COMPOSITION CONTAINING A MATTIFYING AGENT

Abstract

This invention relates to a laundry care composition comprising a laundry care ingredient and a polymeric thiophene mattifying agent.

Description

COMPOSITION CONTAINING A TONING AGENT CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority over U.S. Provisional Patent Application No. 62 / 983,873, entitled Composition Containing Matting Agent, which was filed on March 2, 2020, and is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0002] This invention relates to a laundry care composition comprising a laundry care ingredient and a polymeric thiophene mattifying agent. BACKGROUND

[0003] As consumers increasingly favor lower temperatures and shorter wash cycles to conserve energy, the cleaning efficiency of laundry care formulas may not be as effective as at higher temperatures and longer wash times. Therefore, the use of brightening agents in laundry care formulas provides a technology that offers a whitening benefit to soiled textiles (e.g., clothing and other garments), making them appear brighter and whiter, even at lower wash temperatures and shorter cycle times. The use of harsh bleaching chemicals is also undesirable, as they can shorten the lifespan of textiles and be harmful to the environment.Furthermore, in some cases, consumers prefer a more reddish-violet hue in clothing to mask yellowing of fabrics that cannot be achieved with bleaching formulations. As a result, there is a continuing need to improve the bleaching effect of fabrics treated with laundry compositions containing toning agents. The present invention provides a laundry composition comprising a polymeric thiophene toning agent that has been shown to bleach textile articles, such as cellulose-containing fabrics. The incorporation of this toning agent into a laundry composition provides a possible and successful delivery mechanism for deposition onto a textile substrate. Each time the textile substrate is washed, the toning agent is deposited onto it.Therefore, the textile substrate is continuously bleached and the life cycle of the item can be extended. BRIEF DESCRIPTION

[0004] In one aspect, the invention relates to an aqueous laundry care composition comprising a laundry care ingredient and 0.0001% by weight to 1.0% by weight of a polymeric thiophene mattifying agent having the structure of Formula I: Formula I wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy and polyethylenexy / polypropylenexy copolymers, and wherein each A is independently present in the range of 1 to 20 repeating units of polyethylenexy, polypropylenexy or polyethylenexy / polypropylenexy copolymers; wherein each Ri is independently selected from H, C1-4 alkyl, alkoxy alkyl, halogens, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, CH2CH2C1, -CH=CH2, -CH2CH(OH)2 and their salts; wherein each R2 is independently selected from Ci-is alkyl, aryl, substituted aryl and substituted alkyl.

[0005] In another aspect, the invention relates to an aqueous laundry care composition comprising a laundry care ingredient and 0.0001% by weight to 1.0% by weight of a polymeric thiophene mattifying agent having the structure of Formula I: Formula I wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy and polyethylenexy / polypropyleneoxy copolymers, and wherein each A is independently present in the range of 1 to 5 repeating units of polyethylenexy, polypropylenexy or polyethylenexy / polypropyleneoxy copolymers; wherein each Ri is independently selected from H and C1-4 alkyl.

[0006] In another aspect, the invention relates to an aqueous laundry care composition comprising a laundry care ingredient and 0.0001% by weight to 1.0% by weight of a polymeric thiophene mattifying agent having the structure of Formula II: ινΐΛ / a / zuzz / uiuio □ Formula II wherein each A is independently selected from the group consisting of polyethylenexy, 5 polypropylenexy and polyethylenexy / polypropylenexy copolymers, and wherein each A is independently present in the range of 1 to 5 repeating units of polyethylenexy, polypropylenexy or polyethylenexy / polypropylenexy copolymers.

[0007] In another aspect, the invention relates to a method for manufacturing a polymeric thiophene matting agent containing amide, wherein the amide is formed through the hydrolysis of a nitrile under basic conditions, such as pH > 9.

[0008] In another aspect, the invention relates to a laundry care composition comprising: (1) a wash care ingredient; (2) from 0.0001% by weight to 1.0% by weight of a polymeric thiophene matting agent having the structure of Formula I: Formula I wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy, and polyethylenexy / polypropylenexy copolymers, and wherein each A is independently present in the range of 1 to 20 repeating units of polyethylenexy, polypropylenexy, or polyethylenexy / polypropylenexy copolymers; wherein each R1 is independently selected from H, C1-4 alkyl, alkoxy alkyl, halogens, aryl, substituted alkyl or substituted aryl, -COR?, -CH?COH, -COOR?, -COOH, -SO3H, -CH?COOH, CH2CH2CI, -CH=CH2, -CH2CH(OH)2 and their salts; wherein each R2 is independently selected from Ci-ig alkyl, aryl, substituted aryl and substituted alkyl; and (3) from 0.0001% by weight to 1.0% by weight of a polymeric thiophene matting agent having the structure of Formula X: Formula X wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy and polyethylenexy / polypropylenexy copolymers, and wherein each A is independently present in the range of 1 to 20 repeating units of polyethylenexy, polypropylenexy or polyethylenexy / polypropylenexy copolymers; wherein each Ri is independently selected from H, C1-4 alkyl, alkoxy alkyl, halogens, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, CH2CH2CI, -CH=CH2, -CH2CH(OH)2 and their salts; wherein each R2 is independently selected from Ci-18 alkyl, aryl, substituted aryl and substituted alkyl.

[0009] In another aspect, the invention relates to a laundry care composition comprising: (i) a laundry care ingredient; and (ii) from 0.0001% by weight to 1.0% by weight of a polymeric thiophene mattifying agent having the structure of Formula I: Formula I wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy, and polyethylenexy / polypropylenexy copolymers, and wherein each A is independently present in the range of 1 to 20 repeating units of polyethylenexy, polypropylenexy, or polyethylenexy / polypropylenexy copolymers; wherein each Ri is independently selected from H, C1-4 alkyl, alkoxy alkyl, halogens, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, CH2CH2C1, -CH=CH2, -CH2CH(OH)2 and their salts; wherein each R2 is independently selected from C1-4 alkyl, aryl, substituted aryl and substituted alkyl;and where the laundry care composition imparts a whitening effect to a textile article containing cellulose that is measurably greater than to a textile article containing polyester treated with the laundry care composition, where the whitening effect is measured through a whiteness index on each textile article.

[0010] In another aspect, the invention relates to a process for measurably improving a whitening effect in cellulose-containing textile articles, wherein the improvement is present in an amount greater than that observed in polyester-containing textile articles, wherein the process comprises the following steps: (a) providing a cellulose-containing textile substrate, (b) providing a polyester-containing textile substrate, (c) exposing the textile substrates of steps (a) and (b) to a garment care composition comprising: (i) a garment care ingredient; and (ii) from 0.0001% by weight to 1.0% by weight of a polymeric thiophene matting agent having the structure of Formula I: Formula I wherein each A is independently selected from the group consisting of polyethylenexy, polypropyloxy, and polyethylenexy / polypropylenoxy copolymers, and wherein each A is independently present in the range of 1 to 20 repeating units of polyethylenexy, polypropyloxy, or polyethylenexy / polypropylenoxy copolymers; wherein each Ri is independently selected from H, C1-4 alkyl, alkoxy alkyl, halogens, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, CH2CH2CI, -CH=CH2, -CH2CH(OH)2 and their salts; wherein each R2 is independently selected from Ci-is alkyl, aryl, substituted aryl, and substituted alkyl; and (d) measuring the bleaching effect by evaluating the whiteness index of each textile article.

[0011] In another aspect, the invention relates to a textile article, wherein the textile article contains: (a) a majority by weight of cellulose fiber, and (b) a garment care composition comprising: (i) a garment care ingredient; and (ii) from 0.0001% by weight to 1.0% by weight of a polymeric thiophene matting agent having the structure of Formula III: (pH2CH2O)3H (CH2CH2O)2H Formula III DETAILED DESCRIPTION

[0012] The invention described herein is a laundry care composition comprising a laundry care ingredient and a polymeric thiophene matting agent. In one aspect of the invention, the polymeric thiophene matting agent is added to a textile article via a laundry care composition during a standard washing process. The laundry care composition containing the polymeric thiophene matting agent is added to a washing machine, allowing the molecule to come into direct contact with the textile article. Thus, during the washing process, the polymeric thiophene matting agent is deposited on at least one surface of the textile article, resulting in improved whitening of the treated textile article.

[0013] As used herein, the term alkoxy is intended to include Ci-Cg alkoxy and alkoxy derivatives of polyols having repeating units such as butylene oxide, glycidol oxide, ethylene oxide, or propylene oxide.

[0014] As used herein, unless otherwise specified, the terms alkyl and topped alkyl are intended to include C2 to C10 alkyl groups, C2 to C50 alkyl groups, C5-C25 alkyl groups, or even C10-C20 alkyl groups.

[0015] As used herein, unless otherwise specified, the term aryl is intended to include C6-C12 aryl groups.

[0016] As used herein, unless otherwise specified, the term arylalkyl is intended to include Ci-Cis alkyl groups and, in one respect, alkyl groups Ci-Cg.

[0017] As used herein, unless otherwise specified, the term alkanoyl refers to univalent groups of Formula —C(O)Ra, where Ra is an alkyl group, preferably a C3-C29 alkyl group.

[0018] As used herein, unless otherwise specified, the term alkenyl refers to monovalent groups derived from acyclic olefinic hydrocarbons by the removal of a hydrogen atom from any carbon atom. In the context of this definition, the term acyclic olefinic hydrocarbons refers to acyclic hydrocarbons containing one or more carbon-carbon double bonds.

[0019] The terms ethylene oxide, propylene oxide, and butylene oxide may be shown here by their typical designations of EO, PO, and BO, respectively.

[0020] All percentages and ratios are calculated by weight unless otherwise stated. All percentages and proportions are calculated on the basis of total composition unless otherwise stated.

[0021] Polymeric thiophene matting agents suitable for use in the present invention may contain various groups, such as oxyalkylated, adiated, alkylated, carbonylated, olefined and the like, prepared by introducing such groups individually, alternatively and / or in combination, including for example, derivatives prepared by varying the order of addition of such groups, increasing the number and order of addition of such groups, and the like.

[0022] In one aspect, the invention is an aqueous laundry care composition comprising a laundry care ingredient and from 0.0001% by weight to 1.0% by weight of a polymeric thiophene mattifying agent having the structure of Formula I: N-Ri / Ri Formula I wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy, and polyethylenexy / polypropylenexy copolymers, and wherein each A is independently present in the range of 1 to 20 repeating units of polyethylenexy, polypropylenexy, or polyethylenexy / polypropylenexy copolymers; wherein each Ri is independently selected from H, C1-4 alkyl, alkoxy alkyl, halogens, aryl, substituted alkyl, or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, CH2CH2CI, -CH=CH2 -CH2CH(OH)2 and its salts; where each R2 is independently selected from Ci-iq alkyl, aryl, substituted aryl and substituted alkyl.

[0023] In another aspect, the invention is an aqueous laundry care composition comprising a laundry care ingredient and from 0.0001% by weight to 1.0% by weight of a polymeric thiophene mattifying agent having the structure of Formula I: N~Rl Ri Formula I wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy and polyethylenexy / polypropyleneoxy copolymers, and wherein each A is independently present in the range of 1 to 5 repeating units of polyethylenexy, polypropylenexy or polyethylenexy / polypropyleneoxy copolymers; wherein each Ri is independently selected from H and Ci-4 alkyl.

[0024] In another aspect, the invention is an aqueous laundry care composition comprising a laundry care ingredient and from 0.0001% by weight to 1.0% by weight of a polymeric thiophene mattifying agent having the structure of Formula II: Formula II wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy and polyethylenexy / polypropyleneoxy copolymers, and wherein each A is independently present in the range of 1 to 5 repeating units of polyethylenexy, polypropylenexy or polyethylenexy / polypropyleneoxy copolymers.

[0025] The polymeric thiophene matting agent may be present in the laundry care composition in an amount in the range of 1 ppm to 10000 ppm, or in an amount in the range of 1 ppm to 500 ppm.

[0026] The laundry care composition may contain water in an amount in the range of 3% to 97% based on the total weight of the laundry care composition, or in the range of 10% to 90% based on the total weight of the laundry care composition, or even in the range of 25% to 75% based on the total weight of the laundry care composition.

[0027] The aqueous composition for laundry care of the present invention may be present in liquid form, in unit dose form, or in multi-compartment unit dose form.

[0028] Impurities may also be present in the tinting agent. A person skilled in the art would recognize that impurities related to regioisomers, incomplete reaction, or double coupling of the diazonium salt to the coupler may result when preparing an azo dye. Impurities may include, for example, carboxylic acids, bisamides, regioisomeric amides, or mixtures of carboxylic acids, esters, nitriles, and amides present in the thiophene moiety. Therefore, the aqueous laundry care composition may also contain at least one of the following structures, or salts thereof: (pH2CH2O)3H (CH2CH2O)2H Nx(CH2CH2O)2H NC (pH2CH2O)3H (pH2CH2O)3H (pH2CH2O)3H

[0029] Additional impurities may occur in the manufacturing process of polymeric thiophene matting agents, in which Al may be present as:

[0030] A person skilled in the art will understand that there are a number of other small impurities that may be present in the molecule and that are also covered by the invention.

[0031] In one aspect of the invention, the aqueous laundry care composition contains a laundry care ingredient selected from the group consisting of cationic polymers, surfactants, enhancers, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleaching activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, polymeric dispersing agents, clay soil removal / anti-redeposition agents, brighteners, foam suppressants, dyes, pigments, coloring agents, perfumes, perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, and processing aids.

[0032] A textile article can be treated with the garment care composition of the present invention. As a result, the treated textile article can contain the polymeric thiophene matting agent as described herein. In one aspect of the invention, the textile article is composed of cellulose-containing fiber. The textile article can be in the form of a fabric. Therefore, the invention includes a cellulose-containing fabric containing the polymeric thiophene matting agent as described herein.

[0033] A method for treating a textile article to improve the article's visual appearance includes the steps of: (1) providing a textile article, and (2) exposing the textile article to the laundry care composition containing the polymeric thiophene mattifying agent as described herein. A method for treating a textile article may further comprise the steps of: (i) treating a textile article with the aqueous or non-aqueous laundry care composition as described herein, and (ii) rinsing and drying the treated textile article. The method of treating a textile article with the laundry care composition of the present invention, whether aqueous or non-aqueous, may be free of bleach.

[0034] A method for preparing a polymeric thiophene matting agent containing amide of the present invention may include the formation of the amide by hydrolysis of a nitrile group under basic conditions, such as conditions in which the pH >9. The basic conditions may be formed in the presence of at least one of carbonates, bicarbonates, amines, hydroxides, alkoxides and mixtures thereof.

[0035] The aqueous garment care composition containing the polymeric thiophene tinting agent can impart a desired shade to a textile article with a relative shade angle >270, or a relative shade angle in the range of 270 to 310, or a relative shade angle in the range of 290 to 310.

[0036] In another aspect of the invention, there is a laundry care composition comprising: (1) a laundry care ingredient; (2) from 0.0001% by weight to 1.0% by weight of a polymeric thiophene mattifying agent having the structure of Formula I: Formula I wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy, and polyethylenexy / polypropylenexy copolymers, and wherein each A is independently present in the range of 1 to 20 repeating units of polyethylenexy, polypropylenexy, or polyethylenexy / polypropylenexy copolymers; wherein each Ri is independently selected from H, C1-4 alkyl, alkoxy alkyl, halogens, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, CH2CH2CI, -CH=CH2, -CH2CH(OH)2 and their salts; wherein each R2 is independently selected from Ci-ig alkyl, aryl, substituted aryl and substituted alkyl; and (3) from 0.0001 wt% to 1.0 wt% of a polymeric thiophene matting agent having the structure of Formula X: Formula where each Ri is independently selected from H, C1-4 alkyl, alkoxy alkyl, halogens, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, CH2CH2C1, -CH=CH2, -CH2CH(OH)2 and their salts; where each R2 is independently selected from C1-4 alkyl, aryl, substituted aryl and substituted alkyl.

[0037] In another aspect of the invention, there is a laundry care composition comprising: (1) a laundry care ingredient; (2) from 0.0001% by weight to 1.0% by weight of a polymeric thiophene mattifying agent having the structure of Formula III: ινΐΛ / a / zuzz / uiuio □ x(CH2CH2O)2H Formula III (pH2CH2O)3H ; and (3) from 0.0001 wt% to 1.0 wt% of a polymeric thiophene matting agent having the structure of Formula Y: (pH2CH2O)3H (CH2CH2O)2H Formula Y

[0038] Each polymeric thiophene matting agent is independently present in the composition in an amount in the range of 1 ppm to 10,000 ppm, or even in an amount in the range of 1 ppm to 500 ppm. The polymeric thiophene matting agents of Formula I and the polymeric thiophene matting agent of Formula X are present in a ratio of 1:200 to 200:1, in a ratio of 1:100 to 100:1, or even in a ratio of 1:3 to 3:1. In another aspect of the invention, the polymeric thiophene matting agents of Formula III and the polymeric thiophene matting agent of Formula Y are present in a ratio of 1:200 to 200:1, in a ratio of 1:100 to 100:1, or even in a ratio of 1:3 to 3:1.

[0039] The laundry care composition may be present in powder form, liquid form, unit dose form, or multi-compartment unit dose form.

[0040] Impurities may also be present in the mattifying agent. Impurities may include, for example, carboxylic acids, bisamides, regioisomeric amides, or mixtures of carboxylic acids, esters, nitriles, and amides present in the thiophene moiety. Therefore, the aqueous laundry care composition may also contain at least one of the following structures, or salts thereof: NC Nx(CH2CH2O)2H (pH2CH2O)3H

[0041] The laundry care ingredient may be selected from the group consisting of cationic polymers, surfactants, enhancers, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, polymeric dispersing agents, clay soil removal / anti-redeposition agents, brighteners, foam suppressants, dyes, pigments, coloring agents, perfumes, perfume delivery systems, structural elasticizing agents, fabric softeners, vehicles, hydrotropes, and processing aids.

[0042] The garment care composition can impart a desired hue to a textile article treated with it that has a relative hue angle in the range of 210 to 345, or in the range of 270 to 300.

[0043] A further aspect of the present invention includes a laundry care composition comprising: (i) a laundry care ingredient; and (ii) from 0.0001 wt% to 1.0 wt% of a polymeric thiophene mattifying agent having the structure of Formula I: N~Ri / Ri Formula I wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy, and polyethylenexy / polypropylenexy copolymers, and wherein each A is independently present in the range of 1 to 20 repeating units of polyethylenexy, polypropylenexy, or polyethylenexy / polypropylenexy copolymers; wherein each Ri is independently selected from H, C1-4 alkyl, alkoxyalkyl, halogens, aryl, substituted alkyl or substituted aryl, -COR?, -CH?COH, -COOR?, -COOH, -SO3H, -CH?COOH, CH2CH2CI, -CH=CH2, -CH2CH(OH)2 and their salts; wherein each R2 is independently selected from Ci-ig alkyl, aryl, substituted aryl and substituted alkyl;and where the laundry care composition imparts a whitening effect to a textile article containing cellulose that is measurably greater than to a textile article containing polyester treated with the laundry care composition, where the whitening effect is measured by a whiteness index on each textile article.

[0044] The polymeric thiophene matting agent may be present in an amount in the range of 1 ppm to 10000 ppm, or in an amount in the range of 1 ppm to 500 ppm.

[0045] The textile article containing cellulose may exhibit a whitening effect that is at least twice as strong as a textile substrate containing polyester treated with the garment care composition. The textile article containing cellulose may further exhibit a whitening effect that is at least five times stronger than a textile substrate containing polyester treated with the garment care composition.

[0046] The polymeric thiophene matting agent also provides a whitening bias in a textile article containing cellulose compared to a textile article containing polyester, wherein the whitening bias is measured through the following formula: whitening bias = (change in whiteness of a textile article containing cellulose / change in whiteness of a textile article containing polyester), wherein the whitening effect is measured through the whiteness index of each textile article.

[0047] The textile article containing cellulose may be composed of fiber selected from the group consisting of cotton, linen, rayon, jute, hemp, bamboo, and mixtures thereof. The textile article containing cellulose may be composed primarily by weight of cotton fiber. The textile article containing cellulose may be composed of 100% cotton fiber. The textile article containing polyester may be composed primarily by weight of polyester fiber. The textile article containing polyester may be composed of 100% polyester fiber.

[0048] The presence of Formula I imparts a tint to the cellulose-containing textile article, wherein the tint is determined by measuring the relative tint angle. The cellulose-containing textile article treated with the garment care composition of the present invention may exhibit a relative tint angle in the range of 280 to 345, or in the range of 290 to 320.

[0049] Impurities may also be present in the mattifying agent. Impurities may include, for example, carboxylic acids, bisamides, regioisomeric amides, or mixtures of carboxylic acids, esters, nitriles, and amides present in the thiophene moiety. Therefore, the aqueous laundry care composition may also contain at least one of the following structures, or salts thereof: (pH2CH2O)3H (CH2CH2O)2H NC N, (CH2CH2O)2H (pH2CH2O)3H (pH2CH2O)3H

[0050] The laundry care ingredient may be selected from the group consisting of cationic polymers, surfactants, enhancers, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, polymeric dispersing agents, clay soil removal / anti-redeposition agents, brighteners, foam suppressants, dyes, pigments, coloring agents, perfumes, perfume delivery systems, structural elasticizing agents, fabric softeners, vehicles, hydrotropes, and processing aids.

[0051] The present invention also encompasses a method for increasing the bleaching effect / index in a textile article comprising the steps of (i) treating the textile article with the garment care composition as described herein, and (ii) rinsing and drying the treated textile article. The step of treating the textile article may be free of bleach.

[0052] Also included herein is a process for measurably improving a whitening effect in cellulose-containing textile articles, wherein the improvement is present in an amount greater than that observed in polyester-containing textile articles, wherein the process comprises the following steps: (a) providing a cellulose-containing textile substrate, (b) providing a polyester-containing textile substrate, (c) exposing the textile substrates of steps (a) and (b) to a garment care composition comprising: (i) a garment care ingredient; and (ii) from 0.0001 wt% to 1.0 wt% of a polymeric thiophene mattifying agent having the structure of Formula I: Formula I wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy, and polyethylenexy / polypropylenexy copolymers, and wherein each A is independently present in the range of 1 to 20 repeating units of polyethylenexy, polypropylenexy, or polyethylenexy / polypropylenexy copolymers; wherein each Ri is independently selected from H, Ci-4 alkyl, alkoxyalkyl, halogens, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, CH2CH2C1, -CH=CH2, -CH2CH(OH)2 and their salts; wherein each R2 is independently selected from Ci-ig alkyl, aryl, substituted aryl, and substituted alkyl; and (d) measuring the bleaching effect by evaluating the whiteness index of each textile article.

[0053] In another aspect of the invention there is a textile article, wherein the textile article contains: (a) a majority by weight of cellulose fiber, and (b) a wash care composition comprising: (i) a wash care ingredient; and (ii) from 0.0001% by weight to 1.0% by weight of a polymeric thiophene matting agent having the structure of Formula III: ινΐΛ / a / zuzz / uiu / oj (pH2CH2O)3H (CH2CH2O)2H Formula III

[0054] In one aspect of the invention, the polymeric thiophene matting agent may comprise any suitable alkylenoxy group. Suitable alkylenoxy groups include those of Formula (C) below: (C) to

[0055] In the Formula (C) structure and the other alkylenoxy structures that follow, the carbon atom bonded to R101 is also bonded to the nitrogen atom of the amino group. In the Formula (C) structure, each group R101 and R102 is independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyalkyl, and aryloxyalkyl. R105 is a terminal group for the oxyalkylene and can be selected from the group consisting of hydrogen, alkyl groups (e.g., Ci-C4 alkyl groups), and aryl groups, with hydrogen being preferred. Preferably, each group R101 and R102 is selected independently of the group consisting of hydrogen and alkyl (e.g., Ci-C4 alkyl). The variable a is an integer equal to or greater than 1 (e.g., from 1 to approximately 100). For each monomer unit in the oxyalkylene group, groups R101 and R102 are selected independently of the group mentioned.Thus, when the variable a is greater than 1, the alkylenoxy group may consist of two or more monomeric units covalently bonded to form the alkylenoxy group, or even three or more monomeric units. When the alkylenoxy group comprises two or more monomer units (or even three or more monomer units), these monomer units may be arranged in a block configuration or a random configuration, but a block configuration is generally preferred. In a preferred embodiment, the alkylenoxy group comprises monomeric units selected independently from the group consisting of ethyleneoxy, propylenoxy, and butyleneoxy. A suitable example of such an alkylenoxy group is Formula (CI) below. (CI)

[0056] In the Formula (CI) structure, the variables x, y, and z are selected independently from the group consisting of zero and positive integers (e.g., positive integers from 1 to approximately 100). Preferably, the sum of x, y, and z is 2 or more or 3 or more (e.g., from 2 to 300, from 3 to 300, from 2 to 200, from 3 to 200, from 2 to 100, from 3 to 100, 2 to approximately 50, 3 to approximately 50, 2 to approximately 30, 3 to approximately 30, 2 to approximately 25, 3 to approximately 25, 2 to approximately 20, 3 to approximately 20, 2 to approximately 15, 3 to approximately 15, 2 to approximately 10 or 3 to approximately 10). RIOS is a terminal group for the oxyalkylene and can be selected from the group consisting of hydrogen, alkyl groups (e.g., C1-C4 alkyl groups), and aryl groups, hydrogen being preferred. In certain possibly preferred embodiments, the alkylenoxy group comprises ethyleneoxy and propylenoxy monomeric units arranged in a block configuration. Suitable examples of such alkylenoxy groups include those in Formulas (CU) and (CIII) below (CII). (CU)

[0057] In the structures of Formulas (CII) and (CIII), the variables t, u, v, q, rys are selected independently from the group consisting of zero and positive integers (e.g., positive integers from 1 to about 100). Preferably, the sum of t, u, v, q, rys is 2 or more or 3 or more (e.g., from 2 to about 300, from 3 to about 300, from 2 to 36 approximately 200, from 3 to approximately 200, 2 to approximately 100, 3 to approximately 100, 2 to approximately 50, 3 to approximately 50, 2 to approximately 30, 3 to approximately 30, 2 to approximately 25, 3 to approximately 25, 2 to approximately 20, 3 to approximately 20, 2 to approximately 15, from 3 to approximately 15, from 2 to approximately 10 or from 3 to approximately 10). R105 is a terminal group for the oxyalkylene and can be selected of the group consisting of hydrogen, alkyl groups (e.g., C1-C4 alkyl groups) and aryl groups, with hydrogen being preferred.

[0058] Alkoxylation is carried out by procedures well known to those skilled in the art (see, for example, U.S. Patent Nos. 4,137,243; 5,082,938; 5,135,972; 5,591,833; 6,593,483; 7,587,857; 9,056,963; and 9,068,081). Suitable Ci-Cs alkoxy or polyol alkoxy derivatives having repeating units include alkylene oxides. Alkylene oxides may be selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. The alkylene oxide groups may be in the form of polymer chains known as polyalkyleneoxy chains. The term polyalkylenoxy, as used herein, generally refers to molecular structures containing the following repeating units: -CH2CH2O-, CH2CH2CH2O-, -CH2CH2CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(CH2CH3)OCH2CH2CH(CH3)O-, and any combination thereof.Typical of such groups are polymeric epoxides, such as polyalkylene oxides and their copolymers. Typical polyalkylene oxides and their copolymers include those made from alkylene oxide monomers containing two to twenty carbon atoms, or more preferably, two to six carbon atoms. Examples include polyethylene oxides; polypropylene oxides; polybutylene oxides; oxethanes; tetrahydrafurans; copolymers of polyethylene oxides, polypropylene oxides, and polybutylene oxides; and other copolymers, including block copolymers, in which the majority of the polymeric substituent is polyethylene oxide, polypropylene oxide, and / or polybutylene oxide. Furthermore, such a polyalkylene oxy group can have an average molecular weight in the range of approximately 132 to approximately 10,000, preferably from approximately 176 to approximately 5,000.

[0059] Typically, alkoxy molecules form caps for the ends of the chains comprising the polymeric thiophene matting agent. Therefore, the resulting alkoxylated polymeric thiophene matting agent may have an average degree of alkoxylation of 0.5 to 50, odela50, odela30, or 1 to 20, odela10, or 1 to 1, or 2 to 50, or 2 to 30, or 2 to 20, ode2al0, ode3 to 50, ode3 to 30, or 3 to 20, ode3al0, ode4 to 50, or 4 to 30, ode4 to 20, ode4al0.

[0060] Textile substrates treated with the garment care composition(s) comprising the polymeric thiophene coloring agent(s) of the present invention may be composed of synthetic fibers, natural fibers, or combinations of synthetic and natural fibers. Synthetic fibers include, for example, polyester, acrylic, polyamide, polyolefin, polyaramid, polyurethane, regenerated cellulose (i.e., rayon), and blends thereof. The term polyamide is intended to describe any long-chain polymer having recurring amide groups (--NH—CO--) as an integral part of the polymer chain. Examples of polyamides include nylon 6, nylon 6,6, nylon 1,1, and nylon 6,10. The term polyester is intended to describe any long-chain polymer having recurring ester groups (--C(0)-0--).Examples of polyesters include aromatic polyesters, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and polytriphenylene terephthalate, and aliphatic polyesters, such as polylactic acid (PLA). Polyolefins include, for example, polypropylene, polyethylene, and combinations thereof. Polyaramid includes, for example, poly-phenylene terephthalamide (i.e., Kevlar®), poly-phenylene terephthalamide (i.e., Nomex®), and combinations thereof. Natural fibers include, for example, wool, cotton, linen, and blends thereof.

[0061] The textile substrate may consist of fibers or yarns of any size, including microdenier fibers and yarns (fibers or yarns having less than one denier per filament). The fibers or yarns may have deniers ranging from less than approximately 1 denier per filament to approximately 2000 denier per filament or, more preferably, from less than approximately 1 denier per filament to approximately 500 denier per filament, or even more preferably, from less than approximately 1 denier per filament to approximately 300 denier per filament.

[0062] Furthermore, the textile substrate may be composed partially or entirely of multicomponent or bicomponent fibers or yarns, which may be divisible, or which have been partially or totally dissociated, along their length by chemical or mechanical action. The textile substrate may be composed of fibers such as staple fiber, filament fiber, spun fiber, or combinations thereof.

[0063] The textile substrate may be of any variety, including, but not limited to, woven, knitted, nonwoven, or combinations thereof. The textile substrate may optionally be dyed by a variety of dyeing techniques, such as high-temperature jet dyeing with disperse dyes, vat dyeing, thermosol dyeing, pad dyeing, transfer printing, screen printing, or any other technique common in the art for comparable textile products. The yarns or fibers comprising the textile substrate may optionally be dyed by suitable methods prior to fabric formation, such as by bundle dyeing or solution dyeing.

[0064] Textile substrates include, for example, clothing such as outerwear (e.g., waterproof clothing), workwear (e.g., uniforms), fashion clothing (e.g., shirts, trousers, and other garments); drapery; tablecloths (e.g., tablecloths and napkins); residential upholstery; commercial upholstery; automotive upholstery; wall coverings; floor coverings (e.g., carpets, rugs, and mats); human bedding (e.g., mattresses, mattress covers, and the like); pet bedding; outdoor fabric (e.g., outdoor furniture, awnings, boat covers, and barbecue covers); medical dressings (e.g., fabrics for use in wound care); and any other article capable of possessing discoloration and in which it is desirable to control (e.g., prevent, eliminate, and / or improve) such discoloration.

[0065] The polymeric thiophene matting agent of the present invention can be incorporated into a laundry care composition, including, but not limited to, laundry detergents and fabric treatment compositions. As used herein, the term laundry care composition includes, unless otherwise specified, washing agents and / or fabric treatment compositions in granular, powder, liquid, gel, paste, unit-dose bar, and / or flake form. As used herein, the term fabric treatment composition includes, unless otherwise specified, fabric softening compositions, fabric enhancing compositions, fabric refreshing compositions, and combinations thereof. Such compositions may be, but need not be, rinse-added compositions.

[0066] The laundry care compositions of the present invention comprise one or more polymeric thiophene matting agents and a laundry care ingredient. The polymeric thiophene matting agent can be added to articles using a variety of application techniques. For application to textile articles, the polymeric thiophene matting agent is preferably included as an additive in laundry detergent. Therefore, the application to the textile article actually occurs when a consumer adds laundry detergent to a washing machine. Similarly, rinse-added fabric softener compositions (RAES) are typically added in the rinse cycle, which is after the detergent solution has been used and replaced with the rinse solution in typical washing processes.

[0067] The polymeric thiophene matting agent may be present in the laundry care composition (such as the laundry detergent composition) in an amount of about 0.0001% to about 10% by weight of the composition, more preferably about 0.0001% to about 5% by weight of the composition, and even more preferably about 0.0001% to about 1% by weight of the composition.

[0068] The laundry detergent composition comprises a surfactant in a sufficient amount to provide the desired cleaning properties. In one embodiment, the laundry detergent composition comprises, by weight, from approximately 5% to approximately 90% of the surfactant, and more specifically from approximately 5% to approximately 70% of the surfactant, and even more specifically from approximately 5% to approximately 40%. The surfactant may comprise anionic, nonionic, cationic, zwitterionic, and / or amphoteric surfactants. In a more specific embodiment, the detergent composition comprises an anionic surfactant, a nonionic surfactant, or mixtures thereof.

[0069] Suitable anionic surfactants useful herein may comprise any of the conventional types of anionic surfactants typically used in liquid detergent products. These include alkylbenzene sulfonic acids and their salts, as well as alkoxylated or non-alkoxylated alkyl sulfate materials.

[0070] Exemplary anionic surfactants are alkali metal salts of C11-C16 alkylbenzene sulfonic acids, preferably Cn-n alkylbenzene sulfonic acids. Preferably, the alkyl group is linear, and such linear alkylbenzene sulfonates are known as LAS. Alkylbenzene sulfonates, and particularly LAS, are well known in the art. Such surfactants and their preparation are described, for example, in U.S. Patent Nos. 2,220,099 and 2,477,383. Linear-chain sodium and potassium alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is approximately 11 to 14 are especially preferred. The C11-C14 sodium LAS, e.g. C12, is a specific example of such surfactants.

[0071] Another exemplary type of anionic surfactant comprises ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those that correspond to the formula: R'--O--(C2H4O)n__SO3M where R' is a Cg-CgO alkyl group, n is from about 1 to 20, and M is a salt-forming cation. In one specific embodiment, R' is Ciq-Cs alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In more specific embodiments, R' is a Ci2-Ci6, n is from about 1 to 6 or even from about 1 to 3 or from about 1 to 1.5, and M is sodium.

[0072] Alkyl ether sulfates will generally be used in the form of mixtures comprising varying chain lengths R' and varying degrees of ethoxylation. Frequently, such mixtures will also inevitably contain some non-ethoxylated alkyl sulfate materials, i.e., surfactants of the above ethoxylated alkyl sulfate formula in which n = 0. Non-ethoxylated alkyl sulfates may also be added separately to the compositions of this invention and used as or in any anionic surfactant component that may be present. Specific examples of non-alkoxylated, e.g., non-ethoxylated alkyl ether sulfate surfactants are those produced by the sulfation of higher C8-C20 fatty alcohols.Conventional primary alkyl sulfate surfactants have the general formula ROSO3-M4·, where R is typically a linear Cg-C2o hydrocarbyl group, which may be linear or branched, and M is a water-solubilizing cation. In specific embodiments, R is a C10-C15 alkyl group and M is an alkali metal; more specifically, R is C12-C14 and M is sodium.

[0073] Specific, non-limiting examples of useful anionic surfactants herein include: a) Cn-Cig alkylbenzene sulfonates (LAS); b) C10-C20 branched and random primary alkyl sulfates (AS); c) Cig-Cig secondary (2,3) alkyl sulfates; d) Cig-Cig alkyl alkoxy sulfates (AExS) wherein preferably x is 130; e) Cig-Cig alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) medium-chain branched alkyl sulfates as described in U.S. Patent No. 6,020,303 and U.S. Patent No. 6,060,443; g) medium-chain branched alkoxyalkyl sulfates as described in U.S. Patent No. 6,008,181 and U.S. Patent No. 6,020,303; h) modified alkylbenzene sulfonate (MLAS) as described in WO 99 / 05243, WO 99 / 05242, WO 99 / 05244, WO 99 / 05082, WO 99 / 05084, WO 99 / 05241, WO 99 / 07656, WO 00 / 23549 and WO 00 / 23548; i) methyl ester sulfonate (MES); and j) alpha-olefin sulfonate (AOS).

[0074] Suitable nonionic surfactants useful in the present invention may comprise any of the conventional types of nonionic surfactants typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Preferred for use in the liquid detergent products of the present invention are those nonionic surfactants that are normally liquid.

[0075] Suitable nonionic surfactants for use herein include alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials that correspond to the general formula: R1(CmH2mO)nOH where R1 is a Cs-Cie alkyl group, m is from 2 to 4, and n varies from approximately 2 to 12. Preferably, R1 is an alkyl group, which may be primary or secondary, comprising approximately 9 to 15 carbon atoms, more preferably from approximately 10 to 14 carbon atoms. In one embodiment, alkoxylated fatty alcohols will also be ethoxylated materials containing 2 to 12 ethylene oxide moieties per molecule, more preferably from 3 to 10 or even from 7 to 9 ethylene oxide moieties per molecule.

[0076] The alkoxylated fatty alcohol materials useful in the liquid detergent compositions of the present invention will frequently have a hydrophilic-lipophilic balance (HLB) ranging from approximately 3 to 17. More preferably, the HLB of this material will range from approximately 6 to 15, most preferably from approximately 8 to 15. Nonionic alkoxylated fatty alcohol surfactants have been marketed under the trade names Neodol and Dobanol by Shell Chemical Company.

[0077] Another suitable type of nonionic surfactant useful here comprises amine oxide surfactants. Amine oxides are materials often referred to in the technical term as semipolar nonionic surfactants. Amine oxides have the formula: R(EO)x(PO)y(BO)ZN(O)(CH2R')2·qH2O. In this formula, R is a relatively long-chain hydrocarbyl moiety that may be saturated or unsaturated, linear or branched, and may contain from 8 to 20, preferably from 10 to 16, carbon atoms, and is most preferably a primary alkyl group Ci2-Ci6. R' is a short-chain moiety, preferably selected from hydrogen, methyl, and -CH2OH. When x+y+z is not equal to 0, EO is ethyleneoxy, PO is propylenoxy, and BO is butyleneoxy. Amine oxide surfactants are illustrated by alkyldimethylamine oxide Ci2-24.

[0078] Non-limiting examples of nonionic surfactants include: a) C12-C18 alkyl ethoxylates, such as Shell's NEODOL® nonionic surfactants; b) Cg-Ci2 alkylphenol alkoxylates in which the alkoxylate units are a mixture of ethyleneoxy and propylenoxy units; c) C12-C18 alcohol and Cg-Ci2 alkylphenol condensates with ethylene oxide / propylene oxide block polymers such as BASF's Pluronic®; d) Ci4-C22 medium-chain branched alcohols, BA, as described in the patent of U.S. Patent No. 6,150,322; (e) medium-chain C14-C22 branched alkyl alkoxylates, BAEx, wherein x is 1-30, as described in U.S. Patent No. 6,153,577, U.S. Patent No. 6,020,303 and U.S. Patent No. 6,093,856; (f) Alkylpolysaccharides as described in U.S. Patent No. 4,565,647, issued January 26, 1986; specifically alkylpolyglycosides as discussed in U.S. Patent No. 4,483,780 and U.S. Patent No. 4,483,779; (g) Polyhydroxylated fatty acid amides as described in U.S. Patent No. 5,332,528, WO 92 / 06162, WO 93 / 19146, WO 93 / 19038 and WO 94 / 09099; and (h) ether-topped poly(oxyalkylated) alcohol surfactants as described in U.S. Patent No. 6,482,994 and WO 01 / 42408.

[0079] In the laundry detergent compositions of the present invention, the detergent surfactant component may comprise combinations of anionic and nonionic surfactant materials. When this is the case, the weight ratio of anionic to nonionic surfactant will typically vary from 10:90 to 90:10, more typically from 30:70 to 70:30.

[0080] Cationic surfactants are well known in the art, and non-limiting examples of these include quaternary ammonium surfactants, which can have up to 26 carbon atoms. Additional examples include (a) alkoxylate quaternary ammonium surfactants (AQA) as described in U.S. Patent No. 6,136,769; (b) dimethyl hydroxyethyl quaternary ammonium as described in U.S. Patent No. 6,004,922; (c) polyamine cationic surfactants as described in WO 98 / 35002, WO 98 / 35003, WO 98 / 35004, WO 98 / 35005, and WO 98 / 35006; d) cationic ester surfactants as discussed in U.S. Patent Nos. 4,228,042, 4,239,660, 4,260,529 and U.S. Patent No. 6,022,844; and e) amino surfactants as described in U.S. Patent No. 6,221,825 and WO 00 / 47708, specifically amido propyldimethylamine (APA).

[0081] Non-limiting examples of zwitterionic surfactants include secondary and tertiary amine derivatives, secondary and tertiary heterocyclic amine derivatives, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975, column 19, line 38 to column 22, line 48, for examples of zwitterionic surfactants; betaine, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, Cg to Cig amine oxides (preferably C12 to Gis) and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-l-propane sulfonate where the alkyl group can be Cg to Cig, preferably C12 to Cu.

[0082] Non-limiting examples of ampholytic surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of secondary and tertiary heterocyclic amines in which the aliphatic radical may be linear or branched. One of the aliphatic substituents comprises at least approximately 8 carbon atoms, typically from approximately 8 to approximately 18 carbon atoms, and at least one comprises a water-solubilizing anionic group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975, in column 19, lines 18-35, for examples of ampholytic surfactants.

[0083] As indicated, the compositions may be in the form of a solid, either in the form of tablets or particles, including, but not limited to, particles, flakes, or the like, or the compositions may be in the form of a liquid. The liquid detergent compositions comprise an aqueous, non-surface-active liquid vehicle. In general, the amount of the aqueous, non-surface-active liquid vehicle employed in the compositions of the present invention shall be effective in solubilizing, suspending, or dispersing the components of the composition. For example, the compositions may comprise, by weight, from about 5% to about 90%, more specifically from about 10% to about 70%, and even more specifically from about 20% to about 70% aqueous, non-surface-active liquid vehicle.

[0084] The most effective type of aqueous, non-surfactant liquid carrier is, of course, water itself. Consequently, the non-surface-active aqueous liquid carrier component will generally consist mainly, if not entirely, of water. However, other types of water-miscible liquids, such as alkanols, diols, other polyols, ethers, amines, and the like, and mixtures thereof, may also be added to liquid detergent compositions as co-solvents or stabilizers in addition to or instead of water. Accordingly, the non-surface-active aqueous liquid carrier component of the liquid detergent composition will generally be present in concentrations ranging from about 5% to about 90% by weight of the composition, more preferably from about 20% to about 70% by weight of the composition.

[0085] Detergent compositions may also contain bleaching agents. Suitable bleaching agents include, for example, sources of hydrogen peroxide, such as those described in detail in Kirk Othmer's Encyclopedia of Chemical Technology incorporated herein, 4th ed. (1992, John Wiley & Sons), vol. 4, pp. 271-300 Bleaching Agents (Survey). These sources of hydrogen peroxide include the various forms of sodium perborate and sodium percarbonate, including several coated and modified forms of these compounds.

[0086] The preferred source of hydrogen peroxide used in this document may be any convenient source, including hydrogen peroxide itself. For example, perborate may be used here, e.g., sodium perborate (any hydrate but preferably the mono- or tetrahydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium peroxyhydrate pyrophosphate, urea peroxyhydrate, or sodium peroxide. Sources of readily available oxygen, such as persulfate bleach (e.g., OXONE, manufactured by DuPont), are also useful. Sodium perborate monohydrate and sodium percarbonate are especially preferred. Mixtures of any convenient hydrogen peroxide source may also be used.

[0087] A suitable percarbonate bleach comprises dry particles having an average particle size in the range of about 500 micrometers to about 1000 micrometers, with no more than 10% by weight of such particles being smaller than about 200 micrometers and no more than about 10% by weight of such particles being larger than about 1250 micrometers. Optionally, the percarbonate may be coated with a silicate, borate, or water-soluble surfactant. Percarbonate is available from several commercial sources, such as EMC, Solvay, and Tokai Denka.

[0088] The compositions of the present invention may also comprise a chlorine-type bleaching agent. Such agents are well known in the art and include, for example, sodium dichloroisocyanurate (NaDCC). However, chlorine-type bleaches are less preferred for compositions comprising enzymes.

[0089] (a) Bleach activators Preferably, the peroxygenated bleaching component in the composition is formulated with an activator (peracid precursor). The activator is present at levels of approximately 0.01%, preferably approximately 0.5%, more preferably from about 1% to about 15%, preferably about 10%, more preferably about 8%, by weight of the composition. A bleach activator as used herein is any compound that, when used in conjunction with a source of hydrogen peroxide, leads to the in situ production of the peracid corresponding to the bleach activator. Several non-limiting examples of activators are described in U.S. Patent Nos. 5,576,282; 4,915,854; and 4,412,934. See also U.S. Patent No. 4,634,551 for other typical bleaches and activators useful herein.

[0090] The preferred activators are selected from the group consisting of tetraacetyl ethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulfonate (Ciq-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (Cg-OBS), perhydrolyzable esters, and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam. The bleach activators particularly preferred in the pH range of approximately 8 to approximately 11 are those selected that have an OBS or VL leaving group.

[0091] Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulfonate (NOBS); 4-[N(nonanoyl)aminohexanoyloxy]benzene sulfonate sodium salt (NACA-OBS), an example of which is described in U.S. Patent No. 5,523,434; dodecanoyloxybenzenesulfonate (LOBS or C12-OBS); 10-undecenoyloxybenzenesulfonate (UDOBS or Cn-OBS with unsaturation at the 10 position); and decanoyloxybenzoic acid (DOBA).

[0092] The preferred bleaching activators are those described in U.S. Patent No. 5,998,350 to Burns et al.; U.S. Patent No. 5,698,504 to Christie et al.; U.S. Patent No. 5,695,679 to Christie et al.; U.S. Patent No. 5,686,401 to Willey et al.; U.S. Patent No. 5,686,014 to Hartshorn et al.; U.S. Patent No. 5,405,412 to Willey et al.; U.S. Patent No. 5,405,413 to Willey et al.; U.S. Patent No. 5,130,045 to Mitchell et al.; and U.S. Patent No. 4,412,934 of Chung et al., and Patent Application Pending Serial No. 08 / 064.564, all of which are incorporated herein by reference.

[0093] The molar ratio of peroxygen source (as AvO) to bleaching activator in the present invention generally varies from at least 1:1, preferably from approximately 20:1, more preferably from approximately 10:1 to approximately 1:1, preferably to approximately 3:1.

[0094] Substituted quaternary bleach activators may also be included. The present washing compositions preferably comprise a substituted quaternary bleach activator (QSBA) or a substituted quaternary peracid (QSP, preferably a substituted quaternary percarboxylic acid or a substituted quaternary peroxyimidic acid); more preferably the former. The preferred QSBA structures are described in more detail in U.S. Patent No. 5,686,015 to Willey et al.; U.S. Patent No. 5,654,421 to Taylor et al.; U.S. Patent No. 5,460,747 to Gosselink et al.; U.S. Patent No. 5,584,888 to Miracle et al.; and U.S. Patent No. 5,578,136 to Taylor et al. all of which are incorporated herein by reference.

[0095] The highly preferred bleach activators useful herein are those substituted with amide as described in U.S. Patent Nos. 5,698,504; 5,695,679; and 5,686,014, each of which is cited herein above. Preferred examples of such bleach activators include: (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and mixtures thereof.

[0096] Other useful activators are described in U.S. patents numbers 5,698,504; 5,695,679; and ινΐΛ / a / zuzz / uiuio □ 5,686,014, each of which is cited herein above, and in U.S. Patent No. 4,966,723 of Hodge et al. These activators include benzoxazine-type activators, such as a CgH4al ring fused at positions 1,2 to a C(O)OC(R1)=N- moiety.

[0097] Nitriles, such as acetonitriles and / or ammonium nitriles and other nitriles containing quaternary nitrogen, are another class of activators that are useful here. Non-limiting examples of such nitrile bleaching activators are described in U.S. Patent Nos. 6,133,216; 3,986,972; 6,063,750; 6,017,464; 5,958,289; 5,877,315; 5,741,437; 5,739,327; 5,004,558; and in EP Nos. 790 244, 775 127, 1 017 773, 1 017 776; and in WO 99 / 14302, WO 99 / 14296, WO96 / 40661, all of which are incorporated herein by reference.

[0098] Depending on the activator and the precise application, good bleaching results can be obtained with bleaching systems operating at a pH of approximately 6 to approximately 13, and preferably from around 9.0 to approximately 10.5. Typically, for example, activators with electron-withdrawing moieties are used for near-neutral or sub-neutral pH ranges. Alkalis and buffering agents can be used to ensure such a pH.

[0099] Acyl lactam activators, as described in U.S. Patents Nos. 5,698,504; 5,695,679 and 5,686,014, each of which is cited herein above, are very useful herein, especially acyl caprolactams (see, for example, WO 94-28102 A) and acyl valerolactams (see U.S. Patent No. 5,503,639 of Willey et al. incorporated herein by reference). (b) Organic peroxides, especially diacyl peroxides—these are extensively illustrated in Kirk Othmer, Encyclopedia of Chemical Technology, vol. 17, John Wiley and Sons, 1982, on pages 27–90 and especially on pages 63–72, all incorporated herein by reference. If a diacyl peroxide is used, it should preferably be one that exerts minimal adverse impact on fabric care, including color care.

[00101] (c) Bleaching catalysts containing metals - The compositions and methods of the present invention may also optionally include bleaching catalysts containing metals, preferably bleaching catalysts containing manganese and cobalt.

[00102] A type of bleaching catalyst containing a metal is a catalytic system comprising a transition metal cation of defined bleaching catalytic activity (such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations), an auxiliary metal cation having little or no bleaching catalytic activity (such as zinc or aluminum cations), and a sequestering agent having defined stability constants for the auxiliary and catalytic metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid), and water-soluble salts thereof. Such catalysts are described in U.S. Patent No. 4,430,243 to Bragg.

[00103] Manganese metal complexes - if desired, the compositions in this document may be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts described in U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Patent Applications Nos. 549,271 A1; 549,272 A1; 544,440 A2; and 544,490 Al. Preferred examples of these catalysts include MnIV2 (uO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2~ (PFg) 2, Mnm2(u-0)i (u-OAc) 2(1,4, 7-trimethyl1,4,7-triazacyclononane) 2 (C1O4) 2, MnIV4 (uO) 6(1,4,7-triazacyclononane) 4 (CIO4) 4, MnTIIMnIV4 (uO) 1 (u-OAc) 2-(1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (CIO4)3, MnIV(1,4,7-trimethyl1,4,7-triazacyclononane) - (OCH3) 3 (PF6) , and mixtures thereof.Other metal-based bleaching catalysts include those described in U.S. Patent Nos. 4,430,243 and 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following: U.S. Patent Nos. 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147;. 5,153,161; and 5,227,084.

[00104] Cobalt Metal Complexes: The cobalt bleaching catalysts useful herein are known and described, for example, in U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; and M.L. Tobe, Base Hydrolysis of Transition-Metal Complexos, Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein is the cobalt pentaamine acetate salts having the formula [Co(NH3)50Ac] Ty, wherein OAc represents an acetate moiety and Ty is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)50Ac]Cl2; as well as [Co(NH3)50Ac](OAc)2; [Co(NH3)5OAc] (PF6)2; [Co(NH3)50Ac] (SO4); [Co- (NH3)5OAc] (BF4)2; and [Co (NHa)5OAc] (Νθ3)2 (herein PAC).

[00105] These cobalt catalysts are readily prepared by known procedures, such as those taught, for example, in U.S. patents numbers 6,302,921; 6,287,580; 6,140,294; 5,597,936; 5,595,967; and 5,703,030; in Tobe's article and the references cited therein; and in U.S. Patent No. 4,810,410; J. Chem. ed. ινΐΛ / a / zuzz / u 1 u / oj (1989), 66 (12), 1043-45; The synthesis and characterization of inorganic compounds, WL Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952).

[00106] Macropolycyclic rigid ligand transition metal complexes: The compositions in this document may also suitably include as a bleaching catalyst a macropolycyclic rigid ligand transition metal complex. The amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (where ppb indicates parts per billion by weight and ppm denotes parts per million by weight).

[00107] Macrocyclic rigid ligand transition metal bleaching catalysts suitable for use in the compositions of the invention may generally include known compounds when they conform to the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present washing or laundry uses, and are illustrated in a non-limiting manner by any of the following: Dichloro-5,12-dimethyl-l,5,8,12tetraazabicyclo[6.6.2]hexadecane Manganese(II) Dichloro-5,12-diethyl-l,5,8,12tetraaz abieldo [6.6.2] hexadecane Manganese (II) Diaquo-5,12-dimethyl-l,5,8,12tetraazabicyclo[6.6.2]hexadecane Manganese(II) Hexafluorophosphate Diaquo-5,12-diethyl-l,5,8,12 tetraazabicyclo[6.6.2]hexadecane Manganese(II) Hexafluorophosphate Aquo-hydroxy-5,12-dimethyl-l,5,8,12tetraazabicyclo[6.6.2]hexadecane Manganese(III) hexafluorophosphate Diaquo-5,12-dimethyl-1,5,8,12tetraazabicyclo[6.6.2]hexadecane Manganese(II) Tetrafluoroborate Dichloro-5,12-dimethyl-1,5,8,12 tetraazabicyclo[6.6.2]hexadecane Manganese(III) hexafluorophosphate Dichloro-5,12-diethyl-1,5,8,12 tetraazabicyclo[6.6.2]hexadecane Manganese(III) ινΐΛ / a / zuzz / uiuio □ Hexafluorophosphate Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza bicyclo[6.6.2]hexadecane Manganese (II) Dichloro-5,12-dibenzyl-1,5,8,12tetraazabicyclo[6.6.2]hexadecaneManganese(II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese (II) Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese (II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese (II) .

[00108] As a practical matter, and without limitation, the compositions and methods herein may be adjusted to provide on the order of at least one part per hundred million of the bleaching catalyst active species in the composition comprising a lipophilic fluid and a bleaching system, and preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleaching catalyst species in the composition comprising a lipophilic fluid and a bleaching system.

[00109] (d) Bleaching Enhancers: The compositions of the present invention may comprise one or more bleaching enhancers. The bleaching enhancers provide increased bleaching efficacy in lower temperature applications. The bleaching enhancers work in conjunction with conventional peroxygenated bleaching agents to provide increased bleaching efficacy. This is typically achieved by the in-situ formation of an active oxygen transfer agent such as a dioxirane, an oxaziridine, or an oxaziridinium. Alternatively, preformed dioxiranes, oxaziridines, and oxaziridinines may be used.

[00110] Suitable bleaching enhancers for use according to the present invention include cationic imines, zwitterionic imines, anionic imines, and / or polyionic imines having a net charge of approximately +3 to approximately -3, and mixtures thereof. These imine bleach enhancer compounds of the present invention include those of the following general structure: R3 [A] where R1-R4 can be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl radicals.

[00111] Preferred bleach enhancer compounds include zwitterionic bleach enhancers, described in U.S. Patent Nos. 5,576,282 and 5,718,614. Other bleach enhancer compounds include cationic bleach enhancers described in U.S. Patent Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO 95 / 13351, WO 95 / 13352 and WO 95 / 13353.

[00112] Peroxygen sources are well known in the art, and the peroxygen source employed in the present invention may comprise any of these well-known sources, including peroxygen compounds as well as compounds that, under consumer use conditions, provide an effective amount of peroxygen in situ. The peroxide source may include a hydrogen peroxide source, the in situ formation of a peracid anion through the reaction of a hydrogen peroxide source and a bleaching activator, preformed peracid compounds, or mixtures of suitable peroxygen sources. Of course, a person skilled in the art will recognize that other peroxygen sources may be employed without departing from the scope of the invention. Bleaching enhancers, when present, are preferably employed in conjunction with a peroxygen source in the bleaching systems of the present invention.

[00113] (e) Preformed Peracids - Preformed peracids are also suitable as bleaching agents. The preformed peracid compound as used herein is any convenient compound that is stable and that, under consumer use conditions, provides an effective amount of peracid or peracid anion. The preformed peracid compound may be selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof. Examples of these compounds are described in U.S. Patent No. 5,576,282 to Miracle et al.

[00114] One class of suitable organic peroxycarboxylic acids has the general formula: EITHER II Y—R—c—o—OH where R is an alkylene or substituted alkylene group containing from 1 to approximately 22 carbon atoms or a phenylene or substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl, -C(O)OH or -C(O)OOH. The organic peroxyacids suitable for use in the present invention may contain one or two peroxy groups and may be aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peroxyacid has the general formula: EITHER II Y-(CH2)nC—O—OH where Y can be, for example, H, CH3, CH2C1, C(O)OH or C(O)OOH; yn is an integer from 0 to 20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula: EITHER II Y-C6H4-C—o—OH where Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C(O)OH or C(O)OOH.

[00115] Typical monoperoxy acids useful here include alkyl and aryl peroxyacids such as: (i) peroxybenzoic acid and peroxybenzoic acid substituted on the ring, e.g. peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium hexahydrate salt) and o-carboxybenzimidoperoxyhexanoic acid (sodium salt); (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, e.g. peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxicaproic acid (NAPCA), N,N-(3-octylsuccinoyl)aminoperoxicaproic acid (SAPA) and N,N-phthaloylaminoperoxicaproic acid (PAP); (iii) amidoperoxy acids, e.g. peroxysuccinic acid monononilamide (NAPSA) or peroxyadipic acid monononilamide (NAPAA).

[00116] Typical diperoxy acids useful here include alkyl diperoxy acids and aryl diperoxy acids, such as: (i) 1,12-diperoxidodecanedioic acid; (ii) 1,9-diperoxiazelaic acid; (iii) diperoxybrasilicic acid; diperoxysebacic acid and diperoxyisophthalic acid; (iv) 2-decyldiperoxybutane-l,4-dioic acid; (v) 4,4'-sulfonylbisperoxybenzoic acid.

[00117] Such bleaching agents are described in U.S. Patent Nos. 4,483,781 to Hartman and 4,634,551 to Burns et al.; European Patent Application No. 0,133,354 to Banks et al.; and U.S. Patent No. 4,412,934 to Chung et al. Sources also include acid 6-nonylamino-6-oxoperoxicaproic acid as described in U.S. Patent No. 4,634,551 to Burns et al. Persulfate compounds such as OXONE, commercially manufactured by E.I. DuPont of Nemours of Wilmington, DE, can also be used as a suitable source of peroxymonosulfuric acid. PAP is described, for example, in U.S. Patent Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757 and 5,132,431.

[00118] (f) Photobleachants - The photobleachants suitable for use in the treatment compositions of the present invention include, but are not limited to, the photobleachants described in U.S. Patents Nos. 4,217,105 and 5,916,481.

[00119] (g) Enzymatic bleaching - Enzymatic systems can be used as bleaching agents. Hydrogen peroxide can also be present by adding an enzymatic system (i.e., an enzyme and a substrate) capable of generating hydrogen peroxide at the beginning or during the washing and / or rinsing process. Such enzymatic systems are described in patent application EP 91202655.6 filed on October 9, 1991.

[00120] The compositions and methods of the present invention may utilize alternative bleaching systems such as ozone, chlorine dioxide, and the like. Ozone bleaching may be carried out by introducing ozone-containing gas with an ozone content of approximately 20 to approximately 300 g / m³ into the solution that will come into contact with the fabrics. The gas-to-liquid ratio in the solution should be maintained between approximately 1:2.5 and approximately 1:6. U.S. Patent No. 5,346,588 describes a process for the use of ozone as an alternative to conventional bleaching systems and is incorporated herein by reference.

[00121] The detergent compositions of the present invention may also include any number of additional optional ingredients. These include components of conventional laundry detergent compositions such as non-dyeing agents, detergent enhancers, enzymes, enzyme stabilizers (such as propylene glycol, boric acid, and / or borax), foam suppressants, soil suspending agents, soil release agents, other fabric care benefits, pH regulators, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, dye transfer inhibitors, opacifying agents, optical brighteners, perfumes, and coloring agents.The various optional ingredients of the detergent composition, if present in the compositions of the present invention, shall be used at the concentrations conventionally employed to achieve their desired contribution to the composition or to the washing operation. Frequently, the total amount of such optional ingredients of the detergent composition may range from approximately 0.01% to approximately 50%, more preferably from approximately 0.1% to approximately 30%, by weight of the composition.

[00122] Liquid detergent compositions are in the form of an aqueous solution or a uniform dispersion or suspension of surfactant, polymeric thiophene matting agent, and certain other optional ingredients, some of which may normally be in solid form, combined with the normally liquid components of the composition, such as nonionic liquid alcohol ethoxylate, aqueous liquid vehicle, and any other normally liquid optional ingredient. Such a solution, dispersion, or suspension shall be acceptably phase-stable and shall typically have a viscosity ranging from approximately 100 to 600 cps, more preferably from approximately 150 to 400 cps. For the purposes of this invention, viscosity is measured with a Brookfield LVDV-II+ viscometer apparatus using a #21 spindle.

[00123] The liquid detergent compositions of the present invention can be prepared by combining the components thereof in any convenient order and mixing, for example, by stirring, the resulting combination of components to form a stable-phase liquid detergent composition. In a preferred process for preparing such compositions, a liquid matrix is ​​formed containing at least a majority proportion, and preferably substantially all, of the liquid components, for example, nonionic surfactant, non-surfactant liquid carriers, and other optional liquid components, with the liquid components being thoroughly mixed by imparting shear agitation to this liquid combination. For example, rapid stirring with a mechanical stirrer may be usefully employed. While maintaining shear agitation, substantially all of the anionic surfactants and ingredients in solid form may be added.The mixture is stirred, and if necessary, the speed can be increased at this point to form a solution or a uniform dispersion of insoluble solid-phase particles within the liquid phase. After some or all of the solid materials have been added to this stirred mixture, particles of any enzymatic material to be included, such as enzyme granules, are incorporated. As a variation of the composition preparation procedure described above, one or more of the solid components can be added to the stirred mixture as a solution or suspension of particles premixed with a smaller proportion of one or more of the liquid components. After the addition of all the composition components, the mixture is stirred for a sufficient period of time to form compositions with the required viscosity and phase stability characteristics.This will often involve agitation for a period of approximately 30 to 60 minutes.

[00124] In an alternative embodiment for forming liquid detergent compositions, the polymeric thiophene matting agent is first combined with one or more liquid components to form a polymeric thiophene matting agent premix. This premix is ​​then added to a composition formulation containing a substantial portion, for example, more than 50% by weight, more specifically more than 70% by weight, and even more specifically more than 90% by weight, of the remaining components of the laundry detergent composition. For example, in the methodology described above, both the polymeric thiophene matting agent premix and the enzyme component are added in a final component addition stage.In an additional embodiment, the polymeric thiophene matting agent is encapsulated before being added to the detergent composition; the encapsulated polymeric thiophene matting agent is suspended in a structured liquid, and the suspension is added to a composition formulation containing a substantial portion of the remaining components of the laundry detergent composition.

[00125] The compositions of this invention, prepared as described above, can be used to form aqueous washing solutions for use in washing textile substrates such as fabrics. Generally, an effective quantity of such compositions is added to water, preferably in a conventional automatic fabric washing machine, to form such aqueous washing solutions. The aqueous washing solution thus formed is then brought into contact, preferably under agitation, with the fabrics to be washed. An effective quantity of the liquid detergent compositions herein added to water to form aqueous washing solutions may comprise amounts sufficient to form approximately 500 to 7,000 ppm of composition in aqueous washing solution. More preferably, approximately 1,000 to 3,000 ppm of the detergent compositions of the present invention shall be provided in an aqueous washing solution.

[00126] Fabric treatment compositions / Fabric softening compositions added to the rinse

[00127] In another specific embodiment, the polymeric thiophene matting agent of the present invention may be included in a fabric treatment composition. The fabric treatment composition may consist of at least one polymeric thiophene matting agent and a rinse-add fabric softener composition (RAES, also known as rinse-add fabric conditioning compositions). Examples of typical rinse-add softener compositions can be found in U.S. Provisional Patent Application No. 60 / 687582 filed October 8, 2004. The rinse-add fabric softener compositions of the present invention may comprise (a) a fabric softening active substance (ESA) and (b) a polymeric thiophene matting agent.The fabric softener composition added in the rinse may comprise from about 1% to about 90% by weight of ESA, more preferably from about 5% to about 50% by weight of ESA. The polymeric thiophene mattifying agent may be present in the fabric softener composition added in the rinse in an amount of about 0.5 ppb to about 50 ppm, more preferably from about 0.5 ppm to about 30 ppm.

[00128] In one embodiment of the invention, the active fabric softener is a quaternary ammonium compound suitable for softening fabrics in a rinse step. In one embodiment, the fabric softener is formed from a reaction product of a fatty acid and an amino alcohol, yielding mixtures of mono-, di-, and, in one embodiment, triester compounds. In another embodiment, the fabric softener comprises one or more quaternary ammonium softening compounds, such as, among others, a quaternary monoalkylammonium compound, a quaternary diamido compound, and a quaternary ammonium diester compound, or a combination thereof.

[00129] In one aspect of the invention, the ESA comprises a quaternary ammonium diester compound composition (hereinafter referred to as DQA). In certain embodiments of the present invention, the DQA compound compositions also encompass a description of diamido ESA and ESA with mixed amido and ester linkages, as well as the aforementioned diester linkages, all referred to herein as DQA.

[00130] A first type of DQA (DQA (1)) suitable as an ESA includes a compound comprising the Formula: {R4-m - N+- [(CH2)n - Y - R1] m} X wherein each substituent R is hydrogen, a Cq-Cg alkyl or hydroxyalkyl group, preferably short-chain C1-C3, for example, methyl (most preferred), ethyl, propyl, hydroxyethyl and the like, poly(C2-3-alkoxy), preferably polyethoxy group, benzyl or mixtures thereof; each m is 2 or 3; each n is from 1 to approximately 4, preferably 2; each Y is -O-(O)C-, -C(O)-O-, -NR-C(O)-, or -C(O)-NR- and it is acceptable for each Y to be the same or different; the sum of carbons in each R1, plus one when Y is -O-(O)C- or NR-C(O)-, is Ch2-C22, preferably Ci4-C20, each R1 being a hydrocarbyl, or substituted hydrocarbyl group; it is acceptable for R1 to be unsaturated or saturated and branched or linear and preferably linear; it is acceptable for each R1 to be the same or different and preferably these are the same; and X” can be any anion compatible with the softener, preferably chloride, bromide, methyl sulfate, ethyl sulfate, sulfate,Phosphate and nitrate, more preferably chloride or methyl sulfate. Preferred DQA compounds are normally prepared by reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Some materials that commonly result from such reactions include N,N-di(acyloxyethyl)-N,N-dimethylammonium chloride or N,N-di(acyloxyethyl)-N,N-methylhydroxyethylammonium methyl sulfate, in which the acyl group is derived from animal fats, unsaturated and polyunsaturated fatty acids, for example, tallow, hardened tallow, oleic acid, and / or partially hydrogenated fatty acids, derived from vegetable oils and / or partially hydrogenated vegetable oils, such as canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, resin oil, rice bran oil, palm oil, etc.

[00131] Non-limiting examples of suitable fatty acids are listed in U.S. Patent No. 5,759,990 in column 4, lines 45-66. In one embodiment, ESA comprises active ingredients other than DQA (1) or DQA. In another embodiment, ESA comprises only DQA (1) or DQA and is free or essentially free of any other quaternary ammonium compound or other active ingredients. In yet another embodiment, ESA comprises the precursor amine used to produce DQA.

[00132] In another aspect of the invention, the ESA comprises a compound, identified as DTTMAC, comprising the formula: [R4-m- N(+)- R^] Where each m is 2 or 3, each R1 is a C6-C22 substituted hydrocarbyl or hydrocarbyl substituent, preferably C14-C20, but no more than one being less than approximately C12 and the other at least approximately C16, preferably C10-C20 alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, also sometimes called alkylene), most preferably Ci2-C18z alkyl or alkenyl and branched or unbranched. In one embodiment, the ESA iodine (IV) number is approximately 1 to 70; each R is H or a Ci-Cg alkyl or hydroxyalkyl group, preferably short-chain C1-C3, e.g. methyl (most preferred), ethyl, propyl, hydroxyethyl and the like, benzyl or (R2O)2-4H where each R2 is a Ci-g alkylene group; and A- is a softener-compatible anion, preferably chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, phosphate or nitrate; most preferably methyl chloride or sulfate.

[00133] Examples of these FSAs include dialkyldimethylammonium salts and dialkylenedimethylammonium salts such as disebodimethylammonium and disebodimethylammonium methyl sulfate. Examples of commercially available dialkylenedimethylammonium salts that can be used in the present invention are dihydrogenated tallow dimethylammonium chloride and disebodimethylammonium chloride available from Degussa under the trade names Adogen® 442 and Adogen® 470, respectively. In one embodiment, the FSA comprises active ingredients other than DTTMAC. In another embodiment, the FSA comprises only DTTMAC compounds and is free or essentially free of any other quaternary ammonium compounds or other active ingredients.

[00134] In one embodiment, the FSA comprises an FSA described in U.S. Patent Pub. No. 2004 / 0204337 A1, published October 14, 2004, to Corona et al., paragraphs 30-79. In another embodiment, the FSA is one described in U.S. Patent Pub. No. 2004 / 0229769 A1, published November 18, 2005, to Smith et al., paragraphs 26-31; or U.S. Patent No. 6,494,920, column 1, line 51 et seq., detailing a quaternized fatty acid esterquat or triethanolamine ester salt.

[00135] In one embodiment, the ESA is chosen from at least one of the following: diseboiloxyethyldimethylammonium chloride, dihydrogenated tallow dimethylammonium chloride, disebo dimethylammonium chloride, diseboiloxyethyl dimethylammonium sulfate, dihydrogenated seboiloxyethyl dimethylammonium chloride, dihydrogenated dimethylammonium chloride, seboiloxyethyldimethylammonium chloride, or combinations thereof.

[00136] In one form, the ESA may also include compositions of compounds containing amide. Examples of compounds comprising diamide may include, but are not limited to, methyl-bis(seboamidoethyl)-2-hydroxyethylammonium methyl sulfate (available from Degussa under the trade names Varisoft 110 and Varisoft 222). An example of a compound containing an amide ester is N-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl]-N-methylamine.

[00137] Another specific embodiment of the invention provides an added fabric softening composition in the rinse that further comprises a cationic starch. Cationic starches are described in US document 2004 / 0204337 Al. In one embodiment, the fabric softener composition added in the rinse comprises from about 0.1% to about 7% cationic starch by weight of the fabric softener composition. In one embodiment, the cationic starch is HCP401 from National Starch.

[00138] Suitable ingredients for clothing care

[00139] While not essential to the purposes of the present invention, the non-limiting list of laundry care ingredients illustrated below are suitable for use in laundry care compositions and may desirably be incorporated in certain embodiments of the invention, for example, to aid or improve performance, for the treatment of the substrate to be cleaned, or to modify the aesthetics of the composition, as is the case with perfumes, colorants, dyes, or the like. It is understood that such ingredients are in addition to the components listed above for any particular embodiment. The total amount of such adjuvants may range from approximately 0.1% to approximately 50%, or even from approximately 1% to approximately 30%, by weight of the laundry care composition.

[00140] The precise nature of these additional components and their levels of incorporation will depend on the physical form of the composition and the nature of the operation for which it is to be used. Suitable laundry care ingredients include, but are not limited to, polymers, for example, cationic polymers, surfactants, enhancers, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal / anti-redeposition agents, brighteners, foam suppressants, colorants, additional perfumes and perfume delivery systems, structural elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, and / or coloring agents.In addition to the description below, suitable examples of such other additions and levels of use are found in U.S. Patents Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1, which are incorporated by reference.

[00141] As indicated, laundry care ingredients are not essential to the applicants' laundry care compositions. Therefore, certain embodiments of the applicants' compositions do not contain one or more of the following additives: bleaching activators, surfactants, enhancers, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removers / anti-redeposition agents, brighteners, foam suppressants, dyes, additional perfumes and perfume delivery systems, structural elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, and / or coloring agents. However, where one or more auxiliaries are present, such one or more auxiliaries may be present as detailed below:

[00142] Surfactants: The compositions according to the present invention may comprise a surfactant or a surfactant system wherein the surfactant may be selected from nonionic and / or anionic and / or cationic and / or ampholytic and / or zwitterionic and / or semipolar nonionic surfactants. The surfactant is typically present at a level of approximately 0.1%, approximately 1%, or even approximately 5% by weight of the cleaning compositions to approximately 99.9%, approximately 80%, approximately 35%, or even approximately 30% by weight of the cleaning compositions.

[00143] Aids - The compositions of the present invention may comprise one or more detergent aids or aid systems. When present, the compositions will normally comprise at least about 1% of the improver, or from about 5% or 10% and about 80%, 50%, or even 30% by weight of said improver.Adjuvants include, but are not limited to, alkali metal, ammonium and alkanolammonium polyphosphate salts, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate polycarboxylate compounds, hydroxypolycarboxylate ethers, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as melliphic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof.

[00144] Chelating Agents: The compositions in this document may also optionally contain one or more chelating agents for copper, iron, and / or manganese. If used, the chelating agents will generally comprise from about 0.1% to about 15% by weight of the compositions in this document, or even from about 3.0% to about 15% by weight of the compositions in this document.

[00145] Dye Transfer Inhibitors: The compositions of the present invention may also include one or more dye transfer inhibitors. Suitable polymeric dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, N-vinylpyrrolidone / N-vinylimidazole copolymers, polyvinyloxazolidones, and polyvinylimidazoles, or mixtures thereof. When present in the compositions herein, the dye transfer inhibitors are present at levels ranging from approximately 0.0001%, approximately 0.01%, or approximately 0.05% by weight of the cleaning compositions to approximately 10%, approximately 2%, or even approximately 1% by weight of the cleaning compositions.

[00146] Dispersants - The compositions of the present invention may also contain dispersants. Suitable water-soluble organic materials are homopolymeric or copolymeric acids or their salts, wherein the polycarboxylic acid may comprise at least two carboxyl radicals separated from each other by no more than two carbon atoms.

[00147] Enzymes - Compositions may comprise one or more detergent enzymes that provide cleaning performance and / or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is a cocktail of conventionally applicable enzymes such as protease, lipase, cutinase, and / or cellulase along with amylase.

[00148] Enzyme stabilizers - Enzymes for use in compositions, for example, detergents, can be stabilized by various techniques. The enzymes employed here can be stabilized by the presence of water-soluble calcium and / or magnesium ion sources in the finished compositions, which provide such ions to the enzymes.

[00149] Catalytic Metal Complexes—Applicants' compositions may include catalytic metal complexes. One type of metal-containing bleaching catalyst is a catalyst system comprising a transition metal cation of defined bleaching catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations; an auxiliary metal cation having little or no bleaching catalytic activity, such as zinc or aluminum cations; and a sequestering agent having defined stability constants for the auxiliary and catalytic metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid), and water-soluble salts thereof. Such catalysts are described in U.S. Patent No. 4,430,243.

[00150] If desired, the compositions herein may be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts described in U.S. Patent No. 5,576,282.

[00151] The cobalt bleaching catalysts useful herein are known and described, for example, in U.S. Patents 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known processes, such as those taught, for example, in U.S. Patents 5,597,936 and 5,595,967.

[00152] The compositions herein may also suitably include a transition metal complex of a rigid macropolycyclic ligand, abbreviated as MRL. As a practical matter, and without limitation, the compositions and cleaning processes herein may be adjusted to provide on the order of at least one part per hundred million of the MRL species of the beneficial agent in the aqueous washing medium, and may provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the washing solution.

[00153] The preferred transition metals in the present transition metal bleaching catalyst include manganese, iron, and chromium. The preferred MRLs herein are a special type of ultra-rigid ligand having a cross-bridge, such as 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa-decane. Suitable transition metal MRLs are readily prepared by known procedures, such as those taught, for example, in WO 00 / 32601 and U.S. Patent No. 6,225,464.

[00154] Exemplary formulations of laundry care compositions: Liquid detergent formulations: Table A provides examples of liquid detergent formulations that include at least one polymeric thiophene matting agent of the present invention. Table A - Liquid detergent formulations comprising a polymeric thiophene matting agent Ingredient 1a 1b 1c 1d 1e 1f 4% by weight % by weight % by weight % by weight % by weight Sodium alkyl ether sulfate 14.4% 14.4% 9.2% 5.4% Linear alkylbenzene sulfonic acid 4.4% 4.4% 12.2% 5.7% 1.3% 22.0% Alkyl ethoxylate 2.2% 2.2% 8.8% 8.1% 3.4% 18.0% Amine oxide 0.7% 0.7% 1.5% Citric acid 2.0% 2.0% 3.4% 1.9% 1.0% 1.6% Fatty acid 3.0% 3.0% 8.3% 16.0% Protease 1.0% 1.0% 0.7% 1.0% 2.5% Amylase 0.2% 0.2% 0.2% 0.3% Upase 0.2% Borax 1.5% 1.5% 2.4% 2.9% Calcium sodium formate 0.2% 0.2% Formic acid 1.1% Amine ethoxylate polymers Sodium polyacrylate Sodium polyacrylate copolymer 1.8% 1.8% 2.1% 0.6% 0.2% 3.2% DTPA1 0.1% 0.1% 0.9% DTPMP2 0.3% EDTA3 0.1% Bleaching agent 0.15% 0.15% 0.2% 0.12% 0.12% 0.2% fluorescent ethanol propanediol sorbitol 2.5% 6.6% 2.5% 6.6% 1.4% 4.9% 1.5% 4.0% 4.0% 15.7% ethanolamine 1.5% 1.5% 0.8% 0.1% 11.0% sodium hydroxide eumene sodium sulfonate silicone foam suppressor 3.0% 3.0% 4.9% 2.0% 0.01% 1.9% 1.0% perfume thiophene tinting agent 0.3% 0.3% 0.7% 0.3% 0.4% 0.6% polymeric 0.013% 0.001% 0.005% 0.003% 0.0005% 0.001% Rest water rest rest rest rest rest 100.0% 100.0% 100.0% 100.0% 100.0% 100.0% 1Diethylenetriaminepentaacetic acid, sodium salt2Diethylenetriaminepentaquismethylenephosphonic acid, sodium salt3Ethylenediaminetetraacetic acid, sodium salt4A compact formula, packaged as a unit dose in a polyvinyl alcohol film Granulated detergent formulations: Table B provides examples of granular detergent formulations that include at least one polymeric thiophene tinting agent of the present invention. Table B - Granular detergent formulations comprising polymeric thiophene matting agent Ingredient 2a 2b 2c 2d 2e % by weight % by weight % by weight % by weight % by weight Na linear alkylbenzene sulfonate 3.4% 3.3% 11.0% 3.4% 3.3% Na alkyl sulfate 4.0% 4.1% 4.0% 4.1% Na alkyl sulfate (branched) 9.4% 9.6% 9.4% 9.6% Alkyl ethoxylate 3.5% Zeolite type A 37.4% 35.4% 26.8% 37.4% 35.4% Sodium carbonate 22.3% 22.5% 35.9% 22.3% 22.5% Sodium sulfate 1.0% 18.8% 1.0% Sodium silicate 2.2% Protease 0.1% 0.2% 0.1% 0.2% Sodium polyacrylate 1.0% 1.2% 0.7% 1.0% 1.2% Carboxymethylcellulose 0.1% PEG 600 0.5% 0.5% PEG 4000 2.2% 2.2% DTPA 0.7% 0.6% 0.7% 0.6% Fluorescent bleaching agent 0.1% 0.1% 0.1% 0.1% 0.1% Sodium percarbonate 5.0% 5.0% Sodium nonanoyloxybenzenesulfonate 5.3% 5.3% Silicone foam suppressant 0.02% 0.02% 0.02% 0.02% Perfume 0.3% 0.3% 0.2% 0.3% 0.3% Polymeric thiophene tinting agent 0.004% 0.006% 0.002% 0.004% 0.02% water and various remainder remainder remainder remainder 100.0% 100.0% 100.0% 100.0% 100.0% Compositions for tissue treatment: Table C provides examples of liquid compositions for tissue treatment that include at least one polymeric thiophene matting agent of the present invention. Table C - Liquid compositions for the treatment of tissues comprising a polymeric thiophene matting agent Ingredients 3a 3b 3c 3d Fabric softener active 13.70% 13.70% 13.70% 13.70% Ethanol 2.14% 2.14% 2.14% 2.14% Cationic starch b 2.17% 2.17% 2.17% 2.17% Perfume 1.45% 1.45% 1.45% 1.45% Phase stabilizing polymer c 0.21% 0.21% 0.21% 0.21% Calcium chloride 0.147% 0.147% 0.147% 0.147% DTPA d 0.007% 0.007% 0.007% 0.007% Preservatives 5 ppm 5 ppm 5 ppm 5 ppm Antifoaming agent 0.015% 0.015% 0.015% 0.015% Polymeric thiophene tinting agent 30 ppm 30 ppm 30 ppm 15 ppm Tinopal CBS-X 0.2 0.2 0.2 0.2 Ethoquad C / 25 h 0.26 0.26 0.26 0.26 Ammonium chloride 0.1% 0.1% 0.1% 0.1% Hydrochloric acid 0.012% 0.012% 0.012% 0.012% Deionized water Remainder Remainder Remainder Remainder N,N-di(tallowoxyethyl)-N,N-dimethylammonium achloride. bCationic starch based on common corn or potato starch, containing 25% to 95% amylose and a degree of substitution of 0.02 to 0.09, and having a viscosity measured as Water Flow with a value of 50 to 84. Ethylene oxide terephthalate copolymer having the formula described in US 5,574,179 in column 15, lines 1- 5, wherein each X is methyl, each n is 40, u is 4, each R1 is essentially fractions of 1,4-phenylene, each R2 is essentially ethylene, residues of 1,2-propylene or mixtures thereof. dDiethylenetriaminepentaacetic acid. eKATHON® CG available from Rohm and Haas Co. Silicone antifoaming agent available from Dow Corning Corp. under the trade name DC2310. g 4,4'-bis-(2-sulfostyryl) disodium biphenyl, available from Giba Specialty Chemicals.

[15] ammonium chloride ethoxylated cocomethyl, available from Akzo Nobel. EXAMPLES

[00155] The following examples further illustrate the topic described above but, of course, should not be interpreted as limiting its scope in any way.

[00156] The polymeric thiophene matting agent of Formula I was synthesized and tested for deposition during the wash cycle at various concentrations in laundry detergent compositions and fabric softeners. The washes were performed on fabrics containing cotton and polyester. The detailed synthesis and test results are reported below in more detail.

[00157] Testing procedures:

[00158] Method for determining the relative shade angle (versus AATCC control) (Ref: WO2019075142A1):

[00159] The relative hue angle provided by a hue-enhancing agent to cotton fabrics treated according to Method I described below was determined as follows: a) The a* and b* values ​​of the 4 samples of each solution were averaged and the following formulas were used to determine Aa* and Ab*: Aa* = a*s- a*cy Ab* = b*s- b*c where the subscripts cys refer respectively to the fabric washed with AATCC high performance liquid detergent without brightener (control) and the fabric washed with the laundry care formulation containing the matting agents (sample). b) If the absolute value of Aa* and Ab* < 0.25, no relative shade angle (RHA) was calculated. If the absolute value of Aa* or Ab* is > 0.25, the RHA was determined using one of the following formulas: RHA = ATAN2(Aa*,Ab*) for Ab* > 0 RHA = 360 + ATAN2(Aa*,Ab*) for Ab* < 0.

[00160] Method for determining AWI:

[00161] The WI CIE values ​​of the samples for each washing solution were calculated using the following equation: AWI = WI CIE (after washing) - WI CIE (before washing).

[00162] Method for calculating ΔE:

[00163] The values ​​L*, a*, b* were taken and converted to delta E values ​​by calculating the difference in L, a and b between the post-wash measurements and those of an identical white fabric that had not been washed with a matting agent and then applying the equation: ΔE =7^17+^0^4 / ^2.

[00164] The bias for cotton is determined by the following equation:

[00165] Bias aVW in cotton \WI in PE

[00166] Method I: Wash test method for determining bleaching

[00167] Preparation of test tissues:

[00168] The test fabrics (purchased from Testfabrics, Inc.) included a 60-width open-weave bleached cotton T-shirt fabric style number 437W-60, a textured polyester interlock knit fabric style number 730, and a textured double-knit nylon 6.6 stretch fabric style number 314. Each sample was cut to 16 cm by 16 cm in size. The fabrics were prepared prior to use by washing a full cycle in AATCC liquid laundry detergent without brighteners and then rinsing twice before drying.

[00169] Preparation of the wash water solution containing the toning dye:

[00170] A sufficient volume of wash water containing liquid or powder detergent without brightener was prepared by dissolving the detergent in tap water at room temperature at a concentration of 1 gram per liter. Then, both Comparative Tinting Agent 1 and Tinting Agent 1 of the invention were added to the wash water in quantities sufficient to provide the same absorption capacity in each wash solution. This amount of dye for each experiment corresponds to approximately 3 ppm in the wash water. For multi-wash experiments, the tinting agent was present at 1 ppm in the wash water.

[00171] Washing procedure:

[00172] Wash tests were completed using a tergotometer. For each wash, a fabric blend consisting of 63% cotton, 25% polyester, and 12% nylon was used. The total fabric in the wash water corresponded to a solution-to-fabric ratio of 25:1. The fabrics were agitated at 220 rpm for 15 minutes. After washing, each set of fabrics was rinsed twice with tap water. After rinsing, all fabrics were dried in a dryer for one hour. After drying, the fabric samples were read using an X-Rite Color i7 spectrophotometer. The average reflectance of all samples for each fabric type under each wash condition was used to calculate the L*, a*, b*, and WI-CIE values. ινΐΛ / a / zuzz / uiuio □ EXAMPLE 1

[00173] A polymeric thiophene matting agent was prepared according to the procedure described below.

[00174] Comparative tinting agent 1, prepared with m-toluidine 5EO according to Example 3 of U.S. Patent No. 4,912,203, was treated under basic conditions (pH > 9) to form the tinting agent 1 of the invention. Surprisingly, upon treatment of the comparative tinting agent with base, no decomposition of the azo dye was observed. Instead, selective hydrolysis of a nitrile bond to the amide could be achieved to give the tinting agent 1 of the invention. These two tinting agents were tested against each other for comparative purposes. Comparative nuance agent 1 NH2 Invention's mattifying agent 1

[00175] A polyethylene glycol 200 solution containing 13 g of comparative matting agent 1, prepared according to Example 3 of U.S. Patent No. 4,912,203 (25 mmol), water (33 mL), and 50% aqueous sodium hydroxide (25 mmol) was loaded into a round-bottom flask. The pH was >9. The mixture was heated to 90°C for 1 hour, and UPLC analysis showed that the reaction was complete. The solution was neutralized to pH 7 with acetic acid. A reddish-violet solution containing 3.5 wt% of the matting agent 1 of the invention dissolved was obtained.

[00176] The toning agent 1 of the invention was compared with the comparative toning agent 1 using the test conditions listed above. Table 1 shows the improvements in bleaching and changes in the hue angle in cotton and polyester fabrics after treatment with the composition containing the toning agent 1 of the invention versus the comparative toning agent 1 on cotton fabric at 3 ppm in a load of wash water. Table 1 - Whitening effect of the toning agents Dyeing agent \WI in cotton Relative hue angle in cotton \WI in polyester Relative hue angle in polyester Bias for cotton Comparative hueing agent 1 5.9 268 5.4 271 1.09 Hueing agent 1 of the invention 8.6 301 1.7 295 5.06

[00177] The results of the tests on cotton fabric illustrate that the bleaching performance of the Tinting Agent 1 of the invention improved by almost 3 units over the comparative Tinting Agent 1. In addition, the tint angle in the fabric treated with the Tinting Agent 1 of the invention changed to a more reddish tone, which in some applications is preferred by consumers.

[00178] When the bleaching bias was calculated using the above equation, the bleaching improvement in cotton treated with the Tinting Agent 1 of the invention was five times greater than that of the polyester fabric. In comparison, there was no actual bias when treated with the comparative tinting agent 1. Since cotton fabrics tend to yellow over time when exposed to light, air, and contaminants more than polyester fabrics, the bleaching improvement was five times greater than that of polyester fabrics. 100 synthetic fabrics, it is very important to have a tinting agent that points to cotton over polyester.

[00179] Furthermore, the composition containing the toning agent 1 of the invention showed a leveling effect, in that the ΔE of the fabric did not change compared to the fabric washed without the toning dye of the invention after multiple washes. This result indicates that an equilibrium toning point was reached where the amount of dye deposited through subsequent washes is equal to the dye removed from the fabric in those washes. Therefore, another advantage of the present invention is that an optimum level of toning was achieved in the fabric without staining the fabric. The test results are shown in Table 2. Table 2: Multiple wash data for cotton at 1 ppm in wash water Toning agent ΔΕ* after 1 wash ΔΕ* after 3 washes ΔΕ* after 5 washes ΔΕ* after 8 washes Toning agent 1 of the invention 1.6 2.9 3.2 3.4 101

[00180] The whitening effect was also evaluated using a mixture of toning agents. The fabrics were washed according to the washing method described herein (at a total load of 3 ppm of toning dyes) with varying proportions of Toning Agent 1 of the invention to Toning Agent 2. Toning Agent 2 is represented by Formula Y. The test results are provided in Tables 3 and 4. The test results demonstrate variations in the relative shade angle in the fabric, which may be desirable since different regions of the world have preferences for various shades in fabric. Therefore, it is important to be able to adjust the perceived whitening benefits by adjusting the shade angle.The test results further illustrate that the proportions of the two toning agents (Toning Agent 1 of the invention and Toning Agent 2) can be varied to target a desired hue angle between 270 and 300 in cotton and polyester fabrics. The toning agents alone may produce ranges that are slightly outside the desired hue angle (depending on the detergent and the fabric). 102 Table 3: Relative shade angle in cotton versus the proportion of shade agents at a total load of 3 ppm in the wash water 100% Tinting Agent 2 75% Tinting Agent 2: 25% Tinting Agent of the Invention 1 50% Tinting Agent 2: 50% Tinting Agent of the Invention 1 25% Tinting Agent 2: 75% Tinting Agent of the Invention 1 100% Tinting Agent of the Invention 1 Relative Tint Angle (RHA) of Liquid Detergent AATCC 274 282 295 299 302 Relative Tint Angle (RHA) of Powder Detergent AATCC 268 282 293 296 301 Table 4: Relative shade angle in polyester versus the proportion of shading agents at a total load of 3 ppm in the wash water 100% Tinting Agent 75% Tinting Agent 50% Tinting Agent 25% Tinting Agent 100% Tinting Agent 103 2 2: 25% Tinting agent of the invention 1 2: 50% Tinting agent of the invention 1 2: 75% Tinting agent of the invention 1 of the invention 1 Relative tint angle (RHA) of liquid detergent AATCC 276 275 280 281 292 Relative tint angle (RHA) of powder detergent AATCC 271 272 274 275 295 iviA / a / zuzz / uiu / oj

[00181] Additional tests were conducted to compare each of the Tinting Agents 1 and Tinting Agent 2 of the invention on cotton fabric at loading levels of 1 ppm. The test results are provided in Table 5. The test results demonstrate that both coloring agents accumulate in the fabric, as determined by ΔE, but level off after a certain number of washes. This is advantageous because the tinting agents will not stain the fabric but will provide sufficient tint to eliminate yellowing of the soiled fabric. 104

[00182] Table 5: Multiple wash data for cotton at 1 ppm of matting agent in wash water Matting agent ΔΕ* after 1 wash ΔΕ* after 3 washes ΔΕ* after 5 washes ΔΕ* after 8 washes Matting agent of the invention 1 (100%) 1.2 2.1 2.2 2.2 Matting agent 2 (100%) 1.6 2.9 3.2 3.4

[00183] It should be noted that, unlike many traditional dyes, the polymeric thiophene tinting agents of the present invention and the garment care compositions containing them do not require the inclusion of a bleaching agent to remove excess tinting. The tinting agents and compositions of the invention naturally accumulate and level on the fabric in the desired amounts to impart the desired whitening effect to the consumer, without creating an over-tinted fabric (e.g., 15).

[00184] All references, including publications, patent applications and patents, cited herein are incorporated herein by reference to the same extent as if each reference were indicated individually and specifically 105 to be incorporated by reference and set forth herein in its entirety.

[00185] The use of the terms "a" and "an" and similar references in the context of the description of the subject matter of this application (especially in the context of the following claims) should be construed to cover both singular and plural, unless otherwise stated herein or clearly contradicted by the context. The terms "comprising," "having," "including," and "containing" should be construed as open terms (i.e., meaning "includes, but is not limited to") unless otherwise stated. The enumeration of the ranges of values ​​in this document is intended merely as a shorthand method for referring individually to each separate value within the range, unless otherwise stated herein, and each separate value is incorporated into the specification as if it were individually mentioned herein.All methods described in this document may be performed in any suitable order unless otherwise stated herein or clearly contradicted by the context. The use of any and all examples, or exemplary language (e.g., such as) provided herein is intended to better illustrate the subject matter of the application and not Section 106 represents a limitation on the scope of the invention unless otherwise stated. Nothing in the specification should be construed as indicating that anything not claimed is essential to the practice of the subject matter described herein.

[00186] Preferred embodiments of the subject matter of this application are described herein, including the best means known to the inventors for carrying out the claimed object. Variations of these preferred embodiments may be apparent to those skilled in the art upon reading the foregoing description. The inventors expect that those skilled in the art will employ such variations as appropriate, and the inventors do not intend that the subject matter described herein may be practiced in any manner other than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter mentioned in the appended claims to the extent permitted by applicable law.Furthermore, any combination of the elements described above in all possible variations thereof is covered by this description unless otherwise stated herein or clearly contradicted by the context.

Claims

1. A laundry care composition comprising: (1) a laundry care ingredient; (2) from 0.0001 wt% to 1.0 wt% of a polymeric thiophene mattifying agent having the structure of Formula I: N-Ri Ri Formula I wherein each A is independently selected from the group consisting of polyethylenexy, polypropylenexy, and polyethylenexy / polypropylenoxy copolymers, and wherein each A is independently present in the range of 1 to 20 repeating units of polyethylenexy, polypropylenexy, or polyethylenexy / polypropylenoxy copolymers; where each Ri is independently selected from H, C1-4 alkyl, alkoxy alkyl, halogens, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2CI, -CH=CH2, -CH2CH(OH)2 and their salts; where each R2 is independently selected from Ci-18 alkyl, aryl, substituted aryl and substituted alkyl; and 108 (3) from 0.0001 wt% to 1.0% by weight of a polymeric thiophene matting agent having the structure of Formula X: Ri (A)(Ri) NC Rl']|YN>)(Ri) L zNs A A. Ri / Y ΝγA Vs Ri NC Formula X wherein each A is independently selected from the group consisting of polyethylenexy, polypropyloxy and polyethylenexy / polypropylenoxy copolymers, and wherein each A is independently present in the range of 1 to 20 repeating units of polyethylenexy, polypropyloxy or polyethylenexy / polypropylenoxy copolymers; wherein each Ri is independently selected from H, Ci-4 alkyl, alkoxy alkyl, halogens, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2CI, -CH=CH2, -CH2CH(OH)2 and their salts; where each R2 is independently selected from Ci18 alkyl, aryl, substituted aryl, and substituted alkyl.

2. The laundry care composition of claim 1, comprising (1) a laundry care ingredient; (2) from 0.0001 wt% to 1.0 wt% of a polymeric thiophene matting agent having the structure of Formula III: Formula III; (3) from 0.0001 wt% to 1.0 wt% of a polymeric thiophene matting agent having the structure of Formula Y: (pH2CH2O)3H NC (CH2CH2O)2H Formula Y 10 3. The laundry care composition according to claim 1, wherein each polymeric thiophene mattifying agent is present in an amount in the range of 1 ppm to 10,000 ppm. 15 4. The aqueous laundry care composition according to claim 1, wherein the polymeric thiophene mattifying agent is present in an amount in the range of 1 ppm to 500 ppm. 110 5. The laundry care composition according to claim 1, wherein the polymeric thiophene mattifying agent of Formula I and the polymeric thiophene mattifying agent of Formula X are present in a ratio of 1:200 to 200:

1.

6. The laundry care composition according to claim 1, wherein the polymeric thiophene mattifying agent of Formula I and the polymeric thiophene mattifying agent of Formula X are present in a ratio of 1:100 to 100:

1.

7. The laundry care composition according to claim 1, wherein the polymeric thiophene mattifying agent of Formula I and the polymeric thiophene mattifying agent of Formula are present in a ratio of 1:3 to 3:

1. The laundry care composition according to claim 1 wherein the composition is present in powder form.

9. The composition for laundry care in accordance with which the composition is present in liquid form.

10. The laundry care composition in accordance with which the composition is present in a multi-compartment unit-dose form. 111 11. The laundry care composition according to claim 1, wherein the composition further contains at least one of the following structures, or salts thereof: (CH2CH2O)2H NC (pH2CH2O)3H (CH2CH2O)2H (pH2CH2O)3H 112 12. The laundry care composition according to claim 1, wherein the laundry care ingredient is selected from the group consisting of cationic polymers, surfactants, enhancers, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, polymeric dispersing agents, clay soil removal / anti-redeposition agents, brighteners, foam suppressants, dyes, pigments, coloring agents, perfumes, perfume release systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, and processing aids.

13. A textile article containing the polymeric thiophene matting agents of claim 1.

14. The textile article of claim 13, wherein the article is composed of fiber containing cellulose.

15. A method of treating a textile article to improve the visual appearance of the article comprising the steps of (1) providing a textile article and (2) exposing the textile article to the garment care composition of claim 1. 113 16. The method according to claim 15, wherein the textile article is composed of fiber containing cellulose.

17. The method according to claim 15, wherein the method is bleach-free.

18. A fabric containing cellulose containing the polymeric thiophene matting agents of claim 1.

19. A method for treating a textile article comprising the steps of (i) treating the textile article with the aqueous laundry care composition of claim 1, and (ii) rinsing and drying the treated textile article.

20. The method according to claim 19, wherein the step of treating the textile article is free of bleach.

21. The laundry care composition according to claim 1, wherein the composition imparts a desired hue to a textile article with a relative hue angle in the range of 210 to 345.

22. The laundry care composition according to claim 1, wherein the composition imparts a desired hue to a textile article with a relative hue angle in the range of 270 to 300.