WO2004048506A1

WO2004048506A1 - Dye transfer inhibitors for laundry detergents

Info

Publication number: WO2004048506A1
Application number: PCT/US2003/038680
Authority: WO
Inventors: Carlos A. Piedrahita; Nai Z. Huang; Joseph G. Seebauer
Original assignee: The Lubrizol Corporation
Priority date: 2002-11-26
Filing date: 2003-11-25
Publication date: 2004-06-10
Also published as: AU2003298918A1

Abstract

A dye transfer inhibitor comprising a hydrocarbyl substituted pyridine such as 4-vinylpyridine reacted with a hydrocarbyl sulfonic acid such 2-acrylamido-2-methylpropane sulfonic acid is effective as a dye transfer inhibitor for applications such as laundering clothes. Either of the two components of the dye transfer inhibitor can be a portion of a water soluble oligomer or polymer.

Description

Title: DYE TRANSFER INHIBITORS FOR LAUNDRY DETERGENTS

Field of the Invention

The present invention generally relates to water-soluble dye transfer inhibitors (DTI) and their use in washing textiles and related processes. One component is a hydrocarbyl substituted pyridine in monomer, oligomer or polymer form. A second component is a hydrocarbyl sulfonic acid such as 2-acrylamido-2- methylpropane sulfonic acid (AMPS®) monomer. The first and second components interact with each other as a reaction product or a salt. Dye transfer inhibitors are characterized by their ability to inhibit the tendency of colored fabrics to transfer dye to other fabrics or to other portions of the same fabric during laundering. The mechanism of dye transfer inhibitors is typically to complex or adsorb fugitive dyes in the wash liquor so as to prevent them from re-depositing onto fabrics that did not originally have those dyes. Background of the Invention

One of the most persistent and troublesome problems arising during modern fabric laundering operations is the tendency of some colored fabrics to release dye into the laundering solutions. The dye is then transferred onto other fabrics being washed therewith. One way of overcoming this problem would be to complex or adsorb the fugitive dyes washed out of dyed fabrics before they have the opportunity to become attached to other articles in the wash. Polyvinylpyrrolidone (PVP), by virtue of its dye complexation ability, has been used to inhibit dye deposition during washing of colored fabrics under laundry conditions. The performance of polyvinylpyrrolidone as a dye transfer inhibitor, however, is adversely affected by the presence of high levels of anionic surfactants in the washing process.

U.S. Patent 5,607,618 to Hoechst Aktiengesellschaft discusses the use of water-soluble copolymers, based on acrylamidoalkylenesulfonic acid, vinylacetamide, and, if appropriate, other monomers, as a detergent additive for preventing reabsorption of detached dyestuffs and dyestuff degradation products. U.S. Patent 5,922,088 to Henkel Corp. discusses a process for fixing dyes impregnated in fine-dimensional synthetic textile substrates in an environmentally safe manner using a dye fixative compositions comprising a) polymethacrylic acid, b) copolymers of methacrylic acid with specified other monomers, c) sulfamic acid, and combinations of a, b, and c.

U.S. Patent 6,159,921 to Henkel Corp. discloses a detergent composition comprising an alkali component selected from a group, a dye transfer inhibition additive selected from the group consisting of (i) a sugar surfactant selected from alkyl polyglycosides having a particular formula, (ii) an alkyl sulfate, (iii) an aminocarboxylic acid amphoteric surfactant, and (iv) mixtures of (i), (ii), and (iii). US 6,306,815 to National Starch and Chemical Investment Holding Corp. discloses water-soluble quaternary polyvinylpyrridinium derivative which inhibits dye transfer in detergent compositions without adversely affecting stain or soil removal or soil redeposition.

U.S. Patent 6,432,909 to ISP Investments Inc. discloses dye complexing polymers such as isopropenylpyridine betaines containing a quaternary nitrogen and a carboxylate salt or carboxylic acid group that have effective dye complexing properties for use, for example, in laundry detergent and fabric softener compositions.

Other polymers which have been used in detergent compositions to inhibit dye transfer include polyvinylimidazole, polyvinylpyridine N-oxide, and copolymers of polyvinylpyridine and polyvinylimidazole. DE 2 814 287-A describes detergent compositions containing N-vinyl imidazole homo- or copolymer in combination with anionic and/or nonionic surfactants and other detergent ingredients. WO 95/03390 describes dye inhibiting polymers of polyvinylpyrrolidone, polyamine N- oxide, and vinylimidazole. U.S. Patent No. 5,460,752 describes polyamine N-oxide polymers. U.S. Patent 5,627,151 describes copolymers of vinylpyrrolidone or vinylimidazole, vinylpyridine or dimethylaminoethyl methacrylate or dimethylaminopiOpyl-methacrylamide, including up to 20% vinylacetate, for use in laundry detergents. U.S. Patent No. 5,466,802 describes poly(4-vinylpyridine-N- oxide) and copolymers of vinylpyrrolidone and vinylimidazole. EP 754748 describes vinylpyridine copolymers and formic acid. U.S. Patent No. 5,458,809 describes poly(4-vinylpyridine-N-oxide). WO 95/27038 describes poly(4- vinylpyridine-N-oxide), polyvinylpyrrolidone, polyvinylpyrrolidone-vinylimidazole and copolymers of vinylpyrrolidone and vinylimidazole.

EP 372 291 describes a process for washing discoloration-sensitive textiles. The wash liquor contains anionic/nonionic surfactants and water-soluble polymers, for example, copolymers of 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 describes electrolyte-free liquid detergent compositions comprising zeolite A, nonionic surfactants and homo- and copolymers selected from N-vinylpyrrolidone and/or N-vinylimidazole and/or N-vinyloxazolidone. U.S. Patent No. 5,776,879 describes water-soluble poly(vinylpyridine betaines) containing a quaternary nitrogen and a carboxylate salt, which have effective dye transfer inhibitor properties. U.S. Patent Application Serial No. 09/300,913, filed April 28, 1999, describes polyvinylpyrridinium derivatives containing a quaternary nitrogen and an anionic moiety selected from a sulfonate or a carboxylate functionality, for use in detergent compositions.

Summary of the Invention The invention provides dye transfer inhibitors that are more effective at minimizing redeposition of fugitive dyes and fugitive dye degradation products than prior art dye transfer inhibitors. As a class the dye transfer inhibitors of the invention comprise a combination of a) hydrocarbyl substituted pyridine or a polymer or oligomer including vinylpyridine monomer units and b) a hydrocarbyl sulfonic acid such as 2-acrylamido-2-methylpropane sulfonic acid monomer or a polymer formed from said monomer. The a) and b) components can react together to form an adduct where the α-carbon of the vinyl portion of the vinylpyridine or 2- acrylamido-2-methylpropane sulfonic acid chemically bonds to the nitrogen atom of the pyridine. Alternatively the sulfonic acid of the hydrocarbyl sulfonic acid such as 2-acrylamido-2-methylpropane sulfonic acid can protonate the nitrogen of the pyridine and then the cationic protonated nitrogen atom can form an ionic salt with the anionic sulfonic group of the 2-acrylamido-2-methylpropane sulfonic acid. However, the dye transfer inhibitors of this invention do not include copolymer having backbone repeating units of both vinylpyridine and 2-acrylamido- 2-methylpropane sulfonic acid when the copolymers contain certain protonated pyridinium species disclosed in US 6,306,815.

Generally except for the above exclusions the hydrocarbyl substituted pyridine and the 2-acrylamido-2-methylpropane sulfonic acid can be contained

(copolymerized or otherwise attached) in various water soluble polymers without restriction on the co-monomers present.

Desirably the hydrocarbyl substituted pyridine e.g. vinyl pyridine monomer or the repeat units from polymerizing vinylpyridine is present in the final detergent or soap composition at a concentration from about 0.1 percent to about 50 percent based on the weight of the detergent. Desirably the hydrocarbyl sulfonic acid such as 2-acrylamido-2-methylpropane sulfonic acid is present at a molar ratio of from about 0.5 to about 5 relative to the moles of hydrocarbyl substituted pyridine e.g. vinylpyridine monomer or repeat units from polymerizing the hydrocarbyl substituted pyridine. Other components common to laundry or other textile cleaning products may be included in the final composition for their conventional purposes.

Detailed Description of the Invention This invention relates to water-soluble dye transfer inhibitors. The compounds are useful as dye transfer inhibitors and color protection agents in detergent compositions, especially detergent compositions containing a high level of anionic surfactants.

In accordance with the invention, several reaction products (including salts) of hydrocarbyl sulfonic acid and hydrocarbyl substituted pyridine have been developed that give improved dye transfer inhibition. The hydrocarbyl sulfonic acids can be the AMPS® monomer (2-acrylamido-2-methylpropane sulfonic acid) which has the formula shown below.

AMPS ^R MONOMER

As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

(1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);

(2) substituted hydrocarbon substituents, that is, substituents containing non- hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);

(3) hetero substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl. In general, no more than three, preferably no more than one or two, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

When hydrocarbyl sulfonic acids are described it is preferred that the hydrocarbyl group have from about 6 to about 20 carbon atoms. This description would be relevant to the hydrocarbyl sulfonic acid as a compound (including monomer) or as a repeat unit in a larger oligomer or polymer. However when referring to a polymer that contains a hydrocarbyl sulfonic acid, only the hydrocarbyl sulfonic acid repeat unit will be required to have the specified number of carbon atoms (i.e. the average number of carbon atoms per sulfonic acid in the polymer will not be required to fall within the specified range). Other hydrocarbyl sulfonic acids include styrene sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, allyloxy sulfonic acid, various benzene sulfonic acids, alkyl sulfonic acids, etc. Polymers containing repeating units including a portion of hydrocarbyl sulfonic acid (e.g. 2-acrylamido-2-n ethylpropane sulfonic acid) are within the scope of the disclosure with the proviso that desirably the polymers are water soluble after reacting with the hydrocarbyl substituted pyridine portion of the dye transfer inhibitor.

The hydrocarbyl sulfonic acids do not offer dye transfer inhibition by themselves but must be used in combination with a hydrocarbyl substituted pyridine, in monomer, oligomer, or polymer form. The hydrocarbyl substituted pyridine entities are pyridine molecules substituted with the various hydrocarbyl groups discussed above. Desirably for the hydrocarbyl substituted pyridine the hydrocarbyl group has from about 2 to about 10 carbon atoms and is substantially free of heteroatoms other than nitrogen. A preferred hydrocarbyl group is a vinyl group and most preferably the vinyl group is para to the nitrogen atom of the pyridine (e.g. 4- vinylpyridine).

Typically the hydrocarbyl sulfonic acid and the hydrocarbyl substituted pyridine are allowed to react to form the dye transfer inhibitor. They may undergo a chemical reaction forming a new chemical compound (e.g. adduct(s)) or they may react together to form a salt of the basic pyridine and the acidic sulfonic acid. It is known that some of the materials described above may interact in the final formulation. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses the composition prepared by admixing the components described above. Either the hydrocarbyl sulfonic acid or the hydrocarbyl substituted pyridine may be used as an oligomer or polymer as well as a low molecular weight compound. The preferred embodiments of both of these compounds are readily copolymerizable with a variety of ethylenically unsaturated monomers. Obviously the ethylenically unsaturated monomers should be carefully selected so that the resulting polymer has reasonable water solubility. Any ethylenically unsaturated monomer may be used. Such monomers are known to those skilled in the art. A combination of ethylenically unsaturated monomers may also be used.

In one embodiment of the invention, the ethylenically unsaturated monomers have an anionic charge or become anionic upon treatment with a base. Examples of such monomers are acrylic acid, sodium salt of 2-acrylamido-2-methyl propane sulfonic acid, sodium methallyl sufonate, sodium vinyl sulfonate, sulfonated styrene, sodium salt of allyloxybenzene sulfonic acid, methacrylic acid, alpha-chloro-acrylic acid, alpha-cyano acrylic acid, alpha-chloro-acrylic acid, alpha-cyano acrylic acid, beta methyl-acrylic acid (crotonic acid), alpha-phenyl acrylic acid, beta-acryloxy propionic acid, sorbic acid, alpha-chloro sorbic acid, angelic acid cinnamic acid, p- chloro cinnamic acid, beta styryl acrylic acid (l-carboxy-4-phenyl butadiene- 1,3), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, and tricarboxy ethylene.

In one embodiment of the invention, the ethylenically unsaturated monomers are nonionic nitrogen containing monomers. Examples of such monomers are acrylamide, N, N-dimethylacrylamide, N-octyl acrylamide, N-methylol acrylamide, dimethylaminoethylacrylate, vinyl pyrrolidone, vinyl imidazole, N-vinyl formamide,

N-vinyl acetamide, dimethytaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, dimethyl aminoneopentyl acrylate, dimethyl aminoneopentyl methacrylate, dimethylaminoethylacryla ide, dimethylaminoethylmethacrylamide, diethylaminoethylacrylamide, diethylaminoethylmethacrylamide, dipropylamino- ethylacrylamide, dipropylaminoethylmethacrylamide, dimethylaminopropyl- acrylamide, dimethylaminopropylmethacrylamide, diethylaminopropylacrylamide, diethylaminopropylmethacrylamide, dimethylaminoneopentylacrylamide, dimethyl- aminoneopentylmethacrylamide and dialkylaminobutylacrylamide. In one embodiment of the invention, the water-soluble hydrocarbyl substituted pyridine, e.g. 4-vinylpyridine compound of the invention are made by polymerizing a monomer such as 4- vinylpyridine under suitable polymerization conditions to form a poly(vinylpyridine) intermediate, and then reacting the poly(vinylpyridine) intermediate with a hydrocarbyl sulfonic acid. The reaction product is a salt of the poly(4-vinylpyridine) with the hydrocarbyl sulfonic acid.

In one embodiment of the invention, the dye transfer inhibitor of the invention is used in detergent compositions. The level of the dye transfer inhibitor of the invention in the detergent compositions is from about 0.01 to about 90 weight percent, more preferably from about 0.05 to about 20 weight percent, most preferably from about 0.1 to about 10 weight percent, based on the total weight of the detergent composition. Alternatively the dye transfer inhibitor may be used outside laundry applications in other fabric applications such as in compositions to minimize dye transfer on newly manufactured fabrics, including clothing, upholstery and carpeting. Further the dye transfer inhibitor can be used in other areas where the fabric is contacted with water, e.g. fabric softener treatments or other aqueous treatments of a fabric.

The detergent composition may be a solid or liquid composition. If the detergent composition is solid, the detergent composition may be in any of the usual physical forms, such as for example, powders, beads, flakes, bars, tablets, noodles, pastes, and slurries. If the detergent composition is liquid, the detergent composition preferably disperses or solubilizes the dye transfer inhibitor. The detergent composition may be aqueous or nonaqueous. For example, the dye transfer inhibitor may be dissolved or dispersed in water, in one or more solvents or inert diluents. Preferably the detergent composition is aqueous. The detergent compositions may contain any additional components which are used in detergent compositions. Such additional components are well known to those skilled in the art and include one or more surfactants, builders, ion exchangers, alkalies, anticorrosion materials, antiredeposition materials, optical brighteners, fragrances, dyes, chelating agents, enzymes, whiteners, brighteners, antistatic agents, sudsing control agents, solvents, hydrotropes, bleaching agents, perfumes, bleach precursors, water, buffering agents, soil removal agents, soil release agents, softening agents, opacifiers, inert diluents, buffering agents, corrosion inhibitors, graying inhibitors, and stabilizers. Combinations of such additional components may also be used.

Suitable surfactants are nonionic, anionic, cationic, ampholytic, zwitterionic and semi-polar surfactants. A combination of surfactants may also be used. Anionic surfactants include, for example, from C₈ to C₂₀ alkylbenzenesulfonates, from C₈ to C₂o alkanesulfonates, from C₈ to C₂o alkylsulfates, from C₈ to C₂₀ alkylsulfosuccinates or from C8 to C20 sulfated ethoxylated alkanols.

Nonionic surfactants include, for example, from C₆ to C₁₂ alkylphenol ethoxylates, from C₈ to C₂₀ alkanol alkoxylates, and block copolymers of ethylene oxide and propylene oxide. Optionally, the end groups of polyalkylene oxides can be blocked, whereby the free OH groups of the polyalkylene oxides can be etherified, esterified, acetalized and/or aminated. Another modification consists of reacting the free OH groups of the polyalkylene oxides with isocyanates. The nonionic surfactants also include C₄ to ₈ alkyl glucosides as well as the alkoxylated products obtainable therefrom by alkoxylation, particularly those obtainable by reaction of alkyl glucosides with ethylene oxide.

Cationic surfactants contain hydrophilic functional groups where the charge of the functional groups are positive when dissolved or dispersed in an aqueous solution. Typical cationic surfactants include, for example, amine compounds, oxygen containing amines, and quaternary amine salts.

Amphoteric surfactants contain both acidic and basic hydrophilic groups Amphoteric surfactants are preferably derivatives of secondary and tertiary amines, derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The cationic atom in the quaternary compound can be part of a heterocyclic ring. The amphoteric surfactant preferably contains at least one aliphatic group, containing about 3 to about 18 carbon atoms. At least one aliphatic group preferably contains an anionic water-solubilizing group such as a carboxy, sulfonate, or phosphono. Generally, anionic surfactants, such as linear alkyl sulfonates (LAS) are preferred for use in solid detergent compositions containing the dye transfer inhibitor. Nonionic and anionic surfactant mixtures such as alcohol ethoxylates and

LAS are preferred in liquid detergent compositions containing the dye transfer inhibitor. The surfactants are optionally present in an amount of from about 0 to about 50 weight percent, preferably from about 2 to about 45 weight percent, and more preferably from about 5 to about 40 weight percent, based on the total weight of the detergent composition.

Examples of bleaching agents are perborates, percarbonates, or chlorine- generating substances such as chloroisocyanurates. Examples of silicates used as corrosion inhibitors are sodium silicate, sodium disilicate, and sodium metasilicate. Examples of graying inhibitors are carboxymethylcellulose, methylcellulose, hydroxypropylmethyl-cellulose, and polyacrylic acid and copolymers of acrylic and maleic acid.

Examples of enzymes are proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.

Any conventional builder system is suitable for use in the detergent composition including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Though less preferred for obvious environmental reasons, phosphate builders can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly 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, e.g., SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2O5). The preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. Preferred builder systems for use in the detergent compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS/6), and a water-soluble carboxylate chelating agent such as citric acid.

A suitable chelant for inclusion in the detergent compositions is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.

[0038] Examples of suds suppressors are silicones and silica-silicone mixtures. Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. [0039] Examples of antiredeposition and soil suspension agents are cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homopolymers of acrylic acid and copolymers of maleic acid and acrylic acid.

Examples of optical brighteners are disodium 4,4-bis-(2-diethanolamino-4- anilino-s-triazin-6-ylamino)stilbene-2:2disulphonate, disodium 4,-4-bis-(2- morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2-disulphonate, disodium 4,4- bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2-disulphonate, monosodium 4,4- bis-(2,4-dianilino-s-triazin-6ylamino)stilbene-2-sulphonate, disodium 4,4-bis-(2- anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2- disulphonate, disodium 4,4-bis-(4-phenyl-2,l,3-triazol-2-yl)-stilbene-

2,2disulphonate, disodium 4,4bis(2-anilino-4-(l-methyl-2-hydroxyethylamino)-s- triazin-6-ylamino)stilbene-2,2disulphonate, and sodium 2(stilbyl-4-(naphtho- 1, 2:4,5)- l,2,3-triazole-2-sulphonate.

Other useful polymeric materials which may be added to the detergent compositions are polyethylene glycols, particularly those of molecular weight 1000-

10000, more particularly 2000 to 8000 and most preferably about 4000. These optional polymeric materials including the previously mentioned homo- or copolymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities. Examples of soil release agents are conventional copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements, as well as the ethoxylated/propoxylated polyamines. Modified polyesters may also be used as soil release agents, and include random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and or propane-diol.

The following non-limiting examples illustrate further aspects of our invention.

Example 1 4-vinylpyridine (5 grams) and AMPS monomer (9.85 grams) were combined in 50 grams of methanol. The clear solution was stirred at room temperature for 3 hours and subsequently for 5 hours at 60-65°C. The volatiles were removed with a rotary evaporator to give a light pink solid.

Example 2 4-vinylρyridine (10.5 grams), water (50 grams) and AMPS (20.7 grams) were combined at room temperature until all of the AMPS was dissolved. The reaction was exothermic and stirring was continued for 1 hour. The product was a light red solution.

Example 3 Poly-4- vinylpyridine (1.05 grams) was suspended in water (28 grams) and

AMPS (2.07) (grams) was added. The mixture was stirred at 30-40°C for 15 minutes. The clear solution contained 10% water. The AMPS/ Poly-4- vinylpyridine content could be varied.

In the formulas below the hydrocarbyl group is shown in the para position to the nitrogen atom of the vinylpyridine, but the hydrocarbyl may be in the ortho or meta positions.

Structure I (Example 2)

Structure It (Example 3)

Structure III (Example 1)

While the adduct is shown as being a single 4-Vinylpyridine with a single AMPS molecule, further study has indicated a major amount of an adduct or oligomer from adding the vinyl group from a 4-vinylpyridine to the nitrogen of another 4-vinylpyridine.

In the following table(s) the performance of various experimental dye transfer inhibitors is compared to the performance of several commercial dye transfer inhibitors. The commercial products are polyvinylpyrrolidinone, polyvinylpyridine-

N-oxide and poly(N-carboxymethyl-4-vinylpyridinium chloride) sodium salt.

The effectiveness of both commercial and experimental dye transfer inhibitors in a simulated washing cycle was tested using a modified version of ASTM D5548-99. Though the materials tested could be tested at any desired temperature, they were preferably tested at temperatures of 100°F or 140°F. Direct

Red 80 was the dye used in carrying out the testing. The effectiveness of the dye transfer inhibitor compositions was tested using a six position Terg-O-Tometer instrument. Each washing composition contained 10 ppm of dye, 1 g/1 Wisk laundry detergent and a given amount of dye transfer inhibitor additive. These components were diluted with synthetic hard water (110 ppm Ca:Mg 3:1) to a volume of one liter. Two undyed cotton swatches (Scientific Services SID, Inc.) were immersed in the test solutions. The solutions were agitated for ten minutes. The swatches were then removed, excess solution drained from the Terg-O-Tometer and the swatches rinsed in clean hard water for three minutes. The swatches were then air dried for at least one hour. Reflectance measurements were taken on a Hunter Lab Color Quest colorimeter. The reflectance readings were recorded as ΔE, which is a composite of the degree of whiteness, redness and blueness indices in the dyed cloth. These readings were taken as a direct measure of the degree of dye deposition under the test washing condition. The test parameter percent inhibition was calculated using the "a" value from the ΔE equation where "a" is a measure of the redness and greenness of the sample being measured. To calculate percent inhibition use the following equation:

% Inhibition = ((a_c - a_s)/a_c) x 100 where a_c = "a" value of control fabric swatch with no DTI a_s = "a" value of fabric swatch tested with DTI present The test results are shown in Table 1 below. TABLE I

Typical treat levels of dye transfer inhibitor in laundry detergent are between l-30ppm.

The 4-vinylpyridine / AMPS salt was characterized by NMR and was very effective at dye transfer inhibition, particularly at low levels (5-10ppm), when compared to the commercial materials at the same concentration.

The reaction products of 4-vinylpyridine and AMPS contain adduct structure shown previously and 4-vinylpyridine self -polymerized and oligomerized species.

This adduct demonstrated the same inhibition performance that the salt did at 100°F. The poly(4-vinylpyri dine)/ AMPS salt gave optimal dye transfer inhibition (at

100°F) between 40-50ppm.

While the invention has been described with particular reference to certain- embodiments thereof, it will be understood that changes and modifications may be made by those of ordinary skill in the art within the scope and spirit of the following claims.

Claims

What is claimed is:

1. A detergent or soap composition for treating textiles comprising a wash-active surfactant and an effective amount of dye transfer inhibitor additive for preventing the reabsorbation of dyestuffs and dyestuff degradation products, said additive characterized by including both a) a hydrocarbyl substituted pyridine or pyridinium ring optionally in monomer, oligomer or polymer form and b) a hydrocarbyl sulfonic acid such as 2-acrylamido-2-methylpropane sulfonic acid optionally in monomer, oligomer , or a polymer form; said a) and b) components not being backbone repeating units in the same polymer molecule.

2. A detergent or soap according to claim 1, wherein said additive comprises the reaction products of reacting vinylpyridine with 2-acrylamido-2-methylpropane sulfonic acid.

3. A detergent or soap according to claim 1, wherein said additive comprises the salt of vinylpyridine and 2-acrylan_ido-2-methylpropane sulfonic acid.

4. A detergent or soap according to claim 1, wherein said additive comprises the salt of c) a polymer derived from polymerizing vinylpyridine with itself or one or more other ethylenically unsaturated monomers and said polymer reacted after polymerization with 2-acrylamido-2-methylpropane sulfonic acid; or d) a polymer derived from polymerizing the salt of vinylpyridine and 2-acrylamido-2- methylpropane sulfonic acid, optionally with one or more other ethylenically unsaturated monomers.

5. A laundry detergent or soap composition according to claim 1, comprising 0.01 to 90 weight percent and preferably from 0.05 to 20 weight percent and most preferably from 0.1 to 10 percent by weight, based on the total weight of the detergent or soap composition, of said hydrocarbyl substituted pyridine or pyridinium ring and hydrocarbyl sulfonic acid .

6. A detergent or soap composition according to claim 1, optionally comprising at least one ingredient selected from the group consisting of builders, enzymes and preferably a protease enzyme, enzyme stabilizers, optical brighteners, bleaches, bleach boosters, bleach activators, dye transfer agents, dispersants, enzyme activators, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, and mixtures thereof.

7. A process for inhibiting dye transfer from one fabric to another during fabric laundering operations involving colored fabrics, said process comprises contacting fabrics with a laundering solution comprising both a) a hydrocarbyl substituted pyridine pryidinium, optionally in monomer, oligomer, or polymer form and b) a hydrocarbyl sulfonic acid such as 2-acrylamido-2-methylpropane sulfonic acid optionally in monomer, oligomer, or a polymer form; said a) and b) components not being backbone repeating units in the same polymer molecule. A detergent or soap composition according to claim 4, wherein said polymer has molecular weight (Mw) of 30,000 to 100,000.

8. A detergent composition as claimed in claim 1, further comprising: a) a sequestering agent, b) an optical brightener, c) an enzyme, d) a bleaching agent, e) a stabilizing or activating agent for said bleaching agent or a combination of a stabilizing agent and an activating agent, f) a washing alkali, g) an anti-redeposition agent or combinations thereof.

9. A dye transfer inhibitor characterized by including both a) a hydrocarbyl substituted pyridine or pyridinium ring optionally in monomer, oligomer or polymer form and b) a hydrocarbyl sulfonic acid such as 2-acrylamido-2-methylpropane sulfonic acid optionally in monomer, oligomer , or a polymer form; said a) and b) components not being backbone repeating units in the same polymer molecule.