CN1066192C - Detergent compsn. inhibiting dye transfer - Google Patents

Abstract

A dye transfer inhibiting composition comprising a mixture of polyamine N-oxide polymers having high and low degrees of oxidation, said polyamine N-oxide polymer containing structural units of formula (I),

Where P is a polymerizable unit, the NO group can be attached to or form part of the polymerizable unit. A is (a), (b), (c), -O-, -S-, (d);

X is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group to which the nitrogen on the NO group can be attached or where the N on the NO group is one of these groups part of the group.

Description

Detergent composition for inhibiting dye transfer

Field of the invention

The present invention relates to a composition and method for preventing dye transfer during laundering of fabrics. In particular, the present invention relates to dye transfer inhibiting compositions comprising a mixture of a low degree of oxidation polyamine N-oxide polymer and a high degree of oxidation polyamine N-oxide polymer.

Background of the invention

One of the most persistent and troublesome problems that arise in the modern fabric laundering process is the tendency of some colored fabrics to release dye into the laundry detergent. The dye is then transferred to other fabrics being washed.

One of the solutions to this problem is to complex or absorb the non-persistent dyes that are washed from dyed fabrics before they have a chance to attach to other items in the wash.

Polymers have been used in detergent compositions to prevent dye transfer. EP-A-0102 923 describes the use of carboxyl-containing polymers in aqueous compositions. DE-A-2 814 329 discloses the use of N-vinyloxazolidinone polymers, FA-A-2 144 721 discloses 15-35% polyvinylpyrrolidone and acrylonitrile or maleic anhydride in washing powders Copolymer applications.

EP-265 257 describes detergent compositions comprising carboxymethylcellulose of an alkali metal carboxyl salt, a vinylpyrrolidone polymer and a polycarboxylate polymer.

It has now surprisingly been found that specific combinations of polyamine N-oxide polymers having respectively low and high degrees of oxidation are very effective in eliminating the transfer of various dissolved or suspended dyes. This discovery allows formulation of compositions that exhibit good transfer inhibiting properties for a variety of dyes.

Another embodiment of the present invention also provides a method of laundering colored fabrics.

Summary of the invention

The present invention relates to dye transfer inhibiting compositions comprising mixtures of polyamine N-oxide polymers having high and low degrees of oxidation.

Detailed description of the invention

The compositions of the present invention comprise a mixture of a low degree of oxidation polyamine N-oxide polymer ("LOPAO") and a high degree of oxidation polyamine N-oxide polymer ("HOPAO").

Here "low oxidation degree polyamine N-oxide polymer" means that the ratio of amine to amine N-oxide is from 1000:1 to 1:1, preferably from 100:1 to 1:1, Most preferred are from 10:1 to 1:1 polyamine N-oxide polymers.

Here "high degree of oxidation polyamine N-oxide polymer" means that the ratio of amine to amine N-oxide is from 2:3 to 1:1000000, preferably from 1:4 to 1:1000000, Most preferred are polyamine N-oxide polymers from 1:7 to 1:1000000.

The amount of amine oxide groups in said polyamine N-oxide polymer can be varied according to suitable copolymerization or suitable degree of N-oxidation.

Polyamine N-oxide polymers contain units with the following structure:

Where P is a polymerizable unit, the N-O group may be attached thereto or where the N-O group forms part of the polymerizable unit or both.

X is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof, the nitrogen in the NO group is attached to the above or the nitrogen in the NO group are part of these groups.

The NO group can be represented by the following general structure:

Wherein R ₁ , R ₂ , R ₃ are aliphatic groups, aromatic, heterocyclic or aliphatic groups or combinations thereof, X or/and Y or/and Z are 0 or 1, wherein the nitrogen on the NO group Nitrogens which may be attached to these groups or conjugates or to NO groups form part of these groups.

The N-O group can be part of the polymerizable unit (P), or can be attached to the polymer backbone, or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerizable unit include polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.

One class of said polyamine N-oxides includes polyamine N-oxide groups in which the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, tetrahydropyrrole, piperidine, quinoline, acridine and derivatives thereof.

Another class of said polyamine N-oxides includes polyamine N-oxide groups in which the nitrogen of the N-O group is attached to the R-group.

Other suitable polyamine N-oxides are polyamine oxides in which the N-O groups are attached to polymerisable units. A preferred class of these polyamine N-oxides are polyamine N-oxides of general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen on the N-O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and their derivatives.

Another preferred polyamine N-oxide is a polyamine N-oxide of general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen on the N-O functional group is attached to the Said R group on. Examples of these classes are polyamine oxides where the R group may be aromatic, eg phenyl.

Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has dye transfer blocking properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamines, polyimides, polyacrylates and mixtures thereof.

The polymers of the present invention actually comprise random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is an amine N-oxide or not. The amine oxide units of the polyamine oxides have PK _a <10, preferably PK _a <7 and better PK _a <6.

Polyamine oxides are available in almost any degree of polymerization. The degree of polymerization is not critical provided the starting material has the required water solubility and dye suspending power.

Typically, the average molecular weight is between 500 and 1,000,000; preferably the molecular weight is from 1,000 to 50,000; more preferably the molecular weight is 2,000 to 30,000; most preferably the molecular weight is 3,000 to 20,000.

The polyamine N-oxides of the present invention typically comprise from 0.001 to 10%, more preferably from 0.01 to 2%, most preferably from 0.05 to 1% by weight of the dye transfer preventing composition.

The present composition may conveniently be used as an additive to conventional detergent compositions for washing applications. The present invention also encompasses dye transfer inhibiting compositions which comprise detergent ingredients and are therefore useful as detergent compositions.

Process for the manufacture of polyamine N-oxides:

The production of polyamine N-oxides can be accomplished by polymerizing amine monomers followed by oxidation of the resulting polymer with a suitable oxidizing agent, or the amine oxide monomers themselves can be polymerized to give polyamine N-oxides.

The synthesis of polyamine N-oxide can be exemplified by the synthesis of polyvinylpyridine N-oxide.

Pre-dissolve poly-4-vinylpyridine (mw.50,000, 5.0g, 0.0475mole) in 50ml acetic acid, and pipette with peracetic acid solution (25g glacial acetic acid, 6.4g volume ratio of 30% H ₂ O ₂ solution, a few drops of H ₂ SO ₄ to obtain 0.0523 mol peracetic acid) to treat. The mixture was stirred at ambient temperature (32°C) for more than 30 minutes, then the mixture was heated to 80-85°C in an oil bath for 3 hours and left overnight. The resulting polymer solution was then mixed with 11 ml of acetone under stirring. The resulting brownish-yellow sticky slurry formed at the bottom was washed with 11 ml of acetone to obtain a light-colored crystalline solid. The solid was gravity filtered _, washed with acetone, and dried over _P2O5 .

The amine:amine N-oxide ratio of this polymer is 1:4.

Detergent Additives:

A wide variety of surfactants can be used in detergent compositions. U.S. Patent 3,664,961, issued May 23, 1972 to Norris, gives a list of typical anionic, nonionic, amphoteric and zwitterionic surfactants and classes of such surfactants.

Mixtures of anionic surfactants are especially useful here, especially when the sulfonate and sulfate surfactant weight ratio is from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably The earth is from 3:1 to 1:1. Preferred sulfonates include alkylbenzene sulfonates having 9 to 15, especially 11 to 13, carbon atoms in the alkyl group; and α-sulfonate fatty acid methyl esters, wherein the fatty acid consists of C ₁₂ -C ₁₈ The fatty material, preferably derived from a C ₁₆ -C ₁₈ fatty material. In each instance, the cation is an alkali metal, preferably sodium. Preferred sulfate surfactants are alkyl sulfates having 12 to 18 carbon atoms in the alkyl group, or 10 to 20, preferably 10 to 16 carbon atoms in the alkyl group, with an average degree of ethoxylation For 1 to 6 ethoxysulfate mixes. Examples of preferred alkyl sulfates herein are tallow alkyl sulfates, coconut alkyl sulfates and _C14-15 alkyl sulfates. The cation in each instance is again an alkali metal cation, preferably sodium.

One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety, providing a Hydrophile-Lipophile Balance (HLB) value between 8 and 17, preferably 9.5 to 13.5, more preferably a surfactant between 10 and 12.5. The hydrophobic (lipophilic) moiety can be aliphatic or aromatic in nature, and the length of the ethylene oxide group that can be condensed with any particular hydrophobic group can be easily adjusted to obtain a The balance between water-soluble compounds.

Particularly preferred nonionic surfactants of this class are C ₉ -C ₁₅ primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, especially 6-8 moles of ethylene oxide per mole of alcohol C ₁₄ -C ₁₅ primary alcohols and C ₁₂ -C ₁₄ primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants comprises alkyl polyglycoside compounds, the general formula of which is:

RO(C _n H _2n O) _t Z _x

Where Z is a moiety obtained from glucose; R is a saturated hydrophobic alkyl group containing 12 to 18 carbon atoms; t is 0 to 10, n is 2 or 3; X is 1.3 to 4, and the compound also includes Less than 10% unreacted fatty alcohols and less than 50% short chain alkyl polyglycosides. Such compounds and their use in detergents are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.

Polyhydroxy fatty acid amide surfactants of the formula are also suitable as nonionic surfactants.

Wherein R ¹ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxy n-propyl or a mixture thereof, R ² is C _5-31 hydroxyl, Z is a linear hydrocarbyl chain, A polyhydroxyl hydrocarbon radical having at least 3 hydroxyl groups directly attached to the chain, or an alkoxylated derivative thereof. Preferably, R ₁ is methyl, R ² is a straight C _11-15 alkyl or alkenyl chain, such as coconut alkyl or a mixture thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, Lactose, etc. are obtained in the reductive amination reaction.

The compositions of the present invention also include a builder system. All conventional builder systems are suitable for this, including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as EDTA, metal ions such as aminopolyphosphates Chelating agents, especially diamine tetramethylene phosphonic acid and diethylene triamine 1,5-pentamethylene phosphonic acid. Although less preferred for environmental reasons, phosphate builders can also be used here.

A suitable builder may be an inorganic ion exchange material, usually an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.

Another suitable inorganic builder material is layered silicate, eg SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate composed of sodium silicate (Na ₂ Si ₂ O ₅ ).

Suitable polycarboxylates containing a carboxy group disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370 include lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxyl groups described in German Offenlegenschrift 2,446,686 and 2,446,687 and U.S. Pat. No. 3,935,257 include the water-soluble salts of succinic acid, malonic acid, (Ethylenedioxy) diacetic acid, maleic acid, glycolic acid, tartaric acid, hydroxymalonic acid and fumaric acid, and their ether carboxylates and thionyl as described in Belgian patent 840,623 Carboxylate. Polycarboxylates containing three carboxy groups include, inter alia, the water-soluble citric, aconitic and citraconic acid salts and succinic derivatives such as carboxymethoxysuccinic acid described in British Patent No. 1,379,241 , lactoxysuccinic acid described in Netherlands Patent Application 7205873, and oxidized polycarboxylate salts described in UK Patent No. 1,387,447, such as 2-oxa-1,1,3-propanetricarboxylic acid Salt.

Polycarboxylates containing four carboxyl groups disclosed in British Patent 1,261,829 include oxydisuccinates: 1,1,2,2-ethane tetracarboxylate, 1,1,3,3- Propane tetracarboxylate and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo-substituents include the sulfosuccinic acid derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and U.S. Patent No. 3,936,448, in British Patent No. Sulfonated pyrolyzed citric acid is described in No. 1,082,179, while polycarboxylates containing phosphorus substituents are disclosed in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienated pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis -tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,2,5,5-tetrahydrofuran-tetracarboxylate, 1,2,3,4,5,6-cyclohexane- Hexa-acid salts and methyl derivatives of polyols such as tartrate, mannitol and xylitol. Aromatic polycarboxylates disclosed in British Patent No. 1,425,343 include pyromellitic acid, pyromellitic acid, and pyromellitic acid derivatives.

The above preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, especially citric acid.

Preferred builder systems for use in the compositions of the present invention include a mixture of water-insoluble aluminosilicate builders, such as zeolite A or a layered silicate (SKS/6), and a water-soluble carboxylate chelating agent such as citric acid.

A suitable chelating agent for use in the detergent compositions of the present invention is ethylenediamine-N,N-disuccinic acid (EDDS) or its alkali metal, alkaline earth metal, alkaline earth metal, ammonium, or substituted ammonium salts, or their mixture. Preferred EDDS compounds are the free acid form and the sodium or magnesium salts thereof. Examples of these preferred sodium salts of EDDS include _Na2EDDS and _Na4EDDS . Examples of such preferred magnesium salts of EDDS include MgEDDS and _Mg2EDDS . Magnesium salts are most preferably included in the compositions of the present invention.

For liquids in particular, suitable fatty acid builders for use herein are saturated or unsaturated _C10-18 fatty acids, and the corresponding soaps. Preferred saturated fatty acids or corresponding soaps have 12 to 16 carbon atoms in the alkyl chain. A preferred unsaturated fatty acid is oleic acid.

A preferred builder system for use in granular compositions comprises a mixture of a water-insoluble aluminosilicate builder such as zeolite A and a water-soluble carboxylate chelating agent such as citric acid.

Other builder materials that can form part of the builder system for use in the granular compositions of the present invention include organic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as Organic phosphates, amino polyalkylene phosphates and amino polycarboxylates.

Other suitable water-soluble organic salts are homo- or co-polymeric acids or their salts, wherein the polycarboxylic acid contains at least two carboxyl groups separated by not more than two carbon atoms. Such polymers are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20,000 to 70,000, especially around 40,000.

Detergent builder salts generally comprise from 10% to 80%, preferably from 20% to 70%, most usually from 30% to 60%, by weight of the compositions.

Detergent ingredients which may be used in the detergent compositions of the present invention include bleaching agents.

These bleach components may contain one or more oxygen bleaching agents and, depending on the bleaching agent chosen, one or more bleach activators. When used, the bleaching compounds can be incorporated into the present detergent compositions from about 1% to about 10% of the compositions. Generally, bleaching compounds are optional ingredients in non-liquid formulations such as granular detergents. If added, bleach activators will typically comprise from about 0.1% to about 60%, more typically from about 0.5% to about 40%, of the bleaching composition.

The bleaching agent component useful herein can be any bleaching agent useful in detergent compositions including oxidative bleaches as well as others known in the art.

In another aspect, the present invention also provides a method for using a polyamine N-oxide polymer, optionally a co-detersive surfactant, A method of cleaning fabrics, fibres, textiles in a detergent composition with optional detergency additive ingredients and a bleaching agent.

A bleach suitable for the present invention can be an activated or non-activated bleach.

One class of oxidative bleaches which may be used includes percarboxylic acid bleaches and their salts. Suitable examples of bleaching agents of this type include magnesium monoperoxyphthalate hexahydrate, magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanoic acid. double acid. Such bleaches are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934. Very preferred bleaching agents described in U.S. Patent 4,634,551 also include 6-nonylamino-6-oxoperoxycaproic acid.

Another class of bleaches that can be used includes halogen bleaches. Examples of hypohalide bleaches include, for example, sodium and potassium trichloroisocyanurates and dichloroisocyanurates, N-chloro and N-bromosulfonamides. Such materials are usually added in an amount of 0.5-10% by weight of the finished product, preferably 1-5% by weight of the finished product.

Preferably, bleaches suitable for use herein include peroxygen bleaches. Examples of suitable water soluble solid peroxygen bleaches include hydrogen peroxide releasing agents such as hydrogen peroxide, perborates such as perborate monohydrate, perborate tetrahydrate, persulfates, percarb salts, peroxodisulfates, superphosphates and peroxyhydrates. Preferred bleaching agents are percarbonate and perborate.

Hydrogen peroxide releasers can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5-trimethyl Hexanoloxybenzenesulfonate (ISONOBS, described in EP 120, 591) or pentaacetylglucosinolate (PAG), these substances are perhydrolyzed to form a peracid like active bleach, which can improve bleaching Effect. Suitable activators are also acylated citrates (ATC), disclosed in co-pending European Patent Application No. 91870207.7.

Hydrogen peroxide can also be obtained by adding an enzymatic system (ie an enzyme and its substrate) capable of producing hydrogen peroxide initially or during washing and/or water washing. Such an enzymatic system is disclosed in European Patent Application 91202655.6, filed October 9,1991.

Other peroxygen bleaches suitable herein include organic peroxyacids such as percarboxylic acids.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. One class of non-oxidative bleaching agents of particular interest includes photoactivated bleaching agents such as sulfonated zinc and/or aluminum phthalocyanines. These substances can deposit on the substrate during the washing process. When irradiated with light in the presence of oxygen, such as hanging clothes out to dry during the day, the sulfonated zinc phthalocyanine is activated, and the substrate is bleached as a result. Preferred zinc phthalocyanines and a photoactivated bleaching process are described in U.S. Patent 4,033,718. Typically, detergent compositions comprise from about 0.025% to about 1.25% by weight of sulfonated zinc phthalocyanine.

Other detergent ingredients that can be included are detersive enzymes, which can be included in detergent formulations for a variety of different uses, such as protein-based, carbohydrate-based, or triglyceride-based Remove stains and prevent dye transfer. Enzymes to be incorporated include proteases, amylases, lipases, cellulases and peroxidases, and mixtures thereof. Other types of enzymes may also be included. They may originate from any suitable source, such as plants, animals, bacteria, molds and yeasts.

Enzymes are generally incorporated in amounts sufficient to provide up to about 5 mg, more typically about 0.05 to about 3 mg, of active enzyme per gram of composition.

Examples of suitable proteases are subtilisins obtained from particular strains of Bacillus subtilis and Bacillus licheniformis. Commercially available proteolytic enzymes suitable for removing protein stains include: Alcalase, Sarinase and Esperase sold by Novolndustries A/S (Denmark); Maxatase sold by International Bio-Synthetics, Inc. (The Netherlands); sold by Genencor FNbase; Optimase and opticlean sold by MKC.

Proteolytic enzymes of interest, especially for liquid detergent compositions, are the 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. For example, amylases include those obtained from a particular strain of Bacillus licheniformis, described in detail in British Patent Specification No. 1296839 (Novo). Amylolytic proteins include, for example, Rapidase, Maxanyl (International Bio-Sythetics, Inc.) and Termamyl, (Novo Industries).

Cellulases useful in the present invention include bacterial and fungal cellulases. Preferably, they have an optimum pH range: between 5-9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307 to Barbesgoard et al. which discloses fungal cellulases from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are: a cellulase produced by the Humicala insolens line (Humicola grisea var. thermoidea), especially the Humicola line DSM1800, a cellulase produced by a Bacillus N mold or a 212 -producing cellulase, cellulase extracted from the hepatopancreas of marine mollusks (Dolabella Auricula Solander).

Another suitable cellulase is the cellulase derived from Humicola insulins which has a molecular weight of about 50 KDa, an isoelectric point of 5.5 and contains 415 amino acids. Such cellulases are described in co-pending European Patent Application No. 93200811.3, filed March 19,1993.

Particularly suitable cellulases are cellulases which facilitate color protection. Examples of such cellulases are described in European Patent Application No. 91202879.2, filed November 6, 1991, Carezyme (Novo).

Suitable lipases for use in detergents include those produced by microorganisms of the pseudomonad group, such as Pseudomonas stutzeri ATCC 19.154, disclosed in British Patent 1,372,034. Suitable lipases include those lipases that exhibit positive immunological cross-reactivity with antibodies to lipases, which are produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is commercially available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the brand name Lipase P "Amano", hereinafter referred to as "Amano-P". Particularly suitable lipases are M1 Lipase (Ibis) and Lipolase (Novo).

Peroxidases are used in combination with oxygen sources such as percarboxylates, perborates, persulfates, hydrogen peroxide, and the like. They are used as "solvent bleaches", that is, to prevent the transfer of dyes or pigments removed from substrates during the wash process to other substrates in the wash liquor. Peroxidases known in the art include, for example, horseradish peroxidase, ligninase, haloperoxidases, such as chloro- and bromo-peroxidases. Peroxidase-containing detergent compositions are disclosed in PCT International Application WO 89/099813 filed November 6, 1991 and in European Patent application EP No. 91202882.6.

In liquid formulations, an enzyme stabilization system is preferably used. Enzyme stabilization techniques for use in aqueous detergent compositions are well known in the art. For example, one enzyme stabilization technique in aqueous solution involves the use of free calcium ions, derived from calcium acetate, calcium formate, calcium propionate. Calcium ions may be used in combination with short chain carboxylates, preferably formates. See U.S. Patent 4,318,818. It has also been suggested to use polyols such as glycerol and sorbitol, alkoxyl alcohols, dihydrocarbyl sugar ethers, mixtures of polyols and polyfunctional fatty amines (e.g., diethanolamine, triethanolamine, di-isopropanolamine, etc.), boric acid or alkali metal borates. Enzyme stabilization techniques are additionally disclosed and exemplified by US Patent 4,261,868, US Patent 3,600,319, European Patent Application Publication No. 0,199,405, Application No. 862005866.5. Non-boric acid and borate stabilizers are preferred. Enzyme stabilization systems are also described in U.S. Patents 4,261,868, 3,600,319 and 3,519,570.

Other suitable detergent ingredients that may be added are the enzyme oxidation scavengers described in co-pending European Patent application No. 92870018.6, filed January 31, 1992. An example of such an enzyme oxidation scavenger is ethoxylated tetraethylenepolyamine.

Particularly preferred detergent ingredients are used in combination with a process that provides color protection benefits. Examples of such processes are cellulases, and/or peroxidases and/or metal substituted catalysts used for color protection restoration processes.

Another optional ingredient is a suds suppressor, exemplified by silicones and silica-silicone mixtures. Siloxanes are generally represented by alkyl siloxanes, while silica is generally used in finely divided form, in various silica aerogels, xerogels and hydrophobic Silicon oxide as an example. These materials may be incorporated as granules into a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier in which release of the suds suppressor is facilitated. Alternatively, the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying onto one or more other ingredients.

A preferred silicone suds control agent is disclosed in U.S. Patent 3,933,672 to Bartollota et al. Other particularly useful suds suppressors are the semi-emulsified silicone suds suppressors described in German Patent Application DTOS 2 646 126, published April 28, 1977. An example of such a compound is DC-544, a silicone-glycol copolymer commercially available from Dow Corning. A particularly preferred suds control agent is a suds suppressor system comprising a silicone oil and a mixture of 2-alkyl-alkanols. A suitable 2-alkyl-alkanol is 2-butyl-octanol, commercially available under the tradename Isofol 12R.

Such a foam suppression system is described in co-pending European Patent Application No. 92870174.7, filed November-October 1992.

Preferred silicone suds control agents are described in co-pending European Patent Application No. 92201649.8.

The composition may comprise a silicone/silica mixture in combination with non-porous silica such as Aerosil ^R.

The aforementioned suds suppressors are generally added in an amount of 0.01% to 2% by weight of the composition, preferably 0.01% to 1%.

Other ingredients used in detergent compositions may be used, such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, colorants, non-encapsulated and encapsulated perfumes.

Suitable antiredeposition and soil suspension agents herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymers of polycarboxylic acids and their salts. Such polymers include the aforementioned polyacrylates and maleic acid-acrylic acid copolymers as builders, as well as copolymers of maleic anhydride and ethylene, methyl vinyl ether or isoacrylic acid, and maleic anhydride, which constitute At least 20 mol% of the copolymer. These materials generally comprise from 0.5% to 10% by weight of the composition, preferably from 0.75% to 8%, most preferably from 1% to 6%.

Preferred optical brighteners are anionic in nature, an example of which is 4,4-bis-(2-diethanolamino-4-anilino-S-triazin-6-ylamino)stilbene-2: Disodium 2'-disulfonate, 4,4-bis-(2-morpholino-4-anilino-S-triazin-6-ylamino)stilbene-2:2'-disulfo disodium 4,4-bis-(2,4-dianilino-S-triazin-6-ylamino)stilbene-2:2'-disodium disulfonate, 4',4 "-bis-(2,4-dianilino-S-triazin-6-ylamino)-stilbene-2-sulfonic acid monosodium, 4,4'-bis-(2-anilino-4 -(N-methyl-N-2-hydroxyethylamino)-S-triazin-6-ylamino)stilbene-2,2'-disodium sulfonate, 4,4'-bis- (4-Phenyl-2,1,3-triazol-2-yl)-stilbene-2,2'-disodium sulfonate, 4,4'-bis-(2-anilino- 4-(1-Methyl-2-hydroxyethylamino)-S-triazin-6-ylamino)stilbene-2,2'-disodium sulfonate and 2-(distyryl- Sodium 4-(naphtho-1',2':4,5)-1,2,3-triazole)-2-sulfonate.

Other useful polymers are polyethylene glycols, especially those having a molecular weight of between 1000 and 10000, more preferably between 2000 and 8000, with an optimum molecular weight of about 4000. These materials are present in amounts of about 0.20% to about 5%, preferably about 0.25% to 2.5%, by weight of the composition. These polymers and the aforementioned polycarboxylates are extremely valuable for improving whiteness durability, fabric dust deposition, and cleaning performance on proteinaceous and oxidizable soils in the presence of clay, transition metal impurities.

Soil release agents useful in the compositions of the present invention are conventional copolymers or terpolymers of terephthalic acid and ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0272033. A particularly preferred polymer in EP-A-0 272 033 has the following molecular formula:

(CH ₃ (PEG) ₄₃ ) _0.75 (POH) _0.25 [T-PO) _2.8 (T-PEG) _0.4 ]T(PO-

H) _0.25 ((PEG) ₄₃ CH ₃ ) _0.75

where PEG is -(OC ₂ H ₄ )O-, PO is (OC ₃ H ₆ O) and T is (pcOC ₆ H ₄ CO)

Modified polyesters are also very useful, like random copolymers of the following: dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol, and 1-2-propanediol, mainly composed of sulfo Parabens, secondarily a base consisting of monoesters of ethylene glycol and/or propylene glycol. The aim is to obtain a polymer with sulfobenzoate groups at both ends, "principally", where most of the copolymers referred to herein are capped terminally with sulfobenzoate groups. However, some copolymers are not fully covered, so their end groups may consist of monoesters of ethylene glycol and/or 1,2-propanediol to form a "secondary" class of this compound.

The polyester selected here contains about 46% by weight of dimethyl terephthalate, about 16% of 1,2-propanediol, about 10% of ethylene glycol, about 13% by weight of sulfonic acid Dimethyl benzoate, sulfoisophthalic acid with a weight ratio of about 15%, and a molecular weight of about 3000. Polyesters and their methods of preparation are described in detail in EPA 311 342.

The detergent compositions of the present invention may be in liquid, paste, gel or granular form. The granular compositions of the present invention may also be in "concentrated form", i.e. they may have a higher density than conventional granular detergents, i.e. from 550 to 950 g/l; in this case, the granular detergent compositions of the present invention Contains less "inorganic fillers" than conventional granular detergents; typical filler salts are alkaline earth metal sulfates and chlorides, typically sodium sulfate; "concentrated" detergents typically include no more than 10% filler salts. The liquid compositions of the present invention may also be available in "concentrated form", in which case the liquid detergent compositions of the present invention contain less water than conventional liquid detergents. Typically, concentrated liquid detergents will have a water content of less than 30%, preferably less than 20%, most preferably less than 10% by weight of the detergent composition.

The present invention also relates to a method of inhibiting the transfer of dissolved and suspended dyestuffs from one fabric to another encountered during laundering of colored fabrics.

The method involves contacting the fabric with a wash solution as previously described.

The method of the present invention is easily carried out during the washing process. The washing process is preferably carried out at 5°C to 75°C, especially 20°C to 60°C, but the polymers are not effective at temperatures up to 95°C or even higher. The pH of the treatment solution is preferably 7 to 11, especially 7.5 to 10.5.

The methods and compositions of the present invention are also useful as detergent additive products. Such additive products are intended to supplement or enhance the efficacy of conventional detergent compositions. The detergent compositions of the present invention include substrates for cleaning compositions such as fabrics, fibres, hard surfaces, skin, etc., for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, Automatic and non-automatic dishwashing compositions.

The following examples illustrate the compositions of the present invention and are not necessarily meant to limit or define the scope of the invention, which is defined by the following claims.

Prepared a kind of detergent composition of the present invention, its component is as follows:

% by weight of the total detergent composition Linear Alkylbenzene Sulfonate 10 Alkyl Sulfate 4 Fatty Alcohol (C ₁₂ -C ₁₅ ) Ethoxylate 12 Fatty Acid 10 Oleic Acid 4 Citric Acid 1 NaOH 3.4 Propylene Glycol 1.5 Ethanol 10 table 1

The extent of dye transfer was determined using the Hunter Color measurement. The Hunter Color system evaluates the color of a fabric sample by the DC value representing the change in the Hunter a, b value measured by reflectance spectrophotometry. The DC value is defined by the following equation: Dc={(a _f -a _i ) ² +(b _f -b _i ) ² } ^1/2

The subscripts i and f represent the Hunter values before and after washing, respectively, in the presence of bleeding fabric. The least significant difference is 1 at the 95% confidence level.

Example 1

The degree of dye transfer between fabrics of different colors was studied using a launder-O-meter test simulating a 30 minute wash cycle. The Launder-O-meter beaker contained 200 ml of detergent solution, a 10 cm x 10 cm piece of colored fabric and a swatch of various fibers used as a bleeding dye tracer. Bleeding dye consists of one part Direct Blue 90, one part Direct Blue 112 and one part Direct Violet 47. The multifiber swatches are cotton.

Experimental conditions

pH=7.8

A: A detergent composition according to Table 1 without any dye transfer inhibiting system.

B: A detergent composition containing 10 ppm PVNO (poly(4-7 alkenylpyridine-N-oxide)) according to Table 1, wherein the average molecular weight of PVNO is about 10,000, amine to amine N-oxide The ratio is 1:10 (HOPAO).

C: A detergent composition containing 10 ppm PVNO (poly(4-vinylpyridine-N-oxide)) according to Table 1, wherein the average molecular weight of PVNO is about 30,000, and the ratio of amine to amine N-oxide It is 1:1 (LOPAO).

D: A detergent composition containing 5 ppm PVNO (poly(4-vinylpyridine-N-oxide)) according to Table 1, wherein the average molecular weight of PVNO is about 30,000, and the ratio of amine to amine N-oxide 1:10, and a detergent composition containing 5 ppm PVNO (poly(4-vinylpyridine-N-oxide)), the average molecular weight of PVNO is about 30,000, and the ratio of amine to amine N-oxide is 1 : 1 (HOPAO+LOPAO).

Result: DC value of cotton tracer

Example II (A/B/C/D)

Liquid detergent compositions having the following components are prepared according to the invention:

A B C D Linear alkylbenzene sulfonate 18 - 6 -C ₁₂ -C ₁₅ alkyl sulfate - 16.0 - -C ₁₂ -C ₁₅ alkyl ethoxylated sulfate - 11.0 4.0 25.0C ₁₂ -C ₁₄ N-methyl Glucosamide - 7.0 9.0 9.0C ₁₂ -C ₁₄ Fatty Alcohol Ethoxylate 12.0 5.0 6.0 6.0C ₁₂ -C ₁₆ Fatty Acid 9.0 6.8 14.0 14.0 Fatty Acid 10 10 10 10 Oleic Acid 4 4 4 4 Citric Acid 1 1 1 1 Dioxide Ethyltriamine-1,5-pentylidenephosphonic acid 1.5 1.5 1.5 1.5 Propylene glycol 1.5 1.5 1.5 1.5 Ethanol 10 10 10 10 Ethoxylated tetraethylenepentylamine 0.7 0.7 0.7 0.7 Poly 4-vinylpyridine-N-oxide HOPAO (HOPAO) 0.3 0.3 0.3 0.3 Polyetry 4-ethylene pheibidine -n-oxides (Lopao) 0.3 0.3 0.3 0.3Thermamyl 0.13 0.13 0.13 0.13carezyme 0.014 0.014 0.014fn-BaSE 1.8 1.8 1.8 1.8 Lipin 0.14 Dextranase A 0.53 0.53 0.53 0.53 Foam suppressor (ISOFOLr) 2.5 2.5 2.5 2.5 Add water and trace substances to 100NaOH and/or MEA Adjust pH to 7.8 Example III (A/B/C/D) prepared according to the present invention Concentrated granular detergent composition having the following formulation:

    Based on the weight % of the total detergent composition

A B C D polyhydroxy fatty acid amides 10 - - - alkyl alkoxylated sulfate - 9 9 9 alkyl sulfonate 4.80 4.80 4.80 4.807 times ethoxylated C _4-15 alcohol 4.00 4.00 4.00 4.0011 times ethoxylated tallow alcohol 1.8 1.80 1.8 1.8 disperse Agent 0.07 0.07 0.07 0.07 Silicone Fluid 0.80 0.80 0.80 0.80 Trisodium Citrate 14.00 14.00 14.00 14.00 Citric Acid 3.00 3.00 3.00 3.00 Zeolite 25.00 20.00 20.00 32.50 Diethylene Triamine 60 Phosphine 60 Phosphine 1,5 0.6 Maleic acid acrylic acid copolymer 5.00 5.00 5.00 5.00T-granulated Carezyme 0.2 0.5 0.15 0.3T-granulated Alcalase 0.60 0.60 0.20 0.50T-granulated Lipolase 0.20 0.10 0.25 0.40T-granulated Termamyl 0.3 0.3 0.3 sodium silicate 2.00 2.00 2.00 2.00 Sodium sulfate 3.50 3.50 3.50 3.50 Percarbonate - - 20 - Perborate 15 15 - - TAED - 5 5 - Fragrance encapsulated in micelles 0.2 - - - Fragrance 0.3 0.2 0.3 0.2 Poly(4- Vinylpyridine) N-oxide (HOPAO) 0.3 0.3 0.3 0.3 Poly(4-vinylpyridine) N-oxide (LOPAO) 0.3 0.3 0.3 0.3 Trace material added to 100 parts

Claims (3)

1. A dye transfer inhibiting detergent composition comprising 0.001-10% by weight of a mixture of polyamine N-oxide polymers having low and high degrees of oxidation and an average molecular weight ranging from 500 to 1,000,000, said The polyamine N-oxide polymers contain units having the formula, PA _x -R where P is a polymerizable unit to which the NO group can be attached, or where the NO group forms part of the polymerizable unit; A is NC=O, C(=O)O, C=O, -O-, -S-, -N-; X is 0 or 1; R is selected from pyridine, pyrrole, quinoline, acridine, imidazole, wherein the nitrogen on the NO group forms part of the R group; and wherein Said low degree of oxidation polyamine N-oxide polymer has an amine to amine N-oxide ratio of from 1000:1 to 1:1 and said high degree of oxidation polyamine N-oxide polymer has The ratio of amine to amine N-oxide is from 2:3 to 1:1,000,000. 2. A detergent composition according to claim 1, wherein the polymer backbone is derived from polyvinyl polymer groups. 3. A detergent composition according to claim 1 or 2, in a non-dusting granular or liquid form.