN, in particular 10 to 15 kN. This yields tablets which are readily break-resistant and yet dissolve sufficiently quickly under application conditions, with breaking and flexural strengths of normally 100 to 200 N, but preferably above 150 N.A tablet produced in this way preferably has a weight of 10 g to 50 g, in particular of 15 g to 40 g. The three-dimensional shape of the tablets is arbitrary and can be round, oval, or square, although intermediate shapes are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of square or cuboid-shaped 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), in particular of 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 added in substance or as a solution into an automatic mixer. Examples Example 1: Preparation of a polyester-based comb polymer (P1) based on 1-vinylimidazole a) Production of an unsaturated polyester (PE1)

[0038] 11.6 g of maleic acid, 6.3 g of ethylene glycol, and 48.5 mg of p-toluenesulfonic acid in 100 ml of toluene were stirred under reflux for 5 hours, and the resulting water of reaction was distilled off. After cooling to room temperature, the supernatant toluene was decanted, and the remaining solvent was removed at 40°C under reduced pressure. Yield: 14.6 g (82% of theory) GPC in water: M n 700 g / mol, M w 1000 g / mol b) Preparation of an amino-functionalized prepolymer (PP1)

[0039] 671 mg of 2,2'-azobis[2-methylpropionamidine] dihydrochloride were added to 1.57 g of cysteamine and 19 g of 1-vinylimidazole in 60 ml of water. The mixture was degassed by bubbling with nitrogen. It was stirred overnight at 75°C. After cooling to room temperature, it was poured into 500 ml of tetrahydrofuran (THF), thereby precipitating the product. The solvent was decanted off, and the resulting prepolymer was dried overnight at 40°C in a vacuum drying oven. Yield: 11.7 g (54% of theory) GPC in water: M n 650 g / mol, M w 3000 g / mol c) Production of the polyester-based comb polymer (P1)

[0040] A solution of 0.5 g of the unsaturated polyester PE1 from Example 1a) and 5.28 g of the prepolymer PP1 from Example 1b) in 30 ml of dry dimethyl sulfoxide (DMSO) was stirred at 100°C for 1 week. It was then cooled to room temperature, and the product was precipitated in 300 ml of diethyl ether. The resulting polymer was dried in a vacuum drying oven. Yield: 7.8 g GPC in water: M n 700 g / mol, M w : 3500 g / mol Example 2: Preparation of a polyester-based comb polymer (P2) based on 1-vinylimidazole and N-vinylpyrrolidone a) Preparation of an amino-functionalized prepolymer (PP2)

[0041] 671 mg of 2,2'-azobis[2-methylpropionamidine] dihydrochloride were added to 1.57 g of cysteamine, 11.34 g of N-vinylpyrrolidone, and 9.5 g of 1-vinylimidazole in 60 ml of water. The mixture was degassed by bubbling with nitrogen. It was stirred overnight at 75°C. It was then cooled to room temperature and precipitated in 1000 ml of THF. The solvent was decanted off, and the resulting polymer was dried for 60 hours at 40°C in a vacuum oven. Yield: 18.3 g (82% of theory) GPC in water: M n 2000 g / mol, M w 14000 g / mol b) Production of the polyester-based comb polymer (P2)

[0042] A solution of 0.5 g of the unsaturated polyester PE1 from Example 1a) and 5.28 g of the prepolymer PP2 from Example 2a) in 30 ml of dry DMSO was stirred at 100°C for 1 week. It was then cooled to room temperature, and the product was precipitated in 300 ml of diethyl ether. The resulting polymer was dried in a vacuum drying oven. Yield: 8.0 g GPC in water: M n 2000 g / mol, M w 16000 g / mol Example 3: Color inhibition inhibition

[0043] The dyes listed in the table below (dyed textiles that readily release dye) were washed in the presence of white cotton acceptor fabric (6 cm x 16 cm; Wfk 11 A) and polyamide acceptor fabric (FA Swissatest (406)) at 60°C for 30 minutes. The dyeing of the cotton or polyamide textile was then determined spectrophotometrically and evaluated according to ISO 105 A04 (SSR ratings on a scale of 1 to 5, 1 = strong dyeing, 5 = no dyeing). Wash liquors containing a dye transfer inhibitor-free, aqueous liquid detergent (F; concentration 3.5 g / l) or with equal amounts of otherwise identically composed detergents were used, to which one of the polymers P1 or P2 prepared in Examples 1 and 2 had been added, reducing the amount of water. The following SSR ratings were obtained (each an average of two determinations): Table 1: Results of color inhibition Acceptor Color generator F F+ P1 F+ P 2 Cotton Direct Red 83:1, EMPA 3,0 4,9 4,9 Cotton Direct Black 22, EMPA 3,7 3,8 4,3 Polyamide Direct Black 22, EMPA 3,6 4,1 4,6 Polyamide Direct Orange 39; EMPA 2,6 3,3 3,4

[0044] It can be seen that, compared to the detergent without the addition of the polyester-based comb polymers essential to the invention, the white textiles were less strongly stained when washed with the polyester-based comb polymer additive.

Claims

1. A use of polyester-based comb polymers, obtained by aza-Michael addition of S-substituted primary aminothiols to oligoesters of mono- or diethylenically unsaturated dicarboxylic acids and diols, in order to prevent the transfer of textile dyes from dyed textiles onto undyed textiles or textiles of other colors when washed together in, in particular surfactant-containing, aqueous solutions.

2. A use of polyester-based comb polymers, obtained by aza-Michael addition of S-substituted primary aminothiols to oligoesters of mono- or diethylenically unsaturated dicarboxylic acids and diols, in order to prevent the color impression of dyed textiles from changing when washed in, in particular surfactant-containing, aqueous solutions.

3. A method for washing white or dyed textiles in surfactant-containing aqueous solutions in the presence of textiles of other colors, characterized in that a surfactant-containing aqueous liquor is used which contains a polyester-based comb polymer obtained by aza-Michael addition of S-substituted primary aminothiols to oligoesters of mono- or diethylenically unsaturated dicarboxylic acids and diols.

4. The method according to claim 3, characterized in that 0.0003 g / l to 0.16 g / l, in particular 0.0015 g / l to 0.03 g / l, of the polyester-based comb polymer is used in the aqueous liquor.

5. A washing agent containing surfactant and other conventional washing-agent ingredients, characterized in that it contains a polyester-based comb polymer, obtained by aza-Michael addition of S-substituted primary aminothiols to oligoesters of mono- or diethylenically unsaturated dicarboxylic acids and diols, in a dye transfer-inhibiting amount, the other conventional ingredients of washing agents being selected from builder substances, surface-active surfactants, bleaching agents based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, optical brighteners, graying inhibitors, foam regulators, and dyes and fragrances, and the amount of polyester-based comb polymer being from 0.01 wt.% to 5 wt.%, based on the total washing agent.

6. The agent according to claim 5, characterized in that it contains the polyester-based comb polymer in amounts of from 0.05 wt.% to 1 wt.%.

7. The agent according to claim 5 or 6, characterized in that it additionally contains a further dye transfer inhibitor selected from the polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine N-oxide, or the copolymers thereof.

8. The use according to claim 1 or 2, the method according to claim 3 or 4, or the agent according to one of claims 5 to 7, characterized in that the S-substituted primary aminothiols are selected from those of general formula in which R represents a straight-chain or branched hydrocarbon group having 2 to 12 C atoms or -(CR3R4- CR3R4-O)y-CR3R4-CR3R4-, in which R3 and R4 represent, independently of one another, H or a C1-C3 alkyl group, R1 represents a heterocycle, in particular an N-containing heterocycle, y represents a number from 1 to 12, in particular a number from 1 to 4, and x represents a number from 0 to 30, in particular a number from 5 to 20, where y and x can also have non-integer values; and / or characterized in that the mono- or diethylenically unsaturated dicarboxylic acids are selected from maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, muconic acid and mixtures thereof; and / or characterized in that the diols are selected from those of general formula HO-CHR'-A-CHR'-OH, in which A represents -(CR1R2)m- or - ((CR5R6)p-O-(CR5R6)q)n-, in which R1 and R2 represent, independently of one another, H or a C1-C12 alkyl group, R5 and R6 represent H or a C1-C3 alkyl group, R' represents H or a methyl group, m represents a number from 0 to 10, n represents a number from 0 to 30, and p and q represent, independently of one another, numbers from 1 to 3, and where m, n, p and q can also have non-integer values when diol mixtures are used.

9. The use, method or agent according to claim 8, characterized in that the polyester-based comb polymer has the general formula 10. The use, method or agent according to claim 8 or 9, characterized in that the heterocycle R1 is selected from imidazole and pyrrolidone and mixtures thereof.

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