EP0850292A1

EP0850292A1 - Colour transfer-inhibiting washing agent

Info

Publication number: EP0850292A1
Application number: EP96924815A
Authority: EP
Inventors: Peter Sandkühler; Winfried Pochandke; Eduard Smulders
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1995-07-07
Filing date: 1996-06-29
Publication date: 1998-07-01
Anticipated expiration: 2016-06-29
Also published as: ES2156285T3; ES2156285T5; WO1997003166A1; EP0850292B1; DE59606783D1; ATE200513T1; DE19524451A1; EP0850292B2

Abstract

The invention concerns colour transfer-inhibiting washing agents whose object is to optimize the washing process by minimizing colour transfer, maximizing colour shade maintenance and maximizing cleaning performance. This object is substantially achieved by lowering the content of non-ionic surfactant to amounts of at most 8 wt %. The agents can be used in processes for preventing changes in colour shades and for inhibiting colour transfer to white or differently-coloured laundry when washing coloured laundry, alone or combined with white laundry, in aqueous, surfactant-containing liquor.

Description

"Color transfer inhibiting detergent"

The invention relates to a detergent for use in washing processes for colored laundry, which contains color transfer inhibitor and bleaching agent and, if appropriate, bleach activator, a process for washing colored laundry, a method for preventing color changes and for inhibiting color transfer, and the use of the laundry mentioned ¬ means in such procedures.

Detergents for use in household washing processes for colored laundry, so-called color detergents, are generally free of bleaching agents in order to avoid the oxidative damage to the textile dyes. After multiple washes in particular, there is otherwise the risk that the preservation of the color tone of the colored laundry will be impaired if the dye on the surface of the textiles is oxidized. On the other hand, the use of bleaching agent systems, that is to say combinations of active oxygen compounds with bleach activators which release peroxocarboxylic acid under perhydrolysis conditions, is extremely desirable in detergents, since the bleaching action on laundry soiling increases the cleaning performance of the detergent and the bleaching agents are also graying-inhibiting, germicidal and odor-reducing can act, so that their use also increases hygiene when washing.

Color detergents normally contain active substances for color transfer inhibition in order to prevent discoloration of laundry items, that is to say transfer of dyes which have been detached from the colored laundry and reach the washing liquor, onto textiles of a different color. It is believed that such dye transfer inhibitors complex stabilize the dyes and keep in the wash liquor. As is known, polyvinyl pyrrolidone is one of the particularly effective color transfer inhibitors. It has already been proposed several times, for example in European patent applications EP 628624 and EP 653480, customary heavy-duty detergents which contain a combination of peroxidic bleaching agent, for example perborate or percarbonate, with bleach activator, for example N, N, N ', N '-Tetraacetylethylenediamine (TAED) contain, small amounts, for example up to 1 wt .-%, to add polyvinylpyrrolidone.

From the German patent application DE 4312648 a detergent with discoloration-inhibiting properties is known which contains more than 8% by weight of nonionic surfactant, 10% by weight to 80% by weight builder and 0.1% by weight to 5% by weight. -% contains polyvinylpyrrolidone and up to 10 wt .-% peroxo bleach. Such an agent can also contain bleach activators.

Based on this prior art, it was found in the course of further investigations that, surprisingly, a minimization of the color transfer and a maximization of the color retention as well as a maximization of the cleaning performance can be achieved if the amount of nonionic surfactant is reduced and if necessary certain amounts of bleach activator incorporated.

The invention relates to a color transfer-inhibiting detergent containing surfactant, polyvinylpyrrolidone and bleaching agent based on active oxygen, which is characterized in that it contains nonionic surfactant only in amounts of up to 8% by weight.

Another object of the invention is a color transfer inhibiting detergent containing nonionic surfactant in amounts of up to 8% by weight, bleaching agent based on active oxygen and polyvinylpyrrolidone which additionally contains bleach activator which releases peroxocarboxylic acid under perhydrolysis conditions, the weight ratio of bleach activator to polyvinylpyrrolidone being below 5, preferably below 4 and in particular in the range from 0.5 to 3.5.

Another object of the invention is a method for washing colored laundry, alone or in combination with white laundry, in aqueous, surfactant-containing liquor, which is characterized in that the Wash liquor at least temporarily a concentration of polyvinylpyrrolidone in the range from 0.01 g / 1 to 1 g / 1, in particular from 0.05 g / 1 to 0.2 g / 1, and a concentration of active oxygen in the range from 0.01 g / 1 to 0.2 g / 1, in particular from 0.03 g / 1 to 0.15 g / 1.

A modification of such a method consists in a method for preventing color changes and for inhibiting the color transfer to white or differently colored laundry when washing colored laundry, alone or in combination with white laundry, in an aqueous, surfactant-containing liquor, which characterized in that the washing liquor at least at times has a concentration of polyvinylpyrrolidone in the range from 0.01 g / 1 to 1 g / 1, in particular from 0.05 g / 1 to 0.2 g / 1, and a concentration of active oxygen in the Range from 0.01 g / 1 to 0.2 g / 1, in particular from 0.03 g / 1 to 0.15 g / 1.

In these processes, the concentrations of polyvinyl pyrrolidone and active oxygen are preferably maintained in the wash liquor over a period of from 5 minutes to 90 minutes, in particular from 10 minutes to 70 minutes. The effect of the active oxygen can be enhanced by the in situ formation of peroxocarboxylic acid in the wash liquor from bleach based on active oxygen and bleach activator. The processes mentioned are preferably carried out in such a way that the washing liquor has a temperature of up to 60 ° C., in particular in the range from 30 ° C. to 60 ° C. The use of agents according to the invention in such processes is preferred, but the components can also be metered individually or in combinations not according to the invention into the liquor preferably located in a domestic washing machine.

Color transfer-inhibiting polyvinylpyrrolidone is preferably in amounts according to the invention, which can be liquid, pasty or solid, which should not be understood to mean, in the form of a non-exhaustive list, both pulverulent and compacted, extruded and tableted agents, in amounts of 0.1% by weight. Contain% to 5 wt .-%, in particular 0.4 wt .-% to 2.5 wt .-%. It preferably has a molar mass in the range from 5,000 to 4,000,000, in particular in the range from 10,000 to 100,000. Both from Europe, for example, can be used Patent application EP 262897 known polyvinylpyrrolidones with molecular weights of 15,000 to 50,000 as well as the polyvinylpyrrolidones known from international patent application WO 95/06098 with molecular weights of more than 1,000,000, in particular 1,500,000 to 4,000,000. If desired, the dye may also contain further substances which inhibit color transfer, for example those N-vinylimidazole / N-vinylpyrrolidone copolymers known from German patent applications DE 2814287 or DE 3803630 or international patent applications WO 94/10281, WO 94/26796, WO 95/03388 and WO 95/03382, which: from German patent application DE 2814329 known polyvinyloxazolidones, the copolymers known from European patent application EP 610846 based on vinyl monomers and carboxamides, the polyesters and polyamides containing pyrrolidone groups known from international patent application WO 95/09194 and from international patent application WO 94/29422 known grafted polyamidoamines and polyethyleneimines, the polymers known from German patent application DE 4328254 with amide groups from secondary amines, the polyamine-N-oxide polymers known from international patent application WO 94/02579 or European patent application EP 135217 the European patent application EP 584 738 known polyvinyl alcohols, the copolymers known from the European patent application EP 584709 based on acrylamidoalkenylsulfonic acids, the manganese complexes known from the European patent application EP 630964, the porphine and porphyrin known from the European patent application EP 596 187 - or phthalocyanine complexes and / or enzymatic systems, as are known, for example, from international patent applications WO 92/18687 and WO 91/05839.

Active oxygen-based bleaching agents are preferably present in the agent according to the invention in amounts of 5% by weight to 25% by weight, in particular 6% by weight to 15% by weight. The bleaching agents that are considered include the peroxygen compounds generally used in detergents, such as hydrogen peroxide and perborate, which can be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are present as alkali metal salts, usually as sodium salts. Hydrogen peroxide, alkali perborate monohydrate and / or alkali percarbonate is preferably used. The bleach activator which releases peroxocarboxylic acid under perhydrolysis conditions, if present, is present in the agents according to the invention preferably in amounts of 0.5% by weight to 10% by weight, in particular 1% by weight to 7% by weight. Such bleach activators include the commonly used N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycoluriles, in particular tetraacetylglycoluril, N-acylated hydantoins, as are known, for example, from German patent applications DE 1467582 or DE 4338920 are hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and laetams, such as the N-acyl-valerolaetams known for example from the international patent application WO 95/00626 or those for example from the international patent applications WO 94/27970, WO 94 / 28103 and WO 94/28105 known N-acyl-caprolaetams, also carboxylic anhydrides, especially phthalic anhydride, carbonic acid esters, especially sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, especially pentaacetyl glucose. The pyroglutamic acid derivatives known from German patent application DE 4338922 can also be used. The bleach activator is preferably selected from the linear or branched chain aliphatic, cycloaliphatic or aromatic peroxocarboxylic acid with 2 to 12 carbon atoms and compounds thereof under per hydrolysis conditions. The bleach activators, in particular for use in solid or powdery compositions, can be coated or granulated with Hü11 substances in a known manner to avoid the interaction with the per compounds during storage, with tetraacetylethylenediamine having medium grain sizes granulated with the aid of carboxymethylcellulose from 0.01 mm to 0.8 mm, as can be produced, for example, by the process described in European Patent EP 037026, and / or granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5- triazine, as can be prepared by the process described in German Patent DD 255 884, is particularly preferred.

There is no restriction in the further ingredients of the agents, but since the agents according to the invention are those for use in washing processes for colored laundry, they are preferably free from optical brighteners. If desired, surfactants, in particular anionic and / or nonionic surfactants, can be present in the agents according to the invention, preferably in amounts of in total from 8% by weight to 30% by weight, in particular from 12% by weight to 24% by weight, care must be taken that the amount of nonionic surfactant does not exceed the upper limit of 8% by weight, based on the total agent.

The nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 14 and in particular between 6 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the alkoxylates, in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used. Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used. In addition, there are the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, such as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as are used in accordance with the processes in US Pat 1 985424, US 2016962 and US 2703798 and international patent application WO 92/06984 can be considered. Non-ionic surfactants of the so-called alkyl polyglycoside type which are suitable for incorporation into the agents according to the invention are compounds of the general formula (G) n-OR ¹ , in which R ^{1 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10. The glycoside component (G) _n is an oligomer or polymer from naturally occurring aldose or keto monomers, in particular glucose, mannose, fructose, Ga Lactose, Talose, Gulose, Altrose, Allose, Idose, Ribose, Arabinose, Xylose and Lyxose belong. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization. The degree of oligomerization n generally takes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4. The preferred monomer component is glucose because of its good availability. The alkyl or alkenyl part R ^{1 of} the glycosides preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. In this case, too, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl glycosides contain a coconut fatty alkyl radical, ie mixtures with essentially R ^{1 =} dodecyl and R ¹ = tetradecyl. Nonionic surfactant is preferably contained in an agent according to the invention in amounts of 2% by weight to 8% by weight, in particular 3% by weight to 7% by weight.

Agents according to the invention can instead or additionally obtain further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably up to 22% by weight, in particular from 7% by weight to 18% by weight, in each case on total means included. Synthetic anionic surfactants which are particularly suitable for use in agents of this type are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms, which carry an alkali metal, ammonium or alkyl or hydroxyalkyl substituted ammonium ion as countercation . The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched chain analogs, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. Such alkyl and / or Alkenyl sulfates are contained in the agents according to the invention preferably in quantities of 7% by weight to 18% by weight, in particular 8% by weight to 15% by weight.

The sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 1 to 30, in particular 2 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the .alpha.-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, and also the sulfofatty acids resulting from these by formal saponification.

If both nonionic surfactant and synthetic anionic surfactant are contained, their weight ratio in the agent according to the invention is preferably 1: 8 to 1: 2, in particular 1: 6 to 1: 3.

Soaps are considered as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable. In particular, those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated Ci2-Cιg fatty acid soaps and up to 50% by weight of unsaturated soaps, for example oleic acid soap. Soap is preferably present in amounts of up to 5% by weight, in particular from 0.1% by weight to 2% by weight. In particular, however, higher amounts of soap, as a rule up to 15% by weight, can also be contained in liquid agents.

The other optional ingredients contained in the agents according to the invention often include soiling-releasing substances which are referred to as "soil-release" agents. These include copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units and which, because of their chemical similarity, also include Polyester fibers are particularly effective when washing textiles made of this material, but can also have the desired effect on fabrics made from other materials. Soil-removing copolyesters of the type mentioned and their use in detergents have been known for a long time. For example, German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene-1-glycol copolymers. The German laid-open specification DT 2200911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. German patent publication DT 2253063 mentions acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol. European patent EP 185 427 discloses methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain such a soil release polymer. European patent EP 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and glycerol units. Such soil-release polyesters are preferably present in agents according to the invention in amounts of 0.25% by weight to 5% by weight, in particular from 0.5% by weight to 1.5% by weight.

Other possible ingredients of agents according to the invention include water-soluble and / or water-insoluble builders, in particular selected from alkali alumosilicate, crystalline or amorphous alkali silicate, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof. An agent according to the invention preferably contains 20% by weight to 45% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110 which are accessible by oxidation of polysaccharides. polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also contain small amounts of polymerizable substances without carbon May contain copolymerized acid functionality. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl ester, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as monomers can also be used as water-soluble organic builder substances. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 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 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% vinyl alcohol and / or vinyl acetate. Such a monomer can also include a derivative of an allylsulfonic acid which, in the 2-position, is substituted 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. Preferred polymers then contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight .-%, preferably 15% by weight to 25% by weight of methylailsulfonic acid or methylailsulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. By using such third monomers, predetermined breaking points are presumably built into the polymer, which are responsible for good biodegradability of the polymer. These terpolymers can in particular be prepared by processes which are described in German patent specification DE 4221381 and German patent application DE 43 00 772 and generally have a relative molecular weight between 1000 and 200000, preferably between 200 and 50,000 and especially between 3000 and 10000. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts, and 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% by weight aqueous solutions.

Organic builder substances of this type are preferably present in amounts of up to 15% by weight, in particular up to 12% by weight and particularly preferably from 2% by weight to 10% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.

In particular, water-insoluble, water-dispersible, crystalline or amorphous alkali alumosilicates are used as inorganic builder materials, in amounts of up to 35% by weight, preferably from 10% by weight to 30% by weight and in liquid compositions in particular from 5% by weight to 20 wt .-%, used. Among these, the crystalline alkali alumosilicates in detergent quality, in particular zeolite A, zeolite P and optionally zeolite X, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12837, is in the range from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline or amorphous alkali silicates, which can be present alone or as a mixture with one another. The alkali silicates which can be used as builders in the compositions preferably have a molar ratio of alkali oxide to SiO 2 of 1: 1.1 to 1:12. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na2O: SiO2 molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Porti! (PO. Those with a molar ratio Na 2 O: Si O 2 of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0425427 Crystalline phyllosilicates of the general type are preferably used as crystalline silicates Formula Na2Si _x θ2χ + r_ / H2θ used, in which x, the so-called module, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0164514. Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and ÜT sodium disilicate (Na2Si2θ5 * yH2θ) are preferred. Practically anhydrous crystalline alkali silicates of the abovementioned general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates and can be prepared as described in European patent applications EP 0 548599, EP 0502325 and EP 0452428 in agents which contain a polymer according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda according to the process of European patent application EP 0436835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent specifications EP 0 164552 and / or EP 0293753, are used in a further preferred embodiment of detergents according to the invention, which contain a polymer according to the invention used. The content of alkali silicates, particularly in the case of solid agents according to the invention, is preferably 5% by weight to 30% by weight and in particular 7% by weight to 20% by weight, based on anhydrous active substance. If alkali alumosilicate, in particular zeolite, is also present as an additional builder substance, the alkali silicate content is preferably 5% by weight to 20% by weight and in particular 7% by weight to 15% by weight, based on the water-free active substance . The weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is then preferably 1: 2 to 2: 1.

In addition, the detergents can contain other constituents customary in detergents. These optional components include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, graying inhibitors, for example cellulose ethers, foam inhibitors, for example organopolysiloxanes or paraffins, and solvents and colorants and fragrances.

In addition to water, solvents which are used in particular in liquid compositions according to the invention are preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, iso-propanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the classes of compounds mentioned.

Enzymes which may be present are in particular those from the class of proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, oxidases and peroxidases and mixtures thereof. Enzymatic active ingredients obtained from fungi or bacterial strains are preferably used. They can be obtained in a known manner from suitable microorganisms by fermentation processes. Proteases are commercially available, for example, under the names BLAP (R), Savinese Esperase ( ^R ), Maxatase (R), Optimase00. Alcalase ( ^R ), Durazym ( ^R ) or Maxapem ( ^R ) available. The lipase that can be used can be obtained, for example, from Humicola lanuginosa, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species. Suitable lipases are, for example, under the names Lipolase ( ^R ), Lipozym (R), Lipo¬ max ( ^R ). Amano ipase, Toyo-Jozo (R) lipase, Meito (R) lipase and Diosynth (R) lipase are commercially available. Suitable amylases are commercially available, for example, under the names Maxamyl (R), Duramyl (R) and Termamyl (R). The cellulase which can be used can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5. Such cellulases are known, for example, from German laid-open publications DE 3117250, DE 3207825, DE 3207847, DE 3322950 or European patent applications EP 265832, EP 269977, EP 270974, EP 273125 and EP 339550. Commercially available cellulases are Celluzyme (R) and Carezyme (R) from Novo Nordisk and KAC ( ^R ) from Kao.

The usual enzyme stabilizers which may be present, in particular in liquid agents, include amino alcohols, for example mono-, Di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, as known for example from European patent applications EP 376705 and EP 378261, boric acid or alkali borates, boric acid-carboxylic acid combinations, such as from European patent application EP 451 924 known, boric acid esters, such as known from international patent application WO 93/11215 or European patent application EP 511456, boronic acid derivatives, such as known from European patent application EP 583536, calcium salts, for example the calcium formic acid known from European patent EP 28865 Combination, magnesium salts, such as known from European patent application EP 378262, and / or sulfur-containing reducing agents, such as known from European patent applications EP 080748 or EP 080223.

Suitable foam inhibitors include long-chain soaps, in particular beef soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which can also contain microfine, optionally silanized or otherwise hydrophobized silica. For use in particulate compositions, such foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German patent application DE 3436 194, European patent applications EP 262588, EP 301 414, EP 309931 or European patent EP 150386.

Furthermore, an agent according to the invention can contain graying inhibitors. Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying of the fibers. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, 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.

The production of liquid agents according to the invention presents no problems and can be done by simply mixing their ingredients. Particulate compositions according to the invention can be produced in the simplest way by mixing the individual particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, optional other powdery components and, if desired, also liquid or liquefied components, in particular non-ionic surfactants, but also colorants and fragrances, which can be mixed in by spraying. It is preferred to convert the thermally resilient components into a particulate product in a manner known in principle by spray drying an aqueous slurry and, if appropriate, to mix this with thermally sensitive components, which in particular include the bleaching agents. Known extrusion and / or garnishing processes can also be used to produce particulate compositions according to the invention or their partial products.

Granular detergents according to the invention with a high bulk density can preferably be prepared according to the method of international patent application WO 91/02047. This involves the extrusion of a homogeneous premix of detergent ingredients over perforated shapes, which preferably have an opening width of 0.5 mm to 5 mm, subsequent comminution of the extrudate and subsequent treatment in a rounding device, which results in largely uniform spherical shapes Products. The compacting extrusion step gives granular particles with bulk densities of generally 700 g / 1 to 1050 g / 1. These can be complete detergents or cleaning agents or constituents of such agents, which are added by admixing other components which are usually not co-extrudable, for example solid or solid foam regulators or enzymes. Examples

A powder detergent (BW) with the composition given in Table 1 below was added alone and after adding 1.2% by weight of polyvinylpyrrolidone with an average molar mass of approximately 40,000 (VI), 8% by weight of perborate monohydrate and 2 % By weight of TAED (V2), 1.2% by weight of polyvinylpyrrolidone and 8% by weight of perborate monohydrate (MI) and 1.2% by weight of polyvinylpyrrolidone, 8% by weight of perborate monohydrate and 2% by weight of TAED (M2) tested for the ability to prevent "bleeding" (transfer of textile color from dyed textile to white textile when washing together). For this purpose, white cotton fabric was washed together with the dyed cotton textile specified in Tables 2 and 3 (in each case brand new, previously unwashed textiles) and, after drying, the color change (dE) of the white fabric was measured. Table 2 shows the results of the washing at 40 ° C and Table 3 shows the results of the washing at 60 ° C.

Table 1: Composition [% by weight]

a) 5-fold ethoxylated Ciö / i8 fatty alcohol b) 7-fold ethoxylated C ^ / is-Fe ^ ³ ^ ⁰⁰⁰ ! Table 2: Bleeding [dE] after washing at 40 ° C

Table 3: Bleeding [dE] after washing at 60 ° C

It can be seen that the agents (MI and N2) according to the invention have significantly better ink transfer inhibition performance than the agents which do not contain the combination of bleaching agent and polyvinylpyrrolidone.

Claims

claims

1. Color transfer inhibiting detergent, containing surfactant, polyvinylpyrrolidone and bleach based on active oxygen, characterized in that it contains nonionic surfactant in amounts up to 8 wt .-%.

2. Composition according to claim 1, characterized in that it additionally contains bleach activator which releases peroxocarboxylic acid under the perhydrolysis conditions, the weight ratio of bleach activator to polyvinylpyrrolidone being less than 5, preferably less than 4 and in particular in the range from 0.5 to 3.5 .

3. Composition according to claim 1 or 2, characterized in that it contains 0.1 wt .-% to 5 wt .-%, in particular 0.4 wt .-% to 2.5 wt .-% polyvinylpyrrolidone.

4. Composition according to one of claims 1 to 3, characterized in that the polyvinylpyrrolidone has a molecular weight in the range from 5000 to 4000000, in particular in the range from 10000 to 100000.

5. Composition according to one of claims 1 to 4, characterized in that it contains 5% by weight to 25% by weight, in particular 6% by weight to 15% by weight, of an active oxygen-based bleach.

6. Composition according to one of claims 1 to 5, characterized in that the bleaching agent based on active oxygen is selected from hydrogen peroxide, alkali borate monohydrate, alkali percarbonate and mixtures thereof.

7. Composition according to one of claims 2 to 6, characterized in that it contains 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 7 wt .-% bleach activator.

8. Agent according to one of claims 2 to 7, characterized in that the bleach activator from the linear or under perhydrolysis conditions branched chain aliphatic, cycloaliphatic or aromatic peroxocarboxylic acid with compounds which split off 2 to 12 carbon atoms and their mixtures is selected.

9. Agent according to one of claims 1 to 8, characterized in that it is free of optical brighteners.

10. A process for washing colored laundry, alone or in combination with white laundry, in an aqueous, surfactant-containing liquor, characterized in that the washing liquor at least at times has a concentration of polyvinylpyrrolidone in the range from 0.01 g / 1 to 1 g / 1, in particular from 0.05 g / 1 to 0.2 g / 1, and a concentration of active oxygen in the range from 0.01 g / 1 to 0.2 g / 1, in particular from 0, 03 g / 1 to 0.15 g / 1.

11. A method for preventing color changes and for inhibiting the transfer of color to white or differently colored laundry when washing colored laundry, alone or in combination with white laundry, in an aqueous, surfactant-containing liquor, characterized in that the washing liquor at least temporarily contains a concentration of polyvinylpyrro lidon in the range from 0.01 g / 1 to 1 g / 1, in particular from 0.05 g / 1 to 0.2 g / 1, and a concentration of active oxygen in the range from 0.01 g / 1 to 0.2 g / 1, in particular from 0.03 g / 1 to 0.15 g / 1.

12. The method according to claim 10 or 11, characterized in that the concentrations of polyvinylpyrrolidone and active oxygen are maintained over a period of 5 minutes to 90 minutes, in particular from 10 minutes to 70 minutes.

13. The method according to any one of claims 10 to 12, characterized in that the effect of the active oxygen is enhanced by the in-situ formation of peroxocarboxylic acid in the wash liquor from bleaching agent based on Aktivsauer¬ and bleach activator.

14. The method according to any one of claims 10 to 13, characterized in that the washing liquor has a temperature of up to 60 ° C, in particular in the range from 30 ° C to 60 ° C.

15. Use of an agent according to any one of claims 1 to 9 in a method for washing colored laundry or for preventing color changes and for inhibiting the transfer of color to white or different colored laundry when washing colored laundry.