EP0850292B2 - Colour transfer-inhibiting washing agent - Google Patents

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

The invention relates to a detergent for use in washing processes for coloreds containing color transfer inhibitor and bleach and bleach activator, a process for washing colored laundry, a process for preventing hue changes and inhibiting color transfer, and the use of said laundry detergents in such processes.

Detergents for use in household washing processes for coloreds, so-called color detergents, are as a rule free of bleaching agents in order to avoid the oxidative damage to the textile dyes. In particular, after multiple washes there is otherwise the risk that the maintenance of the color of the coloreds is impaired when it comes to the oxidation of the dye on the surface of the textiles. On the other hand, the use of bleach systems, that is combinations of active oxygen compounds with peroxycarboxylic acid peeling off bleach activators, in laundry detergents extremely desirable because the cleaning effect of the detergent is increased by the bleaching effect on laundry dirt and the bleach can also act graying, germicidal and odor-repellent so that their use additionally increases hygiene during washing.

Color detergents normally contain agents for color transfer inhibition in order to prevent the discoloration of laundry parts, that is, a transfer of dyes that have been detached from the coloreds and get into the wash liquor, on different colored textiles. It is believed that such dye transfer inhibiting agents complex and stabilize the dyes in the wash liquor. Polyvinylpyrrolidone is known to be one of the most effective color transfer inhibitors.

Already several times, for example in the European patent applications EP 0 628 624 A1 and EP 0 653 480 A1 , has been proposed, conventional heavy duty detergents containing a combination of peroxidic bleaching agent, for example perborate or percarbonate, with bleach activator, for example N, N, N ', N'-tetraacetylethylenediamine (TAED), small amounts, for example up to 1 wt. -%, Polyvinylpyrrolidone add.

The European patent application EP 0 508 034 A1 discloses granular detergents which contain surfactant, builder, polyvinylpyrrolidone having molecular weights of 5,000 to 22,000 and up to 15% by weight of inorganic filler salt and which result in polyvinylpyrrolidone concentrations of 5 mg / l to 500 mg / l in the wash solution may contain peroxygen bleach and bleach activator. The not pre-published European patent application EP 0 717 103 A2 relates to laundry detergents containing from 5% to 90% by weight of anionic and / or nonionic surfactant, from 5% to 70% by weight of builder, from 0.1% to 30% by weight of peroxygen compound and 0.005 wt .-% to 2 wt .-% of a manganese-containing complex, wherein the agent additionally polyvinylpyrrolidone in amounts of 0.05 wt .-% to 5 wt .-% have. From the German patent application DE 43 12 648 a detergent with discoloration-inhibiting properties is known, the more than 8 wt .-% of nonionic surfactant, 10 wt .-% to 80 wt .-% builder and 0.1 wt .-% to 5 wt .-% polyvinylpyrrolidone and up to Contains 10 wt .-% peroxy bleach. Such agent may also contain bleach activators.

Based on this prior art, it has been found in further investigations that surprisingly a minimization of color transfer and maximization of color retention and maximization of cleaning performance can be achieved by lowering the amount of nonionic surfactant and incorporating certain amounts of bleach activator.

LAS =

lineares C₁₂ Alkylbenzolsulfonat

AS =

Natriumalkylsulfat

TAS =

Natrium-Talgalkohol-sulfat

45E7 =

C_14-15 primärer Alkohol kondensiert mit einem Durchschnitt von 7 Mol Ethylenoxid

25E3 =

C_12-15 primärer Alkohol kondensiert mit einem Durchschnitt von 3 Mol Ethylenoxid

PC3 =

Percarbonat

PB1 =

Perborat-Monohydrat

PB4 =

Perborat-Tetrahydrat

TAED =

Tetraacetylethylendiamin

PVP =

Polyvinylpyrrolidon

PVNO =

Polyvinylpyridin-N-oxid

PVPVI =

Polyvinylpyrrolidon-Polyvinylimidazol-Copolymer

MnPC =

Mangan-Phtalocyanintetrasulfonat

EDTMP =

Ethylendiamin-tetramethylen-phosphonat

CMC =

Carboxymethylcellulose

• Aufheller1: R = Diethanolamino und R₂ = SO₃Na
• Aufheller2: R = Morpholino und R₂ = SO₃Na
• Aufheller3: R = Anilino, R₂ = SO₃Na oder H.

The invention relates to a dye transfer-inhibiting detergent containing surfactant, polyvinylpyrrolidone, bleaching agent based on active oxygen and peroxycarboxylic acid releasing bleach activator under perhydrolysis conditions, characterized in that it 8 wt% to 30 wt% surfactant, including nonionic surfactant in amounts up to 8 wt. %, and the weight ratio of bleach activator to polyvinylpyrrolidone is less than 5, and does not have the following composition: READ - C ₄₅ AS 7 C ₂₄ AS - TAS - 45E7 7 25E3 - glucamide - Zeolite MAP 38 Na SKS-6 5 citrate 10 carbonate 7 Silicate (ratio 2.0) - PC3 14 PB1 - PB4 - TAED 2.5 Protease (Alcalase®) 2.0 Amylase (Termamyl®) 0.4 Lipase (Lipolase®) 0.4 PVP 1.0 PVNO - PVPVI - MnPC - EDTMP 0.1 CMC 0.8 Suds suppressors Aufhellerl - Aufheller2 0.2 Aufheller3 - Moisture, sulfate and others 6.6 100 with the meanings

LAS =

linear C ₁₂ alkylbenzenesulfonate

AS =

of sodium

TAS =

Sodium tallow alcohol sulfate

45E7 =

C _14-15 primary alcohol condenses with an average of 7 moles of ethylene oxide

25E3 =

C _12-15 primary alcohol condenses with an average of 3 moles of ethylene oxide

PC3 =

percarbonate

PB1 =

Perborate monohydrate

PB4 =

Perborate tetrahydrate

TAED =

tetraacetylethylenediamine

PVP =

polyvinylpyrrolidone

PVNO =

Polyvinyl pyridine-N-oxide

PVPVI =

Polyvinylpyrrolidone-polyvinylimidazole copolymer

MnPC =

Manganese Phtalocyanintetrasulfonat

EDTMP =

Ethylene diamine tetra methylene-phosphonate

CMC =

carboxymethylcellulose

• Brightener1: R = diethanolamino and R ₂ = SO ₃ Na
• Brightener2: R = morpholino and R ₂ = SO ₃ Na
• Brightener3: R = anilino, R ₂ = SO ₃ Na or H.

Another object of the invention is a process for washing colored laundry, alone or in combination with white laundry, in aqueous, surfactant-containing liquor using such agent or all its individual components, which is characterized in that the wash liquor at least temporarily a concentration of Polyvinylpyrrolidone in the range of 0.01 g / l to 1 g / l, in particular from 0.05 g / l to 0.2 g / l, and an active oxygen concentration in the range of 0.01 g / l to 0.2 g / l, in particular from 0.03 g / l to 0.15 g / l.

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

Preferably, in these processes, the concentrations of polyvinylpyrrolidone and active oxygen in the wash liquor are maintained for a period of from 5 minutes to 90 minutes, more preferably from 10 minutes to 70 minutes. The effect of the active oxygen by the in situ formation of peroxycarboxylic acid in the wash liquor of active oxygen bleach and bleach activator. Preferably, the said processes are carried out so that the wash liquor has a temperature of up to 60 ° C, in particular in the range of 30 ° C to 60 ° C. Preference is given to the use of agents according to the invention in such processes, but the components can also be metered individually into the liquor, which is preferably present in a household washing machine.

Color transfer inhibiting polyvinylpyrrolidone may be in inventive compositions which are liquid, pasty or solid, which in non-exhaustive list both powdery and compacted, extruded and tableted agents are to be understood, preferably in amounts of 0.1 wt .-% to 5 wt .-%, in particular 0.4 wt .-% to 2.5 wt .-% contain. It preferably has a molecular weight in the range of 5,000 to 4,000,000, in particular in the range of 10,000 to 100,000. Useful are both the example of the European patent application EP 262,897 known Polyvinylpyrrolidone with molecular weights of 15 000 to 50 000 as well as those from the international Patent Application WO 95/06098 Polyvinylpyrrolidone known with molecular weights above 1 000 000, in particular from 1 500 000 to 4 000 000. If desired, may be included in the additional agents in addition color transfer inhibiting substances, for example those from the German patent applications DE 28 14 287 or DE 38 03 630 or the international one 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 derived from the international Patent Application WO 95/09194 known pyrrolidone group-containing polyesters and polyamides which are from the international Patent Application WO 94/29422 Known grafted polyamidoamines and polyethylenimines derived from German patent application DE 43 28 254 known polymers with amide groups from secondary amines, which are from the international Patent Application WO 94/02579 or the European patent application EP 135 217 known polyamine N-oxide polymers, from the European patent application EP 584 738 known polyvinyl alcohols, from the European patent application EP 584,709 known copolymers based on acrylamidoalkenylsulfonic acids, which are known from the European patent application EP 630 964 known manganese complexes, from the European patent application EP 596 187 known porphine, porphyrin or phthalocyanine complexes and / or enzymatic systems, such as those from the international Patent Applications WO 92/18687 and WO 91/05839 are known.

Active oxygen-based bleaches are preferably present in the composition according to the invention in amounts of 5% by weight to 25% by weight, in particular 6% by weight to 15% by weight. Suitable bleaching agents include the peroxygen compounds commonly used in detergents, such as hydrogen peroxide and perborate, which may be in the form of tetra- or monohydrate, percarbonate, per-pyrophosphate and persilicate, which are present as alkali salts, usually as sodium salts. Preferably, hydrogen peroxide, alkali metal perborate monohydrate and / or alkali metal percarbonate is used.

Under perhydrolysis conditions peroxycarboxylic acid releasing bleach activator is preferably present in the inventive compositions in amounts of 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 7 wt .-%. Such bleach activators include the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, as described, for example, in US Pat German patent applications DE 14 67 582 or DE 43 38 920 Hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and lactams, such as those from the international Patent Application WO 95/00626 known N-acyl-valerolactam or the example of the international Patent Applications WO 94/27970 . WO 94/28103 and WO 94/28105 known N-acyl-caprolactams, in addition carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, especially pentaacetylglucose. Are also useful from the German patent application DE 43 38 922 known pyroglutamic acid derivatives. The bleach activator is preferably selected from the aliphatic, cycloaliphatic or aromatic peroxocarboxylic acid which is linear or branched under perhydrolysis conditions and has compounds which split off from 2 to 12 carbon atoms and mixtures thereof. The bleach activators, in particular for use in solid or powdery agents, may have been coated or granulated in a known manner with shell substances to avoid interaction with the per compounds, with granular tetraacetylethylenediamine having mean particle sizes of 0.01 mm to 0.9 mm with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine 0.8 mm, as for example according to the European patent EP 037 026 and / or granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as described in the German patent DD 255 884 is particularly preferred.

The other ingredients of the compositions are not limited, but since the agents according to the invention are those for use in washing processes for coloreds, they are preferably free from optical brighteners.

Surfactants, in particular anionic and / or nonionic surfactants, are described in US Pat agents according to the invention in amounts of from 8% by weight to 30% by weight, in particular 12% by weight to 24% by weight, it being to be noted that the amount of nonionic surfactant exceeds the stated upper limit of 8 Wt .-%, based on the total mean, does not exceed.

Suitable nonionic surfactants include the alkoxylates, especially 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. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, as described in the international Patent Application WO 90/13533 as well as fatty acid polyhydroxyamides, as prepared according to the methods of U.S. Pat. Nos. 1,985,424 . US 2 016 962 and US 2,703,798 as well as the international ones Patent Application WO 92/06984 can be prepared. Nonionic surfactants of the so-called alkylpolyglycoside type which are suitable for incorporation in 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 one Number between 1 and 10 mean. The glycoside component (G) _n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomerisierungsgrad. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R ^{1 of} the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can be used to prepare useful glycosides. Also useful in this case are the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and also mixtures thereof. Particularly preferred alkyl glycosides contain a Kokosfettalkylrest, that is, mixtures having substantially R ¹ = dodecyl and R ¹ = tetradecyl. Nonionic surfactant is preferably contained in an agent according to the invention in amounts of from 2% by weight to 8% by weight, in particular from 3% by weight to 7% by weight.

Compositions according to the invention may instead or additionally comprise 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 based on the total Means, included. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. Such alkyl and / or alkenyl sulfates are preferably present in the compositions according to the invention in amounts of from 7% by weight to 18% by weight, in particular from 8% by weight to 15% by weight.

Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain from 1 to 30, in particular from 2 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.

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

Other optional surface-active ingredients include soaps, saturated fatty acid soaps, as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, derived soaps are suitable. In particular, those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50% by weight of unsaturated soaps, for example, oleic acid soap. Preferably, soap is included in amounts up to 5% by weight, especially from 0.1% to 2% by weight. In particular, in liquid agents, however, higher amounts of soap of usually up to 15 wt .-% may be included.

Other ingredients that are optionally included in the compositions of the invention often include soil release agents known 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 to polyester fibers, are particularly effective for washing textiles of this material but can also exhibit the desired effect on fabrics of other materials. Dirt-releasing copolyesters of the type mentioned as well as their use in detergents have been known for a long time. For example, German Offenlegungsschrift DT describes 16 17 141 a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. The German patent application DT 22 00 911 relates to detergents containing nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. In German Offenlegungsschrift DT 22 53 063 are called acidic textile finishing agents containing a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol. From the European patent EP 185 427 For example, methyl or ethyl group-endcapped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and laundry detergents containing such soil release polymer are known. The 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 from 0.25% by weight to 5% by weight, in particular from 0.5% by weight to 1.5% by weight.

Other possible ingredients of the compositions of the invention include water-soluble and / or water-insoluble builders, in particular selected from alkali metal aluminosilicate, crystalline or amorphous alkali metal silicate, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof. An agent according to the invention preferably contains from 20% by weight to 45% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and the polymeric (poly) carbon acids, in particular the polycarboxylates of the international, which are obtainable by oxidation of polysaccharides Patent Application WO 93/16110 , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances copolymerized without carboxylic acid functionality. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a 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. It is also possible to use as water-soluble organic builder substances terpolymers which contain two carboxylic acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. Preferred terpolymers contain 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% 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 .-% of vinyl alcohol and / or vinyl acetate. In such polymers may also be a derivative of an allylsulfonic acid as a monomer, which is substituted in position 2 with an alkyl radical, preferably with a C ₁ -C ₄ alkyl radical, or an aromatic radical which is derived preferably from benzene or benzene derivatives is. Preferred polymers then contain 40 wt .-% to 60 wt .-%, in particular 45 to 55 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10 wt .-% to 30 wt. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or 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, sucrose being particularly preferred. By using such third monomers presumably predetermined breaking points are incorporated in the polymer, which are responsible for a good biodegradability of the polymer. These terpolymers can be prepared in particular by methods which are described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1000 and 200,000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. All 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 percent by weight aqueous solutions.

Such organic builders are preferably in amounts up to 15 wt .-%, in particular to to 12 wt .-% and particularly preferably from 2 wt .-% to 10 wt .-%. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.

-Natriumdisilikate (Na₂Si₂O₅·yH₂O) bevorzugt. Auch aus amorphen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1,9 bis 2,1 bedeutet, herstellbar wie in den europäischen Patentanmeldungen EP 0 548 599 , EP 0 502 325 und EP 0 452 428 beschrieben, können in Mitteln, welche ein erfindungsgemäßes Polymer enthalten, eingesetzt werden. In einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es nach dem Verfahren der europäischen Patentanmeldung EP 0 436 835 aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1,9 bis 3,5, wie sie nach den Verfahren der europäischen Patentschriften EP 0 164 552 und/oder EP 0 293 753 erhältlich sind, werden in einer weiteren bevorzugten Ausführungsform von erfindungsgemäßen Waschmitteln, welche ein erfindungsgemäßes Polymer enthalten, eingesetzt. Der Gehalt an Alkalisilikaten beträgt, insbesondere bei festen erfindungsgemäßen Mitteln, vorzugsweise 5 Gew.-% bis 30 Gew.-% und insbesondere 7 Gew.-% bis 20 Gew.-%, bezogen auf wasserfreie Aktivsubstanz. Falls als zusätzliche Buildersubstanz auch Alkalialumosilikat, insbesondere Zeolith, vorhanden ist, beträgt der Gehalt an Alkalisilikat vorzugsweise 5 Gew.-% bis 20 Gew.-% und insbesondere 7 Gew.-% bis 15 Gew.-%, bezogen auf wasserfreie Aktivsubstanz. Das Gewichtsverhältnis Alumosilikat zu Silikat, jeweils bezogen auf wasserfreie Aktivsubstanzen, beträgt dann vorzugsweise 1:2 bis 2:1.Water-insoluble, water-dispersible, crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 35% by weight, preferably from 10% by weight to 30% by weight, and in liquid agents, in particular from 5% by weight, are used as inorganic builder materials 20 wt .-%, used. Among these, the detergent-grade crystalline alkali metal aluminosilicates, particularly zeolite A, zeolite P 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, which according to the data of German patent DE 24 12 837 can be determined ranges from 100 to 200 mg Ca0 per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline or amorphous alkali silicates which may be present alone or in a mixture with one another. The alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali oxide to SiO _{2 of} from 1: 1.1 to 1:12. 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. Such amorphous alkali silicates are commercially available, for example, under the name Portil ^(R) . Those with a molar ratio Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427 getting produced. The crystalline silicates crystalline layer silicates corresponding to general formula are preferably Na ₂ Si _x O _{2x + 1} · yH ₂ O used in the 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, for example, in the European Patent Application EP 0 164 514 described. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and

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 prepared as in the European patent applications EP 0 548 599 . EP 0 502 325 and EP 0 452 428 can be used in agents which contain a polymer according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as is obtained by the process of European Patent Application EP 0 436 835 made from sand and soda. Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as determined by the methods of European patents EP 0 164 552 and or EP 0 293 753 are available, are used in a further preferred embodiment of detergents according to the invention which contain a polymer according to the invention. The content of alkali metal silicates, in particular in the case of solid compositions 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 metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the content of alkali metal silicate is preferably from 5% by weight to 20% by weight and in particular from 7% by weight to 15% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 1: 2 to 2: 1.

In addition, the agents may contain other ingredients common in detergents. These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, grayness inhibitors, for example cellulose ethers, foam inhibitors, for example organopolysiloxanes or paraffins, and solvents and dyes and fragrances.

Solvents which are used in particular in liquid agents according to the invention are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether.

Suitable optionally contained enzymes are in particular those from the class of proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, oxidases and peroxidases and mixtures thereof. Preferably, derived from fungi or bacterial strains enzymatic agents are used. They can be obtained in a known manner by fermentation processes from suitable microorganisms. Proteases are commercially available, for example, under the names BLAP ^(R), Savinase ^(R), Esperase ^(R), Maxatase ^(R), Optimase.RTM ^(R), Alcalase ^(R), Durazym ^(R) or Maxapem ^{(R) are} available. The lipase which 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 known, for example, under the names Lipolase ^(R) , Lipozyme ^(R) , Lipomax ^(R) , Amano ^(R) lipase, Toyo-Jozo ^(R) lipase, Meito ^(R) lipase and Diosynth ^(R) . Lipase commercially available. Suitable amylases are, for example, commercially available under the names Maxamyl ^(R) , Duramyl ^(R) and Termamyl ^(R) . The usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5. Such cellulases are for example from the German Offenlegungsschriften DE 31 17 250 . DE 32 07 825 . DE 32 07 847 . DE 33 22 950 or the European patent applications EP 265 832 . EP 269 977 . EP 270 974 . EP 273 125 such as EP 339,550 known. Commercially available cellulases are Celluzyme ^(R) and Carezyme ^(R) from Novo Nordisk and KAC ^(R) from Kao.

Among the usual, optionally present in liquid detergents usual enzyme stabilizers include amino alcohols, such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, such as from the European patent applications EP 376,705 and EP 378,261 Boric acid or alkali borates, boric acid-carboxylic acid combinations, such as from the European patent application EP 451 924 known, boric acid esters, such as from the international Patent Application WO 93/11215 or the European patent application EP 511 456 known boronic acid derivatives, such as from the European patent application EP 583 536 known, calcium salts, for example from the European patent EP 28,865 known Ca-formic acid combination, magnesium salts, such as from the European patent application EP 378 262 known, and / or sulfur-containing reducing agents, such as from the European patent applications EP 080 748 or EP 080 223 known.

Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents such foam inhibitors are preferably bound to granular, water-soluble carrier substances, such as in the German Offenlegungsschrift DE 34 36 194 , the European patent applications EP 262 588 . EP 301 414 . EP 309 931 or the European patent specification EP 150 386 described.

Furthermore, an agent according to the invention may contain graying inhibitors. Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the 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 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.

The preparation of liquid compositions according to the invention poses no problems whatsoever and can be carried out by simply mixing their ingredients.

The production of particulate compositions according to the invention can be carried out in the simplest manner by mixing the individual particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, whereby optional other pulverulent constituents and, if desired, also liquid or liquefied constituents, to which in particular nonionic surfactants , but also colorants and fragrances may be added by spraying. It is preferred to convert the thermally loadable components in a manner known in principle by spray-drying an aqueous slurry into a particulate product and, if appropriate, to mix this with thermally sensitive constituents, to which in particular the bleaching agents are to be expected. The use of known extrusion and / or Garnulationsverfahren is possible for the production of particulate compositions according to the invention or their partial products.

Granular high-density detergents according to the invention may preferably be prepared according to the method of International Patent Application WO 91/02047 getting produced. This is the strand-like compression of a homogeneous premix of detergent ingredients via hole-forming, which preferably have an opening width of 0.5 mm to 5 mm, followed by comminuting the extrudate and subsequent treatment in a Rondiergerät, which leads to substantially uniformly spherical products. Granular particles having bulk densities of generally 700 g / l to 1050 g / l are obtained by the compacting extrusion step. These may be complete washing or cleaning agents or components of such agents, which are completed by admixing usually not co-extrudable further components, such as solid or formulated foam regulators or enzymes in solid form.

Examples

A powdered detergent ( BW ) of the composition given in Table 1 below was used alone and after addition of 1.2% by weight of polyvinylpyrrolidone having an average molar mass of about 40,000 ( V1 ), 8% by weight perborate monohydrate and 2 % By weight of TAED ( V2 ), 1.2% by weight of polyvinylpyrrolidone and 8% by weight of perborate monohydrate ( V3 ) and 1.2% by weight of polyvinylpyrrolidone, 8% by weight of perborate monohydrate and 2% by weight of TAED ( M1 ) on the ability to prevent "staining" (transfer of textile dye from dyed textile to white textile in the common wash). For this purpose, white cotton fabric was washed in each case together with the dyed cotton textile indicated in Tables 2 and 3 (new, previously unwashed textiles) and, after drying, the color change (dE) of the white fabric was measured. In Table 2, the results of the washes are indicated at 40 ° C, in Table 3 those of the laundry at 60 ° C. Table 1: Composition [% by weight] BW Na dodecylbenzenesulfonate 13 Nonionic surfactant ^a) 1 Nonionic surfactant ^b) 5 Soap 2 citric acid 3 polymeric polycarboxylate 4 Zeolite Na-A 38 sodium silicate 1 sodium 13 Water and sodium sulfate on 100 a) 5-fold ethoxylated C _16/18 fatty alcohol
b) 7-ethoxylated C _12/18 fatty alcohol Bleeding [dE] after washing at 40 ° C dyed textile BW V1 V2 V3 M1 Jeans, dark brown 16.1 14.4 16.2 13.7 12.6 Jeans, blackberry 12.6 5.7 12.8 4.6 4.3 Corduroy pants, red 7.1 4.7 6.9 5.5 4.8 Bleeding [dE] after washing at 60 ° C dyed textile BW V1 V2 V3 M1 Sweatshirt, dark green 13.5 14.8 14.9 13.1 11.9 Jeans, blackberry 21.1 9.6 22.7 9.4 9.4 Bath towel, blue 37.8 17.3 18.3 16.5 15.3 It can be seen that the agent ( M1 ) according to the invention has a significantly better color transfer inhibiting performance than the agents which do not contain the combination of bleach, bleach activator and polyvinylpyrrolidone.

Claims (15)

1. Colour-transfer-inhibiting laundry detergent, comprising surfactant, polyvinyl pyrrolidone, bleaching agent that is based on active oxygen and bleach activator that yields peroxycarboxylic acid under perhydrolysis conditions, characterized in that it contains 8 wt.% to 30 wt.% surfactant, including non-ionic surfactant in amounts of up to 8 wt.%, and the ratio by weight of bleach activator to polyvinyl pyrrolidone is under 5, wherein it does not have the following composition: LAS - C₄₅ AS 7 C₂₄ AS - TAS - 45E7 7 25E3 - Glucamide - Zeolite MAP 38 Na SKS-6 5 Citrate 10 Carbonate 7 Silicate (ratio 2.0) - PC3 14 PB1 - PB4 - TAED 2.5 Protease (Alcalase®) 2.0 Amylase (Termamyl®) 0.4 Lipase (Lipolase®) 0.4 PVP 1.0 PVNO - PVPVI - MnPC - EDTMP 0.1 CMC 0.8 Foam suppressor Optical brightener 1 - Optical brightener 2 0.2 Optical brightener 3 - Moisture, sulfate and various 6.6 100 with the meanings

   LAS linear C₁₂ alkylbenzene sulfonate

   AS sodium alkyl sulfate

   TAS sodium tallow alcohol sulfate

   45E7 C_14-15 primary alcohol condensed with an average of 7 moles ethylene oxide

   25E3 C_12-15 primary alcohol condensed with an average of 3 moles ethylene oxide

   PC3 percarbonate

   PB1 perborate monohydrate

   PB4 perborate tetrahydrate

   TAED tetraacetyl ethylenediamine

   PVP polyvinyl pyrrolidone

   PVNO polyvinyl pyridine-N oxide

   PVPVI polyvinyl pyrrolidone-polyvinyl imidazole copolymer

   MnPC manganese phthalocyanine tetrasulfonate

   EDTMP ethylenediamine tetramethylene phosphonate

   CMC carboxymethyl cellulose

   

   Optical brightener 1: R = diethanolamino and R₂ = SO₃Na
   Optical brightener 2: R = morpholino and R₂ = SO₃Na
   Optical brightener 3: R = anilino, R₂ = SO₃Na or H
2. A detergent as claimed in claim 1, characterized in that the ratio by weight of bleach activator to polyvinyl pyrrolidone is under 4:1 and, more particularly, is in the range from 0.5 to 3.5:1.
3. A detergent as claimed in claim 1 or 2, characterized in that it contains 0.1% by weight to 5% by weight and more particularly 0.4% by weight to 2.5% by weight of polyvinyl pyrrolidone.
4. A detergent as claimed in any of claims 1 to 3, characterized in that the polyvinyl pyrrolidone has a molecular weight of 5,000 to 4,000,000 and more particularly in the range from 10,000 to 100,000.
5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains 5% by weight to 25% by weight and more particularly 6% by weight to 15% by weight of bleaching agent based on active oxygen.
6. A detergent as claimed in any of claims 1 to 5, characterized in that the bleaching agent based on active oxygen is selected from hydrogen peroxide, alkali metal perborate monohydrate, alkali metal percarbonate and mixtures thereof.
7. A detergent as claimed in any of claims 2 to 6, characterized in that it contains 0.5% by weight to 10% by weight and more particularly 1% by weight to 7% by weight of bleach activator.
8. A detergent as claimed in any of claims 2 to 7, characterized in that the bleach activator is selected from the compounds which yield linear or branched, aliphatic, cycloaliphatic or aromatic C_2-12 peroxocarboxylic acid under perhydrolysis conditions and mixtures thereof.
9. A detergent as claimed in any of claims 1 to 8, characterized in that it is free from optical brightener.
10. A process for washing coloured laundry on its own or in combination with white laundry in a water-based surfactant-containing wash liquor using the detergent claimed in any of claims 1 to 9 or all its individual components in the ratios by weight mentioned, characterized in that the wash liquor at least periodically has a polyvinyl pyrrolidone concentration of from 0.01 g/l to 1 g/l and more particularly from 0.05 to 0.2 g/l and an active oxygen concentration of from 0.01 g/l to 0.2 g/l and more particularly from 0.03 g/l to 0.15 g/l.
11. A process for preventing changes of colour and for inhibiting the transfer of dyes to white or differently coloured laundry in the washing of coloured laundry on its own or in combination with white laundry in a water-based surfactant-containing wash liquor using the detergent claimed in any of claims 1 to 9 or all its individual components in the ratios by weight mentioned, characterized in that the wash liquor at least periodically has a polyvinyl pyrrolidone concentration of from 0.01 g/l to 1 g/l and more particularly from 0.05 to 0.2 g/l and an active oxygen concentration of from 0.01 g/l to 0.2 g/l and more particularly from 0.03 g/l to 0.15 g/l.
12. A process as claimed in claim 10 or 11, characterized in that the concentrations of polyvinyl pyrrolidone and active oxygen are maintained for 5 minutes to 90 minutes and more particularly for 10 minutes to 70 minutes.
13. A process as claimed in any of claims 10 to 12, characterized in that the effect of the active oxygen is strengthened by the in situ formation in the wash liquor of peroxocarboxylic acid from bleaching agent based on active oxygen and bleach activator.
14. A process as claimed in any of claims 10 to 13, characterized in that the wash liquor has a temperature of up to 60°C and more particularly in the range from 30°C to 60°C.
15. The use of the detergent claimed in any of claims 1 to 9 in a process for washing coloured laundry or for preventing changes of colour and for inhibiting the transfer of dyes to white or differently coloured laundry in the washing of coloured laundry.