DE102012219403A1 - Use of metal ion chelates obtained by polymerization of monoethylenically unsaturated mono-or di-carboxylic polymers to e.g. prevent the transfer of textile dyes from dyed textiles to undyed textiles, or other color in the common laundry - Google Patents

Abstract

Use of metal ion chelates obtained by the polymerization of monoethylenically unsaturated mono-or di-carboxylic polymers to prevent the transfer of textile dyes from dyed textiles to undyed textiles or other color in the common laundry, preferably aqueous solution containing surfactant, and prevent the change of the color impression of colored textiles with the laundry, is claimed. Independent claims are also included for: (1) washing textiles using aqueous solution containing surfactant that contains the metal ion chelates; and (2) a laundry detergent comprising a color transfer inhibitor in the form of the metal ion chelate.

Description

The present invention relates to the use of certain polymer / metal ion chelates as dye transfer inhibiting agents in the washing of fabrics and detergents containing these polymer / metal ion chelates.

In addition to the ingredients indispensable for the washing process, such as surfactants and builders, detergents generally contain further constituents, which can be summarized by the term washing aids and which comprise such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and enzymes. Such auxiliaries also include substances which are intended to prevent dyed textiles from causing a changed color impression after washing. This color impression change washed, i. Cleaner, textiles can be based on the fact that dye components are removed by the washing process from the textile ("fading"), on the other hand, from other colored textiles detached dyes on the textile precipitate ("discoloration"). The discoloration aspect may also play a role in undyed laundry items when washed together with colored laundry items. In order to avoid these undesirable side effects of removing dirt from textiles by treatment with usually surfactant-containing aqueous systems, detergents, especially if they are provided as so-called color or colored laundry detergents for colored textiles, contain active ingredients which prevent the detachment of dyes from the textile or At least the deposition of detached, located in the wash liquor to avoid dyes on textiles. Many of the commonly used polymers have such a high affinity for dyes that they draw them more from the dyed fiber, resulting in increased color losses.

From the European patent application EP 0 262 897 are color transfer-preventing polyvinylpyrrolidones having molecular weights of from 15,000 g / mol to 50,000 g / mol and from the international patent application WO 95/06098 are known those with molecular weights above 1 000 000 g / mol. As color transfer-preventing active ingredients are also from the German patent applications DE 28 14 287 or DE 38 03 630 or the international patent applications WO 94/10281 . WO 94/26796 . WO 95/03388 and WO 95/03382 known N-vinylimidazole / N-vinylpyrrolidone copolymers, which are known from the German patent application DE 28 14 329 Polyvinyloxazolidone known from the European patent application EP 610 846 known copolymers based on vinyl monomers and carboxylic acid amides, which are known from international patent application WO 95/09194 known pyrrolidone group-containing polyesters and polyamides which are known from the international patent application WO 94/29422 known grafted polyamidoamines and polyethyleneimines, from the German patent application DE 43 28 254 known polymers with amide groups from secondary amines, and those from the international patent application WO 94/02579 or the European patent application EP 0 135 217 known polyamine N-oxide polymers have been proposed.

Surprisingly, it has now been found that certain polymer / metal ion chelates defined below result in unexpectedly high color transfer inhibition when used in detergents. Particularly pronounced is the prevention of dyeing of white or other colored fabrics by washed out of textiles dyes.

The invention relates to the use of metal ion chelates of polymers obtainable by the polymerization of monoethylenically unsaturated mono- or dicarboxylic acids to prevent the transfer of textile dyes from dyed textiles to undyed or differently colored textiles in their common washing in particular surfactant-containing aqueous solutions.

For the preparation of the polymers, preference is given to using acrylic acid, methacrylic acid, maleic acid, itaconic acid or salts, in particular alkali metal salts, of these acids, maleic anhydride, carboxyethyl acrylate, and mixtures of these. If desired, additional hydrophilic monoethylenically unsaturated monomers, such as, for example, acrylamide and / or methacrylamide, may be used in addition to these. The polymers may be homopolymers of a monoethylenically unsaturated mono- or dicarboxylic acid or have as copolymers a plurality of different monomers. In addition, optionally a crosslinking monomer may be present which is polyunsaturated, in particular at least 2-fold, ethylenically unsaturated. Useful difunctionally crosslinking monomers include, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and N, N'-methylenebisacrylamide. The proportion of the crosslinking monomer, based on the polymer, can be up to 20 mol% and is preferably in the range of 0.01 mol% to 15 mol%, in particular less than 10 mol%, with the remainder being 100 mol -% of the monoethylenically unsaturated monomer or monoethylenically unsaturated monomers are formed. Useful polymers are also those from the polymerization of the alkyl esters, in particular the methyl or ethyl esters, mentioned monoethylenically unsaturated carboxylic acids, in particular acrylic acid or methacrylic acid, and subsequent polymer-analogous reaction with hydroxylamine accessible polyhydroxamic acids. The average molecular weight of the polymers is preferably in the range from 1000 g / mol to 150 000 g / mol, in particular from 1100 g / mol to 30 000 g / mol. The mean molar masses indicated here and later, if appropriate, for other polymeric ingredients are weight-average molar masses M _w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement being expediently carried out against an external standard.

The said polymers form chelates upon addition of metal ions, and for the purposes of the present invention preferred metal ions are selected from the group comprising Zn ²⁺ , Mg ²⁺ , Ca ²⁺ , Fe ²⁺ , Al ³⁺ , Fe ³⁺ , Ti ⁴⁺ and mixtures thereof are selected.

Polymer / metal ion chelates used according to the invention preferably have 0.01% by weight to 30% by weight, in particular 1% by weight to 15% by weight, of metal ions and 70% by weight to 99.99% by weight. , in particular 85 wt .-% to 99 wt .-% polymer.

The color transfer-inhibiting chelates contribute to both of the above-mentioned aspects of color constancy, that is, they reduce both discoloration and fading, although the effect of preventing staining, especially when washing white textiles, is most pronounced. Further objects of the invention are therefore the use of said metal ion chelates to avoid the change in the color impression of textiles in their washing in particular surfactant-containing aqueous solutions, and detergents containing said metal ion chelates. The change in the color impression is not the difference between dirty and clean textile to understand, but the difference between each clean textile before and after the washing process. A further advantage is that the above-mentioned metal ion chelates have a particularly pronounced color-protecting effect on polyamide textiles and prevent dyeing of polyamide or polyamide-containing textiles. The color transfer inhibitors according to the invention are therefore preferably used to avoid the color transfer to textiles made of polyamide or with polyamide content.

Another object of the invention is a process for washing dyed textiles in surfactant-containing aqueous solutions, which is characterized in that one uses a surfactant-containing aqueous solution containing a said metal ion chelate. In such a method, it is possible to wash white or undyed textiles together with the dyed textile without the white or undyed textile being dyed.

A detergent can, in addition to the said color transfer-inhibiting metal ion chelate, which it preferably contains in amounts of 0.01 wt .-% to 10 wt .-%, in particular 0.1 wt .-% to 3 wt .-%, preferably conventional Contain compatible ingredients in this ingredient. Thus, it may, for example, additionally contain a further color transfer inhibitor, then preferably in amounts of 0.1 wt .-% to 2 wt .-%, in particular 0.2 wt .-% to 1 wt .-%, containing in one preferred embodiment is selected from the polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or the copolymers thereof. Useful are both polyvinylpyrrolidones having molecular weights of from 15,000 g / mol to 50,000 g / mol and also polyvinylpyrrolidones having higher molecular weights of, for example, up to more than 1,000,000 g / mol, in particular from 1,500,000 g / mol to 4,000,000 g / mol, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers and carboxamides, pyrrolidone group-containing polyesters and polyamides, grafted polyamidoamines and polyethyleneimines, polyamine-N-oxide polymers and polyvinyl alcohols. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which gives hydrogen peroxide in water. 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, whereby also above-mentioned polymeric Farbübertragungsinhibitorwirkstoffe can be used. Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10,000 g / mol to 60,000 g / mol, in particular in the range from 25,000 g / mol to 50,000 g / mol. Among the copolymers, preference is given to those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 with an average molar mass in the range from 5,000 g / mol to 50,000 g / mol, in particular 10,000 g / mol to 20,000 g / mol , In preferred embodiments, however, the detergents are free of such additional color transfer inhibitors.

Detergents, which may be in the form of homogeneous solutions or suspensions in particular as pulverulent solids, in densified particle form, may be used apart from those used according to the invention Active ingredient in principle all known and customary in such agents ingredients. The agents according to the invention may in particular be builders, surface-active surfactants, bleaches 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, grayness inhibitors, foam regulators and colorants Contain fragrances.

The compositions preferably comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.

in der R¹CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The 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 of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 EO and C ₁₂ -C ₁₈ -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. 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. In particular, agents for use in mechanical processes usually extremely low-foam compounds are used. These include preferably C ₁₂ -C ₁₈ -alkylpolyethylenglykol-polypropylene glycol ethers with in each case at to 8 mol ethylene oxide and propylene oxide units in the molecule. One can also use other known low-foaming nonionic surfactants such as C ₁₂ -C ₁₈ alkyl polyethylene glycol polybutylene each having up to 8 moles of ethylene oxide and butylene oxide units in the molecule and end-capped Alkylpolyalkylenglykolmischether. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, so-called hydroxy mixed ethers. The nonionic 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 carbon atoms and G represents 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 an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula

in the R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.

in der R³ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁴ für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R⁵ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nicht-ionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im Allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten „Spacer“ voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, dass die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich im Allgemeinen durch eine ungewöhnlich geringe kritische Micellkonzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. In Ausnahmefällen werden unter dem Ausdruck Gemini-Tenside nicht nur derartig „dimere“, sondern auch entsprechend „trimere“ Tenside verstanden. Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate. Endgruppenverschlossene dimere und trimere Mischether zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so dass sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen. Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide. The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula

in the R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 is} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C ₁ -C ₄ alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] is also obtained here preferably 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 catalyst. Another class of preferred nonionic surfactants 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof. Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants not only such "dimer", but also corresponding to "trimeric" surfactants understood. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. As surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, Olefinsulfonate, that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C ₁₂ -C ₁₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C -Atomen in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are prepared, into consideration. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, although sulfonated products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of α-sulfo fatty acids (MES), but also their saponified disalts are used. Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Examples of alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length which are a synthetic, petrochemical-based contain straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing-technical interest, C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and C ₁₄ -C ₁₅ -alkyl sulfates are particularly preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of Shell Oil Company under the name DAN ^® , are suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of straight-chain or branched C ₇ -C ₂₁ -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols having on average 3.5 mol of ethylene oxide (EO) or C ₁₂ - C ₁₈ -fatty alcohols with 1 to 4 EO. The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate. As further anionic surfactants are particularly soaps into consideration. 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 and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.

The anionic surfactants, including soaps, may be in the form of their sodium, potassium or ammonium salts and 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, in particular in the form of the sodium salts. Surfactants are present in detergents in proportions of normally from 1% by weight to 50% by weight, in particular from 5% by weight to 30% by weight.

A detergent preferably contains at least one detergent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid) , Ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (poly) carboxylic acids, in particular polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative average molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. As water-soluble organic builders, it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) -acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight Vinyl alcohol and / or vinyl acetate. Very particular preference is given to polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose. The use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation 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, in particular their alkali metal salts.

If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.

Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate. As water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used. Among these, the detergent-grade crystalline sodium aluminosilicates, particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.

In addition to or as an alternative to said water-insoluble aluminosilicate and alkali carbonate, further water-soluble inorganic builder materials may be included. In addition to the polyphosphates, such as sodium triphosphate, these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably present in the compositions in amounts of from 1% to 20% by weight, in particular from 5% to 15% by weight. The alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x O used _{2x + 1} · y H ₂ O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in the compositions. In a further preferred embodiment, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Sodium silicates with a modulus in the range 1.9 to 3.5 are used in a further embodiment. In a preferred embodiment of such means is a granular compound of alkali metal silicate and alkali, such as is available, for example under the name Nabion ^® 15 commercially.

Suitable bleaching agents are those based on chlorine, in particular alkali hypochlorite, dichloroisocyanuric acid, trichloroisocyanuric acid and salts thereof, but especially those based on peroxygen Question. Suitable peroxygen compounds are, in particular, organic peracids or persaltic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid, and diperdodecanedioic acid and salts thereof, such as magnesium monoperoxyphthalate, hydrogen peroxide and inorganic salts releasing hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide. Inclusion compounds, such as H ₂ O ₂ -urea adducts, into consideration. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. If a detergent contains peroxygen compounds, they are present in amounts of preferably up to 25% by weight, more preferably from 1% to 20% and most preferably from 7% to 20% by weight.

As bleach-activating peroxycarboxylic acid-yielding compound under perhydrolysis conditions, it is possible in particular to use compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, alone or in mixtures. Suitable bleach activators which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, especially nonanoyl or Isononanoyl- or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), their formal carbonic ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benzenesulfonate (DECOBS), acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose, acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_1-24-Alkyl- oder C_2-24-Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN und -N⁽⁺⁾-CH₂-CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit mindestens einer, vorzugsweise zwei, gegebenenfalls substituierten C_1-24-Alkylgruppe(n) und gegebenenfalls weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6, R⁴ und R⁵ unabhängig voneinander eine voranstehend für R¹, R² oder R³ angegebene Bedeutung haben, wobei mindestens 2 der genannten Reste, insbesondere R² und R³, auch unter Einschluß des Stickstoffatoms und gegebenenfalls weiterer Heteroatome ringschließend miteinander verknüpft sein können und dann vorzugsweise einen Morpholino-Ring ausbilden, und X(^–) ein ladungsausgleichendes Anion, vorzugsweise ausgewählt aus Benzolsulfonat, Toluolsulfonat, Cumolsulfonat, den C_9-15-Alkylbenzolsulfonaten, den C_1-20-Alkylsulfaten, den C_8-22-Carbonsäuremethylestersulfonaten, Sulfat, Hydrogensulfat und deren Gemischen, ist, können eingesetzt werden. Auch sauerstoffübertragende Sulfonimine und/oder Acylhydrazone können eingesetzt werden. In addition to the compounds that form peroxycarboxylic acids under perhydrolysis conditions, other bleach-activating compounds, such as nitriles, from which perimide acids form under perhydrolysis conditions may be present. These include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 -alkyl or alkenyl radical, a substituted C _1-24 -alkyl or C _2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN and -N ⁽⁺⁾ -CH ₂ -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or a substituted alkyl- or alkenylaryl radical having at least one, preferably two, optionally substituted C _1-24 alkyl group (s) and optionally further substituents on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another have the meaning given above for R ¹ , R ² or R ³ , where at least 2 of the radicals mentioned, in particular R ² and R ³ , also include the Nitrogen atom and optionally further heteroatoms ring-closing linked together and then preferably form a morpholino ring, and X ( ^- ) a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, Cumolsulfonat, the C _9-15 -alkylbenzenesulfonates, the C _1-20 Alkyl sulfates, the C _8-22 -Carbonsäuremethylestersulfonaten, sulfate, hydrogen sulfate and mixtures thereof, can be used. Oxygen-carrying sulfonimines and / or acylhydrazones can also be used.

The presence of bleach-catalyzing transition metal complexes is also possible. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Suitable ligands in such transition metal complexes are both inorganic and also organic compounds in question, in addition to carboxylates in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, triazole, 2,2'-bispyridylamine , Tris (2-pyridylmethyl) amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane, (Bis ((1-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl) amine, N, N'- (bis (1-methylimidazol-2-yl) methyl) ethylenediamine, N Bis- (2-benzimidazolylmethyl) aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, N, N, N ', N'-tetrakis- (2-benzimidazolylmethyl) - 2-hydroxy-1,3-diaminopropane, 2,6-bis (bis (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1,3-bis (bis (2-benzimidazolylmethyl) aminomethyl) benzene, Sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and optionally substituted salene, porphins, and porphyrins. The inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO ₂ ) ^- group, that is, a nitro ligand or a nitrito ligand. The (NO ₂ ) ^- group may also be chelated to a transition metal, or it may bridge two transition metal atoms asymmetrically or η ¹ -O-bridge. In addition to the ligands mentioned, the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands. In question, for example, nitrate, actetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate. The anion ligands should provide charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. In particular, such ligands can also act bridging, so that polynuclear complexes arise. In the case of bridged, dinuclear complexes, both metal atoms in the complex need not be the same. The use of binuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands are missing or the presence of anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds to be used according to the invention. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate. Examples of transition metal complex compounds that can be used are Mn (IV) ₂ (μ-O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) -di-hexafluorophosphate, [N, N'-bis [(2 -hydroxy-5-vinylphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1,2 diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-phenylenediamine] manganese (III) acetate, [N, N'- Bis [(2-hydroxyphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-diaminoethane] - manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-sulfonatophenyl) methylene] -1,2-diaminoethane] manganese (III) chloride, manganese oxalato complexes, nitropentammine cobalt ( III) chloride, nitrite pentammine cobalt (III) chloride, hexammine cobalt (III) chloride, chloropentammine cobalt (III) chloride and the peroxo complex [(NH ₃ ) ₅ Co-OO-Co (NH ₃ ) ₅ ] Cl ₄ .

Suitable enzymes which can be used in the compositions are those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable are 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 derived enzymatic agents. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the detergents or cleaners 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 of 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 8000 PE / g. If several enzymes are to be used in the agent according to the invention, this can be carried out by incorporation of the two or more separate or in a known manner separately prepared enzymes or by two or more enzymes formulated together in a granule.

Among the detergents, in particular when they are in liquid or pasty form, usable organic solvents in addition to water include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C Atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the said classes of compounds ethers. Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.

In order to establish a desired pH, which does not result from the mixture 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 metal hydroxides. Such pH regulators are present in the compositions 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.

Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.

Detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents. Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene 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). Mixtures of the aforementioned optical brightener can be used.

In particular, when used in mechanical processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

The preparation of solid agents presents no difficulties and may be accomplished in a known manner, for example by spray-drying or granulation, with enzymes and any other thermally-sensitive ingredients, such as bleach, optionally added separately later. For the production of compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of compositions in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers, the procedure is preferably such that all components - optionally one layer at a time - in a mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN. Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant, yet sufficiently rapidly soluble tablets under application conditions with fracture and flexural strengths of normally 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, in particular 15 g up to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms 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 rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device of the washing machine, is dependent on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) × (34 to 40 mm), in particular of 26 × 36 mm or of 24 × 38 mm.

Liquid or pasty compositions in the form of conventional solvent-containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

Examples

Example 1: Preparation of polymers

A) Preparation of crosslinked polymethacrylic acid

0.23 g of azobis (isobutyronitrile), 8.1 g of ethylene glycol dimethacrylate and 1.36 g of methacrylic acid were dissolved in 200 ml of DMF (dimethylformamide). The solution was degassed and the temperature raised to 75 ° C. The polymerization was carried out for 12 hours under a nitrogen atmosphere. DMF was concentrated, the polymer was slurried in acetone, passed through a frit, washed with hot water, suction filtered and dried.

B) Preparation of crosslinked polyacrylic acid

0.2 g of azobis (isobutyronitrile, 8.1 g of ethylene glycol dimethacrylate and 0.57 g of acrylic acid were dissolved in 200 ml of DMF, the solution was degassed and the temperature was raised to 75 ° C. The polymerization was carried out for 12 hours under a nitrogen atmosphere DMF was concentrated, the polymer was slurried in acetone, passed through a frit, washed with hot water, suction filtered and dried.

C) Preparation of crosslinked polycarboxyethyl acrylate

0.2 g of azobis (isobutyronitrile), 8.1 g of ethylene glycol dimethacrylate and 1.15 g of methacrylic acid were dissolved in 200 ml of DMF. The solution was degassed and the temperature raised to 75 ° C. The polymerization was carried out for 12 hours under a nitrogen atmosphere. DMF was concentrated, the polymer was slurried in acetone, passed through a frit, washed with hot water, suction filtered and dried.

D) Preparation of crosslinked polyitaconic acid

0.2 g of azobis (isobutyronitrile), 8.1 g of ethylene glycol dimethacrylate and 1.04 g of itaconic acid are dissolved in 200 ml of DMF. The solution is degassed and the temperature raised to 75 ° C. The polymerization is carried out for 12 hours under nitrogen atmosphere. DMF is concentrated, the polymer is slurried in acetone, added via frit, washed with hot water, filtered off with suction and dried.

Example 2: Preparation of polymer / metal ion chelates

A) Preparation of the Zn-chelate of crosslinked polymethacrylic acid

4.0 g of crosslinked polymethacrylic acid (Example 1, A) were taken up in water. 8.0 g of ZnCl ₂ were added portionwise, the pH was maintained at 4. The mixture was stirred overnight at room temperature, the chelate was then filtered off with suction and dried. The zinc content of the chelate was determined by elemental analysis to be 1.4% by weight.

B) Preparation of the Zn-chelate of crosslinked polyacrylic acid

4.4 g of crosslinked polyacrylic acid (Example 1, B) were taken up in water. 8.8 g of ZnCl ₂ were added in portions, the pH was maintained at 4. The mixture became overnight stirred at room temperature, the chelate was then filtered off with suction and dried. The zinc content of the chelate was determined by elemental analysis to be 3% by weight.

C) Preparation of the Zn-chelate of cross-linked polycarboxyethyl acrylate

4.5 g of crosslinked polycarboxyethyl acrylate (Example 1, C) were taken up in water. 9.0 g of ZnCl ₂ were added portionwise, the pH was maintained at 4. The mixture was stirred overnight at room temperature, the chelate was then filtered off with suction and dried. The zinc content of the chelate was determined by elemental analysis to be 6.1% by weight.

D) Preparation of the Zn-chelate of crosslinked polyitaconic acid

4.0 g of crosslinked polyitaconic acid (Example 1, D) were taken up in water. 8.0 g of ZnCl ₂ were added portionwise, the pH was maintained at 4. The mixture was stirred overnight at room temperature, the chelate was then filtered off with suction and dried. The zinc content of the chelate was determined by elemental analysis to be 1.5% by weight

Example 3: Color transfer inhibition

The colorants given in the table below (dyed textiles which readily give off dye) were washed in the Linitester (Atlas) in the presence of white polyamide acceptor tissue at 60 ° C. for 30 minutes ( ISO 105 C06 ). Parameters: 100 ml wash liquor, polyester color donor tissue (Disperse blue 2g, Disperse red 1g), acceptor tissue each 6 cm × 16 cm. Thereafter, the staining of the polyamide textiles was determined spectrophotometrically and after ISO 105 A04 evaluated (SSR scores on a scale of 1 to 5, 1 = strong staining, 5 = no staining). The following SSR scores were obtained (mean value from 8-fold determination (2 external replicates, 4 measuring points each)). Was used a color transfer inhibitor-free detergent WM and the same detergent to which each had the specified in the table amount (wt .-%) of one of the polymers or polymer / metal ion chelates prepared in Examples 1 and 2 added. Disperse Red Disperse Blue WM 3.9 3.2 WM + 10% 1A 3.6 3.5 WM + 10% 2A 4.0 4.2 WM + 10% 1B 4.0 4.2 WM + 10% 2B 4.4 4.4 WM + 10% 1C 3.9 4.1 WM + 10% 2C 4.0 4.3 WM + 10% 1D 4.1 4.0 WM + 10% 2D 4.2 4.4

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 0262897 [0003]
• WO 95/06098 [0003]
• DE 2814287 [0003]
• DE 3803630 [0003]
• WO 94/10281 [0003]
• WO 94/26796 [0003]
• WO 95/03388 [0003]
• WO 95/03382 [0003]
• DE 2814329 [0003]
• EP 610846 [0003]
• WO 95/09194 [0003]
• WO 94/29422 [0003]
• DE 4328254 [0003]
• WO 94/02579 [0003]
• EP 0135217 [0003]

Cited non-patent literature

• ISO 105 C06 [0044]
• ISO 105 A04 [0044]

Claims (10)

 Use of metal ion chelates of polymers obtainable by the polymerization of monoethylenically unsaturated monocarboxylic or dicarboxylic acids to prevent the transfer of textile dyes of dyed textiles to undyed or differently colored textiles in their common washing in particular surfactant-containing aqueous solutions.  Use of metal ion chelates of polymers obtainable by the polymerization of monoethylenically unsaturated monocarboxylic or dicarboxylic acids in order to avoid the change in the color impression of dyed textiles during their washing in, in particular, surfactant-containing aqueous solutions. Use according to Claim 1 or 2, characterized in that acrylic acid, methacrylic acid, maleic acid, itaconic acid or salts, in particular alkali metal salts, of these acids, maleic anhydride, carboxyethyl acrylate and mixtures thereof are used for the preparation of the polymers. Use according to Claim 3, characterized in that additionally additional hydrophilic monoethylenically unsaturated monomers, such as acrylamide and / or methacrylamide, are used. Use according to one of Claims 1 to 4, characterized in that the polymer is a polyhydroxamic acid obtainable from the polymerization of the alkyl esters of the monoethylenically unsaturated carboxylic acids and subsequent polymer-analogous reaction with hydroxylamine. Use according to any one of claims 1 to 5, characterized in that the metal ions are selected from the group comprising Zn ²⁺ , Mg ²⁺ , Ca ²⁺ , Fe ²⁺ , Al ³⁺ , Fe ³⁺ , Ti ⁴⁺ and mixtures thereof become. Use according to one of claims 1 to 6, characterized in that the polymer / metal ion chelates have 0.01 wt .-% to 30 wt .-%, in particular 1 wt .-% to 15 wt .-% of metal ions and 70 wt .-% to 99.99 wt .-%, in particular 85 wt .-% to 99 wt .-% polymer. A process for washing textiles in surfactant-containing aqueous solutions, which comprises using a surfactant-containing aqueous solution containing metal ion chelates of polymers obtainable by the polymerization of monoethylenically unsaturated mono- or dicarboxylic acids.  Detergent containing a color transfer inhibitor in the form of a metal ion chelate of polymers obtainable by the polymerization of monoethylenically unsaturated mono- or dicarboxylic acids. Composition according to claim 9, characterized in that it contains the dye transfer inhibitor in amounts of 0.01 wt .-% to 10 wt .-%, in particular 0.1 wt .-% to 3 wt .-%.