JPH07503277A - Detergent composition containing a catalyst, an oxidation scavenger, and a peroxide-generating enzyme and inhibiting dye migration - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] A detergent containing a catalyst, an oxidation scavenger, and a peroxide-generating enzyme that inhibits dye transfer. agent composition Wave Jutsu Branch The present invention relates to compositions and methods for inhibiting dye transfer between fabrics during washing. Ru.

Background technique One of the most persistent and troublesome problems that arise during modern fabric washing operations is the In colored fabrics the dye tends to be released into the wash liquor. Next, dyeing The material travels with it onto other fabrics being washed.

One way to overcome this problem is to remove the particles that become attached to other articles in the cleaning solution. This would be a method of bleaching fugitive dyes eluted from dyed fabrics before dyeing.

Suspended or solubilized dyes can be removed in solution by using known bleaching agents. It can be oxidized to some extent.

British Patent No. 2,101,167 discloses that hydrogen peroxide is activated upon dilution. Stable liquid bleaching compositions containing hydrogen peroxide precursors that produce Ru.

However, at the same time, do not bleach the dye that actually remains on the fabric, i.e. color loss. It is important that no scratches (color damage) occur.

U.S. Patent No. 4,077.768 describes the use of oxidizing bleach and iron porphine. A method is described for inhibiting dye migration in combination with a catalytic compound.

Co-pending EP Patent Application No. 91202655.6 filed October 9, 1991 Specifications include dye transfer inhibitors including enzyme systems and porphine catalysts capable of generating hydrogen peroxide. The present invention relates to a control composition.

Due to the presence of oxidizing agents, the proteases and lipoproteins formulated in the dye transfer inhibiting compositions Detergent enzymes such as amylase, amylase, and cellulase are particularly effective in the absence of bleed dyes. Enzyme activity must be achieved in an oxidizing environment, resulting in loss of activity. .

The improved stability of the enzymes formulated in the enzymatic dye transfer inhibiting compositions is due to the enzyme oxidation scaffolds. It has now been discovered that what can be achieved by adding Venger.

According to one aspect of the invention, optimal dye transfer inhibition while being fully compatible with other enzymes Effective enzymatic dye transfer inhibiting compositions are provided.

Accordingly, dye transfer inhibiting compositions are provided that exhibit optimal dye transfer inhibiting properties.

According to another aspect, the present invention provides an efficient process for laundry operations involving colored fabrics. provide

Demonstration of invention The present invention (A) (a) metalloporphins and water-soluble or water-dispersible derivatives thereof; (b) metalloporphyrins and water-soluble or water-dispersible derivatives thereof; (C) Metal phthalocyanine and its water-soluble or water-dispersible derivatives A metal catalyst selected from; (B) Enzyme oxidation scavenger (C) Enzyme system that can generate hydrogen peroxide The present invention relates to a dye transfer inhibiting composition comprising:

According to another aspect of the invention, steps for laundering operations involving colored fabrics are also provided.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention (A) (a) metalloporphins and water-soluble or water-dispersible derivatives thereof; (b) metalloporphyrins and water-soluble or water-dispersible derivatives thereof; (C) Metal phthalocyanine and its water-soluble or water-dispersible derivatives Metal catalyst selected from: (B) Enzyme oxidation scavenger (C) Enzyme system that can generate hydrogen peroxide Provided is a dye transfer inhibiting composition comprising:

hydrogen peroxide precursor Hydrogen peroxide, an oxidizing agent, is produced by using an enzymatic hydrogen peroxide generation system. It happens on the spot.

The use of an enzymatic hydrogen peroxide generation system allows for the continuous generation of small amounts of hydrogen peroxide. and provides a practical way to control steady state small amounts of hydrogen peroxide. maximum effective Hydrogen peroxide has a similar rate of oxidative removal of dyes in wash water. Occurs when the amount is such that it is replenished by The enzyme used in the present invention is an oxidant It is

The oxidase is present in an amount of 0.1 to 20,000 units, preferably 0.5 units per gram of the composition. ~5000 units exist. One unit converts 1 μmol of substrate per minute. is the amount of enzyme required for

Suitable oxidases include urate oxidase, galactose oxidase, a alcohol oxidase, amine oxidase, amino acid oxidase, cholesterol Role oxidase and glucose oxidase, malate oxidase, glucose licorate oxidase, hexose oxidase, aryl alcohol oxidase Dase, L-gulonolactose oxidase, pyranose oxidase, L-so rubose oxidase, pyridoxine 4-oxidase, 2-2-hydroxy acid oxidase, choline oxidase, and ecdysone oxidase.

Preferred enzyme systems include alcohol and aldehyde oxidase, glucose oxidase It is Sidase.

A more preferred system for granular detergent applications is a solid alcohol, e.g. It is catalyzed by cose oxidase to form glucuronic acid and generate hydrogen peroxide. glucose.

A more preferred system for liquid detergent applications is a liquid detergent that can also act as a solvent, e.g. This would include Lecole. - An example is ethanol/ethanol oxidase .

The amount of oxidase to be used in the composition according to the invention is at least is sufficient to consistently generate 0.005 to 10 ppm of A0 in the cleaning solution. Should. For example, in the case of glucose oxidase, this means that and constant aeration in the washing process at pH 6-11, preferably 7-9. Below, glucose oxidase 1-20000U/ff, glucose 0.0 05-0.5%.

metal catalyst The preferred range of use of the catalyst in the cleaning solution is 10-8 mol - 10 mol, more preferably is 10-6 to 10-4 mol.

The inventive metalloporphine structure is visible as indicated in Formula I in the accompanying drawings. can be converted into In formula I, the atomic positions of the porphine structure are numbered in the usual way and Insert the double bond as usual. In other formulas, double bonds are omitted in the drawings. However, it actually exists in the same way as ■.

Preferred metalloporphine structures include carbons (methods) at positions 5, 10, 15 and 20 of formula I. (in the formula, n and m may be 0 or 1; A is a sulfate, sulfonate, phosphate or carboxylate group; may also be C-C1o alkyl, polyethoxyalkyl or hydroxyalkyl; kill) substituted with a phenyl or pyridyl substituent selected from the group consisting of .

Preferred molecules are substituted -CH2CH(OH)CH with phenyl or pyridyl groups. 503-1S O3 is selected from the group consisting of:

Particularly preferred metalloporphins have carbons at positions 5.1o, 15, and 20 of the molecule. is substituted with a substituent.

This preferred compound is a metal tetrasulfonated tetraphenylporphine. Known. The symbol X1 is (″cy-) (in the formula, each Y independently represents hydrogen, chlorine, bromine or meso-substituted alkyl, cycloalkyl, aralkyl/aryl, alkali or heteroaryl).

The symbol X2 in formula I represents an anion, preferably OH- or C1-. of formula I The compound may contain C1-C1o alkyl, hydroxyl at one or more of the remaining carbon positions. may be substituted with alkyl or oxyalkyl groups.

As phorfin derivatives, chlorophyll, chlorin, i.e., isobacterium Also mentioned are lorin and bacteriochlorin.

Metalloporphyrins and their water-soluble or water-dispersible derivatives have the formula ■ (wherein, X is alkyl, alkylcarboxy, alkylhydroxyl, vinyl, alkenyl, alkyl sulfate, alkyl sulfonate, sulfate, sulfate sulfonate, can be aryl) It has the structure given by .

The symbol X2 in formula H represents an anion, preferably OH- or 01-.

Symbol X is alkyl, alkylcarboxy, alkylhydroxyl, vinyl, alkyl Lukenyl, alkyl sulfate, alkyl sulfonate, sulfate, sulfate It can be Honate.

Metal phthalocyanine and its derivatives have the structure shown in the formula ■ (phthalocyanine Atomic positions in the structure are numbered as usual). The anionic group in the structure is Sodium and potassium cations or this structure remain water soluble Contains cations selected from the group consisting of other non-interfering cations. preferred phthalocyanine Anine derivatives include metal phthalocyanine trisulfonate and metal phthalocyanine trisulfonate. is tetrasulfonate.

Other forms of substitution possible for this invention are Fe, Mn, Co, Rh, Cr, Ru%Mo or substitution of the central metal by another transition metal.

In addition, when selecting modifications or substituents of the basic porphine or azaporphine structure, Many considerations are important. First, it is available or easily synthesized. I would choose a compound.

Besides this, the choice of substituents controls the solubility of the catalyst in water or in detergent solutions. can be used to In addition, it is especially effective at attacking dyes attached to solid surfaces. If it is desired to avoid substituents, the affinity of the catalytic compound for the surface can be controlled. Thus, strongly negatively charged substituted compounds, e.g. Sulfonated porphins are repelled by negatively charged stains or dirty surfaces. and therefore have a tendency to cause little attack on the fixed dye. stiffly In contrast, are cations or zwitterants attracted to such dirty surfaces? , or at least may not be repulsed.

Enzyme oxidation scavenger According to the present invention, improved stability of enzymes formulated in enzymatic dye transfer inhibiting compositions is achieved by: It has now been found that this can be achieved by adding enzymatic oxidative scavengers .

Enzymatic oxidation scavengers are enzymes that are more easily oxidized than enzymes in the presence of an enzymatic dye transfer inhibition system. refers to compounds that are oxidized to dyes but are not as easily oxidized as dye bleed from fabrics. Taste. The enzymatic oxidation scavenger of the present invention satisfies the following criteria.

First, the presence of the enzymatic oxidation scavenger formulated in the dye transfer inhibiting composition of the present invention The residual activity of the enzyme in the presence of Preferably it should be greater than 75%.

The amount of enzymatic oxidation scavenger to be used in the present invention is determined by the amount of enzymatic oxidation scavenger chosen. should be such that it depends on the operator and the above criteria are met. like this In addition, according to the present invention, it does not adversely affect the activity of the enzyme formulated with it. Dye transfer inhibiting compositions are provided that inhibit dye transfer while also inhibiting dye transfer.

Preferred enzymatic oxidation scavengers suitable for the present invention are amines, preferably of the formula %formula% (In the formula, R,, R 11, R2 is a C1-c18 alkyl group, aryl group, alkyl alcohol or is any aromatic compound, or R, , R1, R2 is a nitrogen-containing fat tertiary amines (which may be part of an aromatic ring structure). most A preferred tertiary amine is one in which R1 and R2 are C2H5 and R3 is C2H4OH. A compound having formula I.

Other amines suitable for use as enzymatic oxidation scavengers in the present invention include It is a koxylated polyamine.

Such a substance may conveniently have the formula %formula%) (In the formula, R'1 and R'2 are C1-c18 alkyl group, 71J-l group, alkyl group, or alkyl alcohol, nil, and X is alkyl, aryl, substituted alkyl or aryl, alkoxy) repeating unit can be represented as a molecule of experimental structure.

R'l, R'2 are cH2, and X is (CH2CH20)moH, and polyamide with 1<n<12.5<m<20 most preferred.

The amount of enzymatic oxidation scavenger in the detergent composition is preferably between 0.0005 and 1 0%, more preferably 0.001-7%, most preferably 0.005-5%. Ru.

The composition is conveniently used as an additive to main wash cycle detergent compositions. be done.

The present invention may also include detergent ingredients and thus serve as a detergent composition. dye transfer inhibiting compositions.

Enzymes that can be formulated in the present compositions can be active in removing stains or stains. Enzymes, such as proteases, lipases, amylases, carboxylases, Oxidase, cellulase or a mixture thereof.

Detergent ingredients A wide variety of surfactants can be used in detergent compositions. Anionic surfactant, non-ionic surfactants, amphoteric surfactants and zwitterionic surfactants, and their surfactants A typical list of species of agents may be found in U.S. Pat. No. 3,664,961.

Mixtures of anionic surfactants, especially from 5:1 to 1:2, preferably from 3:1 to 2 23, more preferably 3:1 to 1:1 weight ratio of sulfonate surfactant and surfactant. Mixtures with ruphate surfactants are particularly suitable here.

Preferred sulfonates include 9 to 15, especially 11 to 13 sulfonates in the alkyl group. alkylbenzene sulfonates having carbon atoms of α-sulfonated methyl derived from a 18 fat source, preferably a 016-C18 fat source Examples include fatty acid esters. In each case the cation is an alkali metal, preferably Or sodium. Preferred sulfate surfactants include in the alkyl group Alkyl sulfates having 12 to 18 carbon atoms (optionally alkyl having 10 to 20, preferably 10 to 16 carbon atoms in the group and an average ethyl (a mixture with ethoxy sulfate having a degree of sulfurization of 1 to 6). preferred here Examples of alkyl sulfates are tallow alkyl sulfate, coconut alkyl sulfate, Rusulfate, and C14-15 alkyl sulfate. in each case The cation is again an alkali metal cation, preferably sodium.

One type of nonionic surfactant useful in the present invention has an average hydrophilic-lipophilic balance of (HLB) 8-17, preferably 9.5-13.5, more preferably 10-12 ．． A condensate of a hydrophobic moiety and ethylene oxide to provide a surfactant with 5 It is. The hydrophobic (oleophilic) moiety may be aliphatic or aromatic in nature and may be The length of the polyoxyethylene group condensed with a given hydrophobic group is determined by the length of the hydrophilic element and the hydrophobic group. to produce water-soluble compounds with the desired balance between Easy to adjust.

Particularly preferred nonionic surfactants of this type are from 3 to 8 moles per mole of alcohol. 09-C15 primary alcohol ethoxylate containing ethylene oxide , especially C14 containing 6 to 8 moles of ethylene oxide per mole of alcohol ~C15 primary alcohol and 3 to 5 moles of ethylene per mole of alcohol It is a C12-C14 primary alcohol containing oxide.

Another type of nonionic surfactant has the general formula %) (wherein Z is a moiety derived from glucose; R has 12 to 18 carbon atoms is a saturated alkyl hydrophobic group having; t is 0 to 10, n is 2 or 3; ; X is 1.3 to 4) (the compound is an unreacted fat Contains less than 10% fatty alcohols and less than 50% short chain alkyl polygel compounds) Consisting of

Compounds of this type and their use in detergents are described in EP-B 0070 077; Disclosed in Specification No. 0.075.996 and Specification No. 0.094.118. ing.

R1 (In the formula, R is H or R1 is C 1-4 hydrocal bir, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof Yes, R2 is a C5-31 hydrocarbon and Z has at least 3 hydroxyls directly linked to the chain. Polyhydroxyhydrocarbyl having a linear hydrocarpyl chain or its alkyl coquinated derivative) Polyhydroxy fatty acid amide surfactants are suitable as nonionic surfactants. be. Preferably R1 is methyl and R2 is 011-15 alkyl or alkyl. rukenyl straight chain, such as coconut alkyl or a mixture thereof, and Z is In the original amination reaction, glucose, fructose, maltose, lactose Which reducing sugar is derived from?

The composition according to the invention may further include a builder system. aluminosilicate silicates, polycarboxylates and fatty acids, ethylenediaminetetra Substances such as acetates, sequestering agents such as aminopolyphosphonates, especially Ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepenta Any conventional builder system may be used here, including methylene phosphonic acid. suitable. Although less preferred for obvious environmental reasons, phosphate builders can also be used here.

Suitable builders are inorganic ion exchange materials, usually inorganic hydrated aluminosilicate materials. , more particularly hydrated synthetic zeolites, such as hydrated zeolite A, XSB or HS It can be.

Other suitable inorganic builder materials are layered silicates, such as 5KS-6 (Hex ). 5KS-6 is sodium silicate (Na2Sl205) It is a crystalline layered silicate consisting of

Polycarboxylate builders suitable for use herein include citric acid ( preferably in the form of a water-soluble salt), formula R-CH(COOH)CH2(COOH) (formula where R is CIO~20 alkyl or alkenyl, preferably C12~16 or R can be substituted with hydroxyl, sulfosulfoxyl or sulfone substituents. Examples include succinic acid derivatives. Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, 2-succinate -tetradecenyl. The succinate builder is preferably a succinate builder. Including alkanol ammonium salts, potassium salts, ammonium salts and alkanol ammonium salts. It is used in water-soluble salt form.

Other suitable polycarboxylates are oxodisuccinate and tartrate. Mixtures of monosuccinic acid and tartrate disuccinic acid, e.g. U.S. Pat. It is described in the specification of No. 63°071.

Fatty acid builders suitable for use herein, particularly in the case of liquid formulations of the invention. are saturated or unsaturated C1O-18 fatty acids as well as the corresponding soaps. preferred A highly saturated column has 12 to 16 carbon atoms in the alkyl chain. preferred unsaturation The fatty acid is oleic acid. Another builder system preferred for liquid compositions is Dodecace Based on nyl succinic acid.

Preferred builder systems for use in granular compositions include water-insoluble builder systems such as Zeolite A. Aluminosilicate builders and water-soluble carboxylate chelates such as citric acid including mixtures with oxidizing agents.

Can also form part of a builder system for use in granular compositions for the purposes of the present invention The builder substances include alkali metal carbonates, bicarbonates, silicates, etc. organic substances, and organic phosphonates, aminopolyalkylenephosphonates, amino Examples include organic materials such as polycarboxylates.

Other suitable water-soluble organic salts include homopolymer or copolymer acids or salts thereof (polymers). Ricarboxylic acids are composed of at least two dicarboxylic acids separated from each other by no more than two carbon atoms. (contains a carboxyl group).

Polymers of this type are disclosed in British Patent No. 1,596,756.

Examples of such salts include polyacrylates with a molecular weight of 2,000 to 5,000; and maleic anhydride (such copolymers have a molecular weight of 20,000 to 70,000, particularly approximately 40,000).

The detersive builder salt usually accounts for 10-80% by weight of the composition, preferably 20-70%. % by weight, most commonly 30-60% by weight.

The compositions of the invention should not contain conventional bleaching agents.

Other ingredients used in detergent compositions, such as foam boosters or foam inhibitors, enzymes and stabilizers or activators for stains, anti-staining agents, antifouling agents, optical brighteners, polishing Agents, bactericides, anti-fog agents, colorants, and fragrances may also be used. seed of becoming Particularly favorable is the combination with enzyme technology, which also provides color care benefits. . An example is a color maintenance/rejuvenation cellulase.

These ingredients, especially enzymes, optical brighteners, colorants, and fragrances, are preferably It should be chosen to be compatible with the bleach component of the formulation.

The detergent composition according to the invention can be in liquid, paste or granular form.

The granular composition according to the invention can also be in "compact form", i.e. It may have a relatively higher density than granular detergents, i.e. 550-950 g/N. ; In such cases, the granular detergent composition according to the present invention is more effective than ordinary granular detergents. and will contain small amounts of "inorganic filler salts"; typical filler salts include sulfuric acid and alkaline earth metal salts of chlorides, typically sodium sulfate; Impact' detergents typically contain up to 10% filler salts.

The present invention also provides solutions for solubilized suspension dyes encountered during fabric laundering operations involving colored fabrics. The present invention relates to a method for inhibiting dye transfer from one fabric to another.

The method consists of contacting the fabric with a washing liquid as described above.

The method of the invention is conveniently carried out in a course of washing procedures.

The washing process is preferably carried out at a temperature between 5°C and 90°C, especially between 20 and 60°C, but the catalyst is Effective up to 5°C. The pH of the treatment liquid is preferably 7 to 11, particularly 7.5 to 1. It is 0.5.

The methods and compositions of the invention can also be used as additives during laundry operations.

The following examples are meant to illustrate compositions of the invention, but do not limit the scope of the invention. The foregoing scope does not necessarily imply or otherwise stipulate that determined according to the range of

General test conditions To assess the stabilizing effect of enzymatic oxidation scavengers on enzymes, samples were It is necessary that no fees are included. The reason is that dyes are also enzymatic oxidation scavengers. This is because it works in this way. The stability of enzymes formulated in dye transfer inhibiting compositions is Compare in the absence and presence of elementary oxidizing scavengers. In more detail, The stability of iron porphine catalysts and glucose oxidase/glucose Measured in the presence of the system.

■) In the absence of enzymatic oxidation scavengers ■) In the presence of enzymatic oxidation scavengers Protease activity Protease activity was determined spectrophotometrically by measuring absorbance at a wavelength of 410 ns. Lightly lit. This is succinyl-Ala-Ala-Pro-Phe-p-di) (+Production of p-nitroaniline, the product of protease cleavage of anilide) respond to changes in 1 ml dimethyl sulfoxide (DMSO) for 50 mg substrate using this pNA substrate (i.e. succinyl A 1 a-A 1 a -- -) is dissolved in dimethyl sulfoxide (DMSO). Keep dissolved substrate frozen One. Before testing protease activity, solutions of PNA substrate were prepared in a 1:20 volume ratio. Prepare the substrate by diluting it into Tris buffer, pH 8.0, using

Approximately 100 μg of diluted pNA substrate was added to the analyte solution (1) or (I) in the cell. Add to 1 ml of sample I). The sample was then introduced into the spectrophotometer and 410 ns Monitor the absorbance at ' for about 5 minutes. The absorbance curve is for the first few minutes (approximately 3 minutes) It should be a straight line across. If this is not true, solution (1) or (II) should be diluted with Tris buffer. For example, Genoncol at the above concentration. Samples that give a linear response using protease B from and 900 μg of Tris buffer, pH 8.0 (ie, 1:9 dilution ratio). Said A sample of a solution containing savinase (5av4naseR) at a concentration of gives a response (ie, no dilution is necessary).

The slope of the absorbance curve is an indicator of protease activity.

The residual activity of solutions (1) and (II) is determined by the iron porphine catalyst and glucose /Compare with the gradient obtained before adding the osidase system.

Dye oxidation: The extent of dye oxidation is determined in 100 ml of 100 mM phosphate buffer. magnetic Stir the buffer continuously in the beaker at a constant speed using a stirrer. oxidation The percentage of dye added is determined spectrophotometrically.

Example 1 A 0.1M phosphate buffer was prepared and its pH was adjusted to 8.0. Then, Four 100 ml samples with the following composition were prepared in separate beakers.

Solution A: 0.1 glucose oxidase unit/m1Fe (m)TPP3 10ppm Glucose 0.1% BPN’ (made by Genonkol) 1. lpppmppm solution Liquid-liquid A + Scavenger Solution C: 0.1 glucose oxidase unit/m1Fe (III) TPP5 10p pm glucose 0.1% Direct Blue (CI#24410) 40ppm.

Absorbance peak at 600 rv Solution D: Solution C + Scavenger The solution was stirred at room temperature using a magnetic stirrer. Protease stability and acids The amount of dye converted was determined according to the method described in the text.

Oxidized solution Residual activity rate of protease Dye 510 minutes after 30 minutes No scavenger 4577 Dimethylaminoethanol 0.05% 7576 solution now contains 1% detergent Using the same concentrations and experimental conditions as in Example 1 except for Protease B (Genocol) The stability of the product (manufactured by J.D.) was studied at pH 7 and 8. The tertiary amine used in this test was 3 Ethoxylated tetraethylenepentamine (MW-4800) at a concentration of 0 ppm. It was.

Oxidized solution Residual activity rate of protease Dye 510 minutes after 30 minutes No scavenger 25 100 Except for the details described below, this experiment was performed using a Ni Gelcose oxidase concentration = 2 units/ml F e (III) TPPS; Agricultural content: 5ppm Enzyme: Sabinase R (manufactured by Novo) 32E-6KNPU/ml Cid Red 151 (CI#26900) 40ppm.

Absorbance peak at 480-490 nm 0.1M phosphate buffer at pH 10.5 Solution to be oxidized Remains of protease Reactive activity rate Dye 510 minutes after 30 minutes No scavenger 1695 A liquid dye transfer inhibiting composition according to the present invention having the following composition is prepared.

% Linear alkylbenzene sulfonate 10 Alkyl sulfate 4 Fatty alcohol (012-C15) ethoxylate 12 fatty acids lO Oleic acid 4 Citric acid I N　a　OH3,4 Propanediol 1.5 Ethanol 5 Ethanol oxidase 5 u / ml ferric tetrasulfonated tetrafe Nirupol 0.1 fin Ethoxylated Tetraethylene Pentamine 0.3 Genoncor Protease B O, 33 trace component balance (assumed to be 100) sail y A granular dye transfer inhibiting composition according to the present invention having the following formulation was prepared. Ru.

disaster Linear alkylbenzene sulfonate 11.40 tallow alkyl sulfate 1. 80 7x ethoxylated C45 alcohol 4,0011x ethoxylated taro - Alcohol 1.80 Dispersant 0.07 Silicone fluid 0.80 Trisodium citrate 14.00 Maleic acid-actylic acid copolymer 5.00D E T M P A 1.00 Cellulase (active protein) 0.03 Alcalase/B A N O, l iO lipase 0.36 Sodium silicate 2.00 Sodium sulfate 3.50 Ferric tetrasulfonated tetraphenylporglucose oxidase 10 0 u/ml diethylaminoethanol 0.05 Trace component balance (assumed to be 100) Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE) , 0A (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD.

TG), BB, BG, BR, CA, CZ, FI, HU.

JP, KP, KR, LK, MG, MN, MW, No, NZ, PL, R○, R U, SD, SK, UA, US (72) Inventor Johnston, James Piyot Oberisse, Tbelgian, Pay Plan, 17

Claims (26)

[Claims] 1. (A) (a) metalloporphins and water-soluble or water-dispersible derivatives thereof; (b) metalloporphyrins and water-soluble or water-dispersible derivatives thereof; (c) Metal phthalocyanine and its water-soluble or water-dispersible derivatives A metal catalyst selected from; (B) Enzyme oxidation scavenger (C) Enzyme system that can generate hydrogen peroxide A dye transfer inhibiting composition comprising: 2. the amine base catalyst stabilizer is selected from imidazole and its derivatives; The dye transfer inhibiting composition according to claim 1. 3. The enzymatic oxidation scavenger has the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (In the formula, R1, R2, R3 are C1 to C18 alkoxy groups, aryl groups, alkyl is either an alcohol or an aromatic compound, or R1, R2, R3 are nitrogen can be part of an aliphatic or aromatic ring structure containing The dye transfer inhibiting composition according to claim 1 or 2, which is selected from the following. 4. According to claim 3, R1 and R2 are C2H5 and R3 is C2H4OH. A dye transfer inhibiting composition. 5. The enzymatic oxidation scavenger has the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (In the formula, R'1 and R'2 are an alkyl group, an aryl group, an alkoxy group, or an alcohol group. n<1, and X is alkyl, alkyl, or aryl. The dye transfer inhibitor according to claim 1 or 2, which is selected from polyamines having Composition. 6. R′1, R′x are CH2, X is (CH2CH2O)mH, and 1< The dye transfer inhibiting composition according to claim 5, wherein n<12 and 5<m<20. 7. The enzyme system contains oxidase and alcohol, aldehyde or 7. A dye transfer inhibiting composition according to claims 1 to 6, comprising a combination of both. 8. contains a metal porphine derivative, and the iron porphine is at least one meso position. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼(In the formula, n and m may be 0 or 1, A is sulfate, selected from the group consisting of sulfonate, phosphate, and carboxylate groups. , B is C1-C10 alkyl, C1-C10 polyethoxyalkyl and C1- (selected from the group consisting of C10 hydroxyalkyl) Dye transfer according to claims 1 to 7, substituted with phenyl or biridyl substituents. Inhibitory composition. 9. The substituent on the phenyl or pyridyl group is -CH3, -C2H5, -CH2C H2CH2SO3-, -CH2COO-, -CH2C-H(OH)CH2SO3-, and -SO3 The dye transfer inhibiting composition according to claim 5. 10. contains a metal porphine derivative, and the metal porphin is at least at the meso position. There are also ▲mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X1 is (-CY-) (wherein each Y independently represents hydrogen, chlorine, bromine or meso Substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or is a teloaryl) 8. Substituted with a phenyl substituent selected from the group consisting of A dye transfer inhibiting composition. 11. The catalyst compound is a metal tetrasulfonated tetraphenylporphine. 8. The dye transfer inhibiting composition according to claim 7. 12. The metal of the metal catalyst is Fe, Mn, Co, Rh, CR, Ru, Mo or 2. The dye transfer inhibiting composition of claim 1, wherein the composition is substituted with other transition metals. 13. The concentration of the metal catalyst is 10-8 to 10-3 mol, preferably 10-6 to 10- 4. The dye transfer inhibiting composition of claim 1, wherein the composition is 4 moles. 14. The oxidase is 0.1 to 20,000 units per gram of the composition, preferably 0. ．． 5. The dye transfer inhibiting composition of claim 4, wherein 5 to 5000 units are present. 15. The dye transfer inhibiting composition according to claim 4, wherein the substrate is glucose. 16. The dye transfer inhibitor according to claim 4, wherein the substrate consists of a C1-C6 alcohol. control composition. 17. 17. The dye transfer inhibiting composition of claim 16, wherein the substrate is ethanol. 18. Dye transfer according to claim 3, wherein the substrate is present from 0.1 to 50% by weight of the composition. Inhibitory composition. 19. Generates hydrogen peroxide at a concentration of 0.005 to 10 ppm/min during the cleaning process The dye transfer inhibiting composition according to claim 1. 20. The enzymatic oxidation scavenger is present in an amount of 0.0005 to 10% by weight of the total composition. A dye transfer inhibiting composition according to claim 1, wherein the dye transfer inhibiting composition is present. 21. The enzymatic oxidation scavenger is present in an amount of 0.005 to 5% by weight of the total composition. The dye transfer inhibiting composition according to claim 20. 22. 22. A detergent additive according to claims 1 to 21, which is a detergent additive in dust-free granulate or liquid form. The dye transfer inhibiting composition described above. 23. The dye transfer inhibiting composition according to any one of the preceding claims, Detergents characterized in that they further contain surfactants, builders and other customary detergent ingredients Composition. 24. A method for inhibiting dye transfer between fabrics during washing operations involving colored fabrics, the method comprising: The fabric is brought into contact with a washing liquid containing the dye transfer inhibiting composition according to claims 1 to 23. A method characterized by: Inhibition of dye migration according to claim 24, carried out at a temperature within the range of 25.5°C to 90°C. Law. 26. Dye transfer according to claim 24 or 25, wherein the pH of the bleaching bath is between 7 and 11. suppression method.