MXPA98000573A - Detergent compositions that inhibit the transfer of colorant based on vinilpirid copolymers - Google Patents

Abstract

A composition that inhibits the transfer of dye comprising a vinylpyridine copolymer

Description

DETERGENT COMPOSITIONS THAT INHIBIT THE TRANSFER OF COLORANT BASED ON VINYL PYRIDINE COPOLYMERS FIELD OF THE INVENTION The present invention relates to a composition and method for inhibiting the transfer of dye between fabrics during washing. More particularly, the present invention relates to detergent compositions comprising water-soluble vinylpyridine copolymers.

BACKGROUND OF THE INVENTION One of the most persistent and worrisome problems that arise during modern fabric washing operations is the tendency of some fabrics dyed to release dye in the washing solutions. The dye is then transferred to other fabrics being washed with it. One way to overcome this problem would be to complex or adsorb fugitive dyes washed from dyed fabrics before they have the opportunity to be fixed to other articles in the wash. Polymers have been used within detergent compositions to inhibit dye transfer. One type of said polymers are homo- and copolymers of N-vinylimidazole.

Examples of such polymers are described in prior art documents such as DE 2 814 287-A which relates to detergent compositions comprising 0.1 to 10% by weight of water-soluble or water-soluble homo- or copolymer of N-vinylimidazole. dispersing in water in combination with anionic and / or nonionic surfactants and other detergent ingredients. EP 372 291 relates to a process for washing fabrics sensitive to discoloration. The washing liquid contains anionic / non-ionic surfactants and water-soluble polymers, for example, (co) polymers N-vinylimidazole, N-vinyloxazolidone or N-vinylpyrrolidone. EP 327 927 describes a granular detergent additive comprising water-soluble polymeric compounds based on N-vinylpyrrolidone and / or N-vinylimidazole and / or N-vinyloxazolidone and cationic compounds. DE 4027832-A discloses electrolyte-free liquid detergent compositions comprising zeolite A, nonionic surfactants and polymers that inhibit dye transfer. Polymers that inhibit dye transfer are homo- and copolymers selected from N-vinylpyrrolidone and / or N-vinylimidazole and / or N-vinyloxazolidone. Polyamine N-oxide is described in European Patent Application No. 93201198.4. It has now been discovered that water-soluble vinylpyridine copolymers are very efficient in eliminating the transfer of solubilized or suspended dyes. This discovery allows the formulation of detergent compositions exhibiting excellent dye transfer and cleaning properties. In accordance with another embodiment of this invention, a process for washing operations involving dyed fabrics is also provided.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to compositions that inhibit the transfer of dye comprising a polymer selected from water-soluble vinylpyridine copolymers.

DETAILED DESCRIPTION OF THE INVENTION THE VINILPIRIDINE C0P0LIMER0 The present invention comprises as an essential ingredient a polymer selected from the class of water-soluble vinylpyridine copolymers. The vinylpyridine copolymers have an average molecular weight of 5000-1,000,000. Highly preferred polymers for use in compositions that inhibit dye transfer according to the present invention comprise a polymer selected from vinylpyridine copolymers wherein said polymer has an average molecular weight in the range of 5,000 to 100,000, more preferable from 10,000 to 30,000, very preferable from 10,000 to 20,000. The average molecular weight scale was determined by light scattering as described in Barth H. G. and Mays J. W. Chemical Analysis Vol 113. "Modern Methods of Polymer Characterization". In addition, it has been found that an excellent overall detergency performance of detergent compositions comprising vinylpyridine copolymers can be obtained by selecting a specific scale of average molecular weight from 5,000 to 50,000.; more preferable from 8,000 to 30,000; very preferable from 10,000 to 20,000. Vinylpyridine copolymers characterized by having said average molecular weight scale provide excellent properties that inhibit dye transfer without adversely affecting the cleaning performance of the detergent compositions formulated therewith. Any copolymerizing group can be used as long as the polymer formed is soluble in water and has properties that inhibit dye transfer. Examples of suitable copolymerizing groups include formic acid, acrylic acid, maleic acid, vinylpyrrolidone, vinyl acetate. Preferred copolymers are based on 4-vinylpyridine with vinyl pyrrolidone, acrylic acid and maleic acid. The vinylpyridine copolymerizing monomer of the present invention has a molar ratio of copolymer to vinylpyridine from 1 to 0.01, preferably from 0.5 to 0.05, most preferably from 0.3 to 0.05.

The vinylpyridine copolymers can be linear or branched. Vinylpyridine copolymers are typically present from 0.001 to 10%, more preferably from 0.01 to 2%, most preferred from 0.05 to 1% by weight of the composition that inhibits dye transfer. The present compositions are conveniently used as additives for conventional detergent compositions for use in washing operations. The present invention also encompasses compositions that inhibit dye transfer which will contain detergent ingredients and thus serve as detergent compositions. The level of the vinylpyridine copolymer present in the detergent compositions is from 0.01 to 10%, more preferably from 0.05 to 5%, most preferably from 0.1 to 1% by weight of the detergent composition.

METHOD FOR MAKING THE VINYL PYRIDINE COPOLYMER The polymer is usually prepared by copolymerizing vinylpyridine with water-soluble monomers in one or a mixture of water, methanol, isopropanol and acetone in the presence of polymerization initiator (s) such as water soluble azo initiators, sodium persulfate and / or sodium peroxide. hydrogen, and optionally a chain transfer agent. The typical reaction temperatures are 70-9O ° C and the pH is 3-7.

DETERGENT ATTACHMENTS In another embodiment of the present invention, the liquid detergent composition may comprise one or more of a surfactant selected from a wide variety of surfactants. A typical list of anionic, non-ionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in the U.S. Patent. No. 3,666,961, issued to Norris on May 23, 1972. The highly preferred anionic surfactants include the alkyl sulfate surfactants which herein are water soluble salts or acids of the formula ROSO3M wherein R is preferably a C10 hydrocarbyl. C24, preferably an alkyl or hydroxyalkyl having a C10-C18 alkyl component, more preferably an alkyl or hydroxyalkyl of Cio-Cis, and M is H or a cation, for example, an alkali metal cation (e.g., sodium , potassium, lithium), a substituted ammonium or ammonium cation (eg, monoethanolamine, methyl-, dimethyl- and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and quaternary ammonium cations alkylamines derivatives such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Especially preferred are branched alkyl sulphates.

Preferred anionic surfactants include alkoxylated alkylsulfate surfactants which are herein water soluble salts or acids of the formula RO (A) mS? 3M wherein R is an alkyl or hydroxyalkyl group of C10-C2-; unsubstituted having a C10-C2 alkyl component, preferably a C12-C18 alkyl or hydroxyalkyl, most preferably an alkyl or hydroalkyl group of C12-C15, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6; most preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), a cation of ammonium or substituted ammonium (eg, monoethanolamine, methyl-, dimethyl- and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine , triethylamine, and mixtures thereof, and the like). Ethoxylated alkyl sulfates as well as propoxylated alkyl sulphates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethylammonium and di-ethylpiperidinium cations and those derivatives of alkylamines such as ethylamine., diethylamine, triethylamine, mixtures thereof and the like. Examples of surfactants are C12-C15 polyethoxylated alkyl sulfate (Ci2-C? SE (1.0) M), C12-C15 polyethoxylated alkyl sulfate (C12-Ci5E (2.25) M), polyethoxylated alkyl sulfate (3.0)? of C12-C15 (Ci2-Ci5E (3.0) M), and C12-C15 polyethoxylated alkylsulfate (4.0) (Ci2-C? ßE (4.0) M), wherein M is conveniently selected from sodium and potassium. Other suitable anionic surfactants to be used are alkyl ester sulfonate surfactants which include linear esters of C8-C20 carboxylic acids (ie, fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of The American Oil Chemists Society ", 52 ((1975), pp. 323-329. Suitable starting materials would include natural fatty substances such as tallow derivatives, palm oil, etc. The preferred alkyl ester sulfonate surfactant, especially for laundry applications, it comprises alkyl estersulfonate surfactants of the structural formula: R3-CH-C-OR * SO3M wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or a combination thereof, 4 is a hydrocarbyl of Ci-Cβ, preferably an alkyl or a combination thereof, and M is a cation which forms a water-soluble salt with the alkyl estersulfonate. Suitable salt forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R3 is C10-Ci6 alkyl, and * is methyl, ethyl or isopropyl. Especially preferred are these methyl sulphonates wherein R3 is C10-C16 alkyl. Other anionic surfactants useful for detersive purposes can also be included in the liquid detergent compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di and triethanolamine salts) of soap, C9-C20 linear alkyl benzenesulfonates, C8 primary or secondary alkanesulfonates. C22, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, for example, as described in British Patent Specification No. 1,082,179, polyglycol ether alkyl sulfates of C8-C2-4 (containing up to 10 moles of ethylene oxide); alkylglyceryl sulfonates, fatty acyl glyceryl sulphonates, oleylglyceryl fatty sulphonates, alkylphenolthylethate ether sulphates, paraffinsulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyltaurates, alkylsuccinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 6 -C 12 diesters), acyl sarcosinates, alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (the non-sulphonated nonionic compounds described below), branched primary alkyl sulphates and alkylpolyethoxycarboxylates such as those of the formula RO (CH2CH2?) K -CH2C00-M + wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as colophonic acids, hydrogenated rosin acids and resin acids and hydrogenated resin acids present in or derived from wood oil. Additional oils are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally described in the U.S. Patent. 3,929,678, issued December 30, 1975 Laughlin and others in Column 23, line 58 to Column 29, line 13 (incorporated herein by reference). Upon inclusion, the detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of said surfactants. One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic portion to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range of 8 to 17, preferably 9.5. to 14, more preferably from 12 to 14. The hydrophobic (lipophilic) portion can be aliphatic or aromatic in nature and the length of the polyoxyethylene group that is condensed with any particular hydrophobic group can be readily adjusted to give a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Especially preferred surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the primary C12-C15 alcohols containing 5-8 moles of ethylene per mole of alcohol. Another class of suitable nonionic surfactants comprises alkyl polyglycoside compounds of the general formula RO (CnH2n0) tZx wherein Z is a glucose derived portion; R is a saturated hydrophobic alkyl group containing from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergents are described in EP-B 0 070 077, 0 075 996 and 0 094 118. The highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula R2-C-N-Z, Wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl or a mixture thereof, R2 is C5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R * is methyl, R2 is a straight alkyl or C11-15 alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction. Other suitable nonionics are amine oxide surfactants. The compositions of the present invention can comprise amine oxide according to the general formula I: Rl (E0) ((P0) and (B0) IN (0) (CH2R ') 2.qH20 (I) In general, it can be Note that the structure (I) provides a long chain portion Rl (EO) * (P0) and (B0)? and two portions of short chain, CH2R '. R 'is preferably selected from hydrogen, methyl and -CH2OH. In general, R1 is a primary or branched hydrocarbyl portion which may be saturated or unsaturated, preferably Ri is a primary alkyl portion. When x + y + z = 0, R is a hydrocarbyl portion having a chain length of about 8 to about 18. When x + y + z is different from 0, R1 may be somehow longer, having a length of chain on the scale of C12-C2-;. The general formula also encompasses amine oxides wherein x + y + z) 0, R 1 = C β -Ciß, R '= H and q = 0-2, preferably 2. These amine oxides are illustrated by alkyldimethyl amine oxide of C12-14, hexadecyl dimethylamine oxide, octadecylane oxide and its hydrates, especially the dihydrates as described in US Pat. 5,075,501 and 5,071,594, incorporated herein by reference. The invention also encompasses amine oxides wherein x + y + z is nonzero, specifically x + y + x is from about 1 to about 10, R1 is a primary alkyl group containing 8 to about 24 carbon atoms, preferably from about 12 to about 16 carbon atoms; in these modalities y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; E0 represents ethyleneoxy; P0 represents propyleneoxy; and B0 represents butyleneoxy. Said amine oxides can be prepared by conventional synthetic methods, for example, by the reaction of alkyl ethoxy sulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide. Preferred embodiments include dodecyldimethylamine, tetradecyldimethylaminoxydehydrate, hexadecyldimethylaminoxydehydrate and octadecyldi ethylamine dihydrate oxide. Although in some preferred embodiments R1 = H, there is some latitude with respect to having R 'slightly longer than H. Specifically, the invention further encompasses embodiments wherein R' = CH2OH, such as hexadecylbis (2-hydroxyethyl) oxide amine, sebobis (2-hydroxyethyl) amine oxide, stearylbis (2-hydroxyethyl) amine oxide and oleylbis (2-hydroxyethyl) amine oxide, dodecyldimethyl (2-hydroxyethyl) amine oxide dihydrate. Other suitable nonionic surfactants comprise alkyl polyglycoside compounds of the general formula RO (CnH2r.0) tZ * wherein Z is a glucose derived portion; R is a saturated hydrophobic alkyl group containing from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergents are described in EP-B 0 070 077, 0 075 996 and 0 094 118. When included herein, the liquid detergent compositions of the present invention typically comprise nonionic surfactants in the present invention. the weight ratio of anionic surfactant to nonionic surfactant from 6: 1 to 1: 3, preferably from 5: 1 to 2: 1. Suitable cationic detersive surfactants for use in the liquid detergent compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants such as alkyl dimethyl onion halide and those surfactants having the formula: [R2 (0R3) >;,] [R4 (0R3) and] 2R5N + X "wherein R2 is an alkyl or alkylbenzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH (CH3) -, -CH2CH (CH20H) -, -CH2CH2CH2-, and mixtures thereof, each R * is selected from the group consisting of C1-C4 alkyl, hydroxyalkyl of Ci -C « , benzyl, ring structures formed by the joining of two groups *, -CH2CHOH-CHOHCOR6CHOHCH2OH where R * is any hexose or hexose polymer having a molecular weight less than about 1,000, and hydrogen when and is not 0; R5 is the same as R * o is an alkyl chain in which the total number of carbon atoms of R2 plus R5 is no more than about 18, each y is from 0 to about 10, and the sum of the y-values is 0 at about 15, and X is any compatible anion.The preferred cationic surfactants are the ammonium quaternary compounds. Water-soluble nanos useful in the present composition having the formula: Ri R2R3 RA N + X- (i) wherein R1 is Cs-Cis alkyl, each of R2, R3 and A is independently Ci-C4 alkyl, hydroxyalkyl of Ci-d, benzyl, and - (C2HAO) XH wherein x has a value of 1 to 5, and X is an anion. No more than one of R2, R3 or R ?, must be benzyl. The preferred alkyl chain length for R is C12-C15 particularly wherein the alkyl group is a mixture of chain lengths derived from palm or coconut fat or is synthetically derived by the formation of olefin or by synthesis of alcohols 0X0. Preferred groups for R2R3 and RA are methyl and hydroxyethyl groups and the anion X can be selected from halide, methosulfate, acetate and phosphate ions. Examples of suitable quaternary ammonium compounds of the formula (i) for use herein are: coconut trimethyl ammonium chlorine or bromine; chlorine or ammonium bromide of coconut methyl hydroxyethyl; decyltriethyl ammonium chlorine; decylmethylhydroxyethyl ammonium chlorine or bromine; chlorine or ammonium bromine of C12-15 dihydroxyethyl ethyl; chlorine or ammonium bromide of coconut dimethylhydroxyethyl; ammonium methylsulfate of my ristyltrimethyl; chlorine or ammonium bromide of lauryl-ethylbenzyl; chlorine or ammonium bromide of lauryl dimethyl (ethenoxy) 4; colin esters (compounds of the formula (i) wherein Ri is alkyl of -CH2-0-C (0) -Ci2-i4 and R2R3R4 are methyl). Other cationic surfactants useful herein are also described in the U.S. Patent. 4,228,044, Cambre, issued October 14, 1980. When included herein, the detergent compositions of the present invention typically comprise from 0.5% to about 5%, preferably from about 1% to about 3% by weight of said cationic surfactants. The compositions according to the present invention may further comprise a builder system. Any detergency builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as polyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene acid. pentamethylene phosphonic triamine. Although they are less preferred for environmental reasons, phosphate builders can also be used. Polycarboxylate builders suitable for use herein include citric acid, preferably in the form of a water soluble salt, succinic acid derivatives of the formula R-CH (C00H) CH2 (C00H) wherein R is alkyl or C10-20 alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfosulfoxyl or sulfone substituents. Specific examples include lauryl succinate, myristyl succinate, pal ityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts. Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic acid and tartrate disuccinic acid such as described in US Pat. 4,663,071. Fatty acid builders suitable for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Another preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid. Builder salts are usually included in amounts of 10% to 80% by weight of the composition, preferably 20% to 70% and more usually 30% to 60% by weight. Other detergent ingredients that may be included are detersive enzymes which may be included in the formulations herein for a wide variety of purposes including, for example, removal of protein-based, carbohydrate-based or triglyceride-based spots, and to avoid the transfer of migratory dyes. Enzymes to be incorporated include proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. Other types of enzymes can also be included. They can be of any suitable origin, such as plant, animal, bacterial, mycotic and yeast origin. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, very typically about 0.05 mg to about 3 mg of active enzyme per gram of the composition. Suitable examples of proteases are the subtilicins that are obtained from particular strains of B.subtilis and B.licheniforms. Commercially available proteolytic enzymes suitable for removing protein-based stains include those sold under the trademarks Alacalase, Savinase and Esperase of Novo Industries A / S (Denmark) and Maxatase of International Bio-Synthetics, Inc. (The Netherlands) and FN-base by Genencor, Optimase and Opticlean by MKC. Of interest in the category of proteolytic enzymes, especially for liquid detergent compositions, are enzymes referred to herein as Protease A and Protease B. Protease A is described in European Patent Application 130,756. Protease B is described in European Patent Application Serial No. 87303761.8. Amylases include, for example, -amylases obtained from a special strain of B.licheniforms. described in more detail in British Patent Specification No. 1,296,839 (Novo). Amylocytic proteins include, for example, Rapidase, Maxamyl (International Bio-Synthetics, Inc.) and Termamyl, (Novo Industries). The cellulase that can be used in the present invention includes both bacterial and fungal cellulase. Ideally, they should have an optimum pH of between 5 and 9.5. Suitable cellulases are described in the U.S. Patent. 4,435,307, Barbesgoard et al., Which describes fungal cellulase produced by the Humicola insolens. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-0S-2,247,832. Examples of said cellulases are cellulases produced by a chain of Humicola insolens (Humicola grísea var. Thermoidea). particularly the Humicola DSM 1800 chain, or a fungal cellulase 212-producer of Bacillus N belonging to the genus Aeromonas. and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricular Solander). Other suitable cellulases originated from Humicola Insulens having a molecular weight of approximately 50KDa, an isoelectric point of 5.5 and containing 415 amino acids. Said cellulases are described in copending European Patent Application No. 93200811.3, filed on March 19, 1993. Especially suitable cellulases are cellulases having color care benefits. Examples of said cellulases are cellulases described in European Patent Application No. 91202879.2, filed on November 6, 1991, Carezyme (Novo). In general, cellulases are preferred enzymes, since the cellulases achieve a smoothing benefit of multiple cycle, which is restricted to cotton-containing fabrics, penetrating and helping in the removal of cellulose fibrils. These are normally formed in the fibers during the normal washing process, and increase after consecutive washes and during the aging of the fabric. The interaction of these fibrils with each other imparts a degree of rigidity on the surface of the fabric that the consumer feels rough, which is alleviated by the use of cellulase enzymes. The cellulases can be added in combination with silicone softeners. The softening silicones have a smoothing benefit from a single cycle by depositing directly on the fabric. Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomona stutzeri ATCC 19,154, as described in British Patent 1,372,034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the microorganism Psudomonas Fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trademark Lipase P "Amano", which from here on is designated co or "Amano-P". Especially suitable lipases are lipases such as Lipase Ml (Ibis) and Lipolase (Novo). The peroxidase enzymes are used in combination oxygen supplies, eg, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching solutions", that is, to avoid transfer of dyes or pigments removed from the substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and halogenperoxidase such as chloroperoxidase and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099813 and in European Patent Application EP No. 91202882.6, filed on November 6, 1991. In liquid formulations, a stabilization system of enzyme is preferably used. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, a technique for stabilizing enzyme in aqueous solution involves using calcium-free ions from sources such as calcium acetate, calcium formate and calcium propionate. The calcium ions can be used in combination with short chain carboxylic acid salts, preferably formats. See, for example, Patent of U.S.A. 4,318,818.

It has also been proposed to use polyols such as glycerol and sorbitol. Alkoxy alcohols, dialkyl glycol ethers, mixtures of polyvalent alcohols with polyfunctional aliphatic amines (eg, such as diethanolamine, triethanolamine, diisopropanolamine, etc.), and boric acid or alkali metal borate. Enzyme stabilization techniques are further described and exemplified in the U.S. Patent. 4,261,868, Patent of E.U.A. 3,600,319, and European Patent Application Publication No. 0 188 405, Application No. 86200586.5. Stabilizers without boric acid or borate are preferred. The borate can conveniently be incorporated into heavy duty liquid detergent in the form of a solution. Boric acid has a solubility in water of about 13% at 60 ° C. Sodium metaborate is commercially available as a solution with activity of 10.1% (expressed in terms of B203) at 20 ° C. For compact liquids it is preferred that the solution be concentrated. More concentrated solutions can be obtained by neutralizing boric acid with organic amines, such as monoethanolamine (MEA). A highly preferred borate solution can be prepared by heat treatment of aqueous borate solution. A solution heated to a temperature above 60 ° C, and preferably above 90 ° C, and maintained at said temperature for at least 5 minutes, preferably between 30 and 60 minutes, will be stable at 20 ° C for at least one month.

Using this method of heat treatment, a solution with activity of at least 33% (expressed in terms of B203) can be made and stored without separation or precipitation. Although several counterions can be used in the solution, for example, sodium, potassium, MEA, triethanolamine, etc., sodium is preferred. The preferred molar ratio of Na20: B203 is from 0.15: 1 to 0.38: 1, more preferable 0.22: 1 to 0. 35: 1. Boric acid, metaborate or borax can be used as starting materials. Other polyols such as glycerol can also be incorporated into the concentrated solution. Enzyme stabilization systems are also described, for example, in U.S. Patents. 4,261,868, 3,600,319 and 3,519,570. Other suitable detergent ingredients that may be added are enzyme oxidation scavengers which are described in co-pending European Patent Application No. 92870018.6, filed on January 31, 1992. Examples of said enzyme oxidation scavengers are ethoxylated tetraethylene polyamines. Another optional ingredient is a foam suppressant, exemplified by silicones and a silicone-silica blend. Silicones can generally be represented by alkylated polysiloxane materials whereas silica is normally used in finely divided forms exemplified by silica aerogels and gerogels and hydrophobic silicas of different types. These materials can be incorporated as particles wherein the foam suppressant is advantageously and freely incorporated into a waterproof or water-dispersible surfactant detergent impermeable vehicle. Alternatively, the foam suppressant can be dissolved or dispersed in a liquid vehicle and applied by spraying on one or more of the other components. A preferred silicone foaming agent is described in Bartollota et al., U.S. 3,933,672. Other particularly useful foam suppressors are self-emulsifying silicone foam suppressors, described in the German Patent Application DTOS 2,646,126 published April 28, 1977. An example of a compound as such is DC-544, commercially available from Dow Corning, which is a siloxane / glycol copolymer. The essentially preferred foam controlling agents are the foam suppressor system comprising a mixture of silicone oils and 2-alkyl alkanols. Suitable 2-alkyl-alkanols are 2-butyl-octanol which are commercially available under the brand name Isofol 12 R. Such foam suppressor systems are described in co-pending European Patent Application No. 92870174.7, filed November 10, 1992. Particularly preferred silicone foam controlling agents are described in co-pending European Patent Application No. * 92201649.8. Said compositions may comprise a silicone / silica mixture in combination with non-porous smoke silica such as Aerosil.RTM. Other preferred foam controlling agents are described in EP 495 345. These foam controlling agents comprise a silicone anti-foam compound, a carrier material and an organic coating material containing glycerol at a weight ratio of anti-foam compounds. -Silicone foam from 1: 2 to 3: 1. The foam suppressors described above are normally employed at levels of 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight. Other components used in detergent compositions can be used, such as soil suspending agents, soil release agents, optical brighteners, bleaches, bactericides, rust inhibitors, coloring agents and / or encapsulated or non-encapsulated umes. Suitable anti-redeposition and soil suspending agents herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts. Polymers of this type include the polyacrylates and copolymers of anhydro-acrylic maleic acid previously mentioned as detergency builders, as well as the anhydromalelic copolymers with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole% of the copolymer. These materials are normally used at levels of 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferred from 1% to 6% by weight of the composition. Other useful polymeric materials are polyethylene glycols, particularly those of molecular weight of 1000-10000, more particularly 2000 to 8000 and most preferred about 4000. These are used at levels of 0.20% to 0.5%, more preferably 0.25% to 2.5%. % in weigh. These polymers and the abovementioned homo- or co-polymeric polycarboxylate salts are valued to improve the maintenance of whiteness, fabric position, and cleaning ormance in clay, and protein and oxidizable dirt in the presence of transition metal impurities. The soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and / or propylene glycol units in various arrangements. Examples of said polymers are described in the patents of E.U.A. Commonly assigned Nos. 4116885 and 4711730 and European Published Patent Application No. 0272033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula (CH3 (PEG) A3) or.7s (POH) o.2sCT-PO) 2.8 (T-PEG) or.4] T (PO- H)? 25 ((PEG) A3CH3)? 7S where PEG is - (OC2H4) 0-, P0 is (OC3H6O) and T is Also very useful are polyesters modified as random copolymers of dimethyl terephthalate, sulfoisophthalate of dimethyl, ethylene glycol and 1-2 propane diol, the final groups consisting mainly of sulfobenzoate and secondarily of ethylene glycol monoesters and / or propane diol. The target is to obtain a polymer capped at both ends by sulfobenzoate groups, "firstly", in the present context most of said copolymers will be capped at the ends with sulfobenzoate groups. However, some copolymers will be less than completely capped at the ends and therefore their end groups may consist of ethylene glycol monoester and / or propane 1-2, thereof consisting "secondarily" of said species. The polyesters selected herein contain about 46% by weight of dimethylterephthalic acid, about 16% by weight of propane diol -1.2, about 10% by weight of ethylene glycol, about 13% by weight of dimethylsulfobenzoic acid and about 15% by weight of sulphuric acid, and have a molecular weight of about 3,000. The polyesters and their method of preparation are described in EPA 311 342. Preferred polymers for incorporation into the dye transfer inhibiting composition of the present invention include polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidone, polyvinyloxazolidone and polyvinylimidazole.

Said polymers are described in EP 622 447. The detergent compositions according to the invention can be in liquid, paste, gels, stick or granulated forms. The granular compositions according to the invention can also be in "compact form", ie they can have a relatively higher density than conventional granular detergents, ie from 550 to 950 g / 1; in such a case, the granular detergent compositions in accordance with the present invention will have a smaller amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulfate and chlorides, typically sodium sulfate; "Compact" detergents typically comprise no more than 10% filler salt. The liquid compositions according to the present invention are in "concentrated form"; in such a case, the liquid detergent compositions in accordance with the present invention will have a lower amount of water, compared to conventional liquid detergents. Typically, the water content of the concentrated liquid detergent is less than 305, more preferably less than 20%, most preferably less than 10% by weight of the detergent compositions. The present invention also relates to a process for inhibiting the transfer of dye from one fabric to another of solubilized and suspended dyes that are encountered during fabric washing operations involving dyed fabrics. The method comprises that the fabrics make contact with a solution for washing as described above. The process of the invention is conveniently carried out in the course of the washing process. The washing procedure is preferably carried out at 5 ° C to 75 ° C, especially 20 ° C to 60 ° C, but the polymers are effective up to 95 ° C and higher temperatures. The pH of the treatment solution is preferably from 7 to 11, especially from 7 to 10.5. The process and compositions of the invention can also be used as detergent additive products. Said additive products are intended to supplement or boost the performance of conventional detergent compositions. The following examples should exemplify the compositions of the present invention, but should not necessarily limit or otherwise define the scope of the invention, said scope being determined in accordance with the claims below. A liquid detergent composition according to the present invention is prepared, having the following compositions: TABLE I% by weight of the total detergent composition Fatty acid 10 Oleic acid 4 Citric acid 1 NaOH 3.4 Propanodiol 1.5 Ethanol 10 EXAMPLE 1 The degree of dye transfer of different stained fabrics is studied by using a test that measures the wash that simulates a wash cycle of 30 min. The container that measures the wash contains 200 ml of a detergent solution, a piece of lOc x lOcm of the dyed fabric and a sample of muitifibers that is used as a tracer for the blood dye. The multifiber sample consists of 6 pieces (1.5cm x 1.5cm each) of the different material (polyacetate, cotton, polyamide, polyester, wool and orlon) that are woven together. The degree of dye transfer is ensured by a Hunter color measurement. The Hunter color system evaluates the color of a fabric sample in terms of the DE value that represents the change in the L, a, b Hunter values that are determined by reflex spectrometry. The DE value is defined by the following equation: DE - C (af - ai) 2 + (bf - bi) 2 + (Lf - Li) 2] i where the letters i and f refer to the Hunter value before and after washing in the presence of the fabric with blood, respectively. The minimum significant difference is 1 to 95% confidence level. Example I shows the improved performance which inhibits the transfer of dye from the vinylpyridine copolymers.

EXPERIMENTAL CONDITIONS ° C / city water A: a detergent composition in accordance with Table I that does not contain any dye transfer inhibition system. B: a detergent composition in accordance with Table I containing poly (4-vinyl pyridine) -co- (acrylate) with a ratio of 4-vinylpyridine / acrylate of 85/15. The level of copolymer in solution is 7ppm. Results: DE values for cotton EXAMPLE II (A / B / C) A liquid detergent composition according to the present invention is prepared, having the following compositions: % by weight of the total detergent composition to. Linear alkylbenzene sulfonate 10 Alkoxylated alkylsulfate Polyhydroxy fatty acid - 9 C12-C14 trimethylammonium chloride Alkylsulfate 4 4 4 C12-C15 ethoxylate 12 12 fatty 12 Fatty acid 10 10 10 Oleic acid 4 4 4 Citric acid 1 1 1 Diethylenetriaminpentamethylene 1.5 1. 5 1. 5 Phosphonic acid NaOH 3.4 3.4 3.4 Propanodiol 1.5 1. 5 1. 5 Ethanol 10 10 10 Tetraethylenepentane ethoxylated 0.7 0. 7 0.7 Poly (4-vinylpiperine) -co- (acrylate) 0-1 0-1 0-1 Thermamyl 0.13 0.13 0.13 Carezyme 0.014 0.014 0.014 Base FN 1.8 1.8 1.8 Lipolase 0.14 0.14 0.14 Endoglucanase A 0.53 0.53 0.53 Foam suppressor (IS0F0LR) 2.5 2.5 2.5 Minors up to 100 EXAMPLE III (A / B / C) A compact granular detergent composition according to the present invention having the following formulation was prepared: % by weight of the total detergent composition 6. B. e. Linear alkyl benzene sulfonate 11.40 Alkoxylated alkylsulfate - 10 - Polyhydroxy fatty acid - 9 C4 - C14 trimethyl ammonium chloride - Tallow alkyl sulfate 1.80 1.80 1.80 C45 Alkylsulfate 3.00 3.00 3.00 C45 alcohol 7 times ethoxylated 4.00 4.00 4.00 Tallow alcohol 11 times ethoxylated 1.80 1.80 1.80 Dispersant 0.07 0.07 0.07 Silicone fluid 0.80 0-80 0.80 Trisodium citrate 14.00 14.00 14.00 Citric acid 3.00 3.00 3.00 Zeolite 32.50 32.50 32.50 Maleic acid copolymer / 5.00 5.00 5.00 acrylic acid Cellulase (active protein) 0.03 0.03 0.03 Alcalasa / BAN 0.60 0.60 0.60 Lipase 0.36 0.36 0.36 Sodium silicate 2.00 2.00 2.00 Sodium sulphate 3.50 3.50 3.50 Poly (4-vinylpi ridine) -co- (acrylate) 0 0--11 0-1 0-1 Minor 1lasta 100 The above compositions (Example II (A / B / C) and III (A / B / C)) showed very well excellent performance of detergent and clay with outstanding color care performance in dyed fabrics and mixed loads of dyed fabrics and fabrics white

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1. - A composition that inhibits the transfer of dye comprising a vinylpyridine copolymer.

2. A composition that inhibits the transfer of dye according to claim 1, further characterized in that the molar ratio of copolymerizing monomer to vinylpyridine is from 1 to 0.01, preferably from 0.5 to 0.05, more preferably from 0.3 to 0.05.

3. A composition that inhibits the transfer of dye according to claims 1 and 2, further characterized in that the copolymer is selected from formic acid, acrylic acid, maleic acid, vinylpyrrolidone and vinylacetate.

4. A composition that inhibits the transfer of dye according to claims 1-7, further characterized in that the average molecular weight varies from 5000 to 100,000, preferably from 5,000 to 100,000.

5. A detergent composition in accordance with claims 3, further characterized in that the average molecular weight of the vinylpyridine copolymer is from 5,000 to 50,000.

6. A detergent composition comprising the composition that inhibits the transfer of dye according to claims 1 to 5, characterized also because it comprises a nonionic surfactant.

7. A detergent composition according to claims 5 and 6, further characterized in that it comprises polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone, polyvinyloxazolidone and polyvinylimidazole.

8. A detergent composition according to claims 5 to 7, further characterized in that it is in the form of a granulate, liquid gel, paste or stick.

9. A composition that inhibits the transfer of dye according to claims 1 to 4, further characterized in that it is a detergent additive in the form of a granule or liquid that does not form powder.