Composition containing a hue adjuster

Abstract

To provide a laundry care composition comprising a laundry care ingredient and a polymeric thiophene hueing agent.SOLUTION: A laundry care composition comprises: (i) a laundry care ingredient; and (ii) 0.0001 wt.% to 1.0 wt.% of a polymeric thiophene hueing agent having a structure of Formula I. The polymeric thiophene hueing agent provides a whitening bias on a cellulose-containing textile article when compared to a polyester-containing textile substrate, where the whitening bias is measured via the following formula: (whitening bias)=(change in whitening of the cellulose-containing textile article / change in whitening of the polyester-containing textile article), where the whitening effect is measured via a whiteness index on each textile article.SELECTED DRAWING: None

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001]

[0001] This application claims priority to U.S. Provisional Patent Application No. 62 / 983,880, entitled "Compositions Containing Hue Adjusters," filed March 2, 2020, the entire contents of which are incorporated herein by reference. [Technical Field]

[0002] FIELD OF THE INVENTION This invention relates to laundry care compositions comprising laundry care ingredients and polymeric thiophene color adjusters. background

[0003] While consumers are increasingly seeking lower temperatures and shorter wash cycles for laundry to conserve energy, the cleaning efficiency of laundry care compositions may not be as effective as that achieved with higher temperatures and longer wash times. Therefore, the use of color adjusters in laundry care compositions provides a technique for providing whitening benefits to soiled textile articles (e.g., clothing and other decorative items) even at lower wash temperatures and shorter cycle times, making them appear brighter and whiter. The use of harsh bleaching chemicals is also undesirable because it can shorten the textile article's life cycle and be environmentally unfriendly. Furthermore, in some instances, consumers prefer a more reddish, blue-purple shade on clothing to conceal fabric yellowing, which cannot be achieved with bleach formulations. Consequently, there remains a need for improved whitening effects on textile articles treated with laundry care compositions containing color adjusters. The present invention provides laundry care compositions containing polymeric thiophene color adjusters that have been demonstrated to whiten textile articles, such as cellulose-containing fabrics. The incorporation of this hue adjuster into laundry care compositions provides a feasible and successful delivery mechanism for deposition onto textile substrates. Each time the textile substrate is washed, the hue adjuster is deposited onto the textile substrate. Thus, the textile substrate can be frequently brightened, extending the life cycle of the article. Quick Overview

[0004] In one aspect, the present invention provides a laundry care ingredient comprising 0.0001% to 1.0% by weight of a compound of formula I:

[0003] [ka]

[0004] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 20 repeat units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Each R1 is H, C 1~4 independently selected from alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, —COR 2 , —CH 2 COH, —COOR 2 , —COOH, —SO 3 H, —CH 2 COOH, —CH 2 CH 2 Cl, —CH═CH 2 , —CH 2 CH(OH) 2 , and salts thereof; each R 2 is independently selected from C 1~18 independently selected from alkyl, aryl, substituted aryl, and substituted alkyl. The present invention relates to an aqueous laundry care composition comprising a polymeric thiophene hue adjuster having the structure:

[0005] In another aspect, the present invention provides a laundry care ingredient and 0.0001% to 1.0% by weight of a compound of formula I:

[0006] [ka]

[0007] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 5 polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer repeat units; Each R1 is H and C 1~4 alkyl] The present invention relates to an aqueous laundry care composition comprising a polymeric thiophene hue adjuster having the structure:

[0008] In a further aspect, the present invention provides a laundry care ingredient comprising from 0.0001% to 1.0% by weight of a compound of formula II:

[0009] [ka]

[0010] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 5 polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer repeat units. The present invention relates to an aqueous laundry care composition comprising a polymeric thiophene hue adjuster having the structure:

[0011] In yet a further aspect, the present invention relates to a method for making an amide-containing polymeric thiophene hue modifier in which an amide is formed by hydrolysis of a nitrile under basic conditions, eg, pH>9.

[0012] In another aspect, the present invention provides a laundry care ingredient comprising: (1) a laundry care ingredient; and (2) 0.0001% to 1.0% by weight of a compound of Formula I:

[0013] [ka]

[0014] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 20 repeat units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Each R1 is H, C 1~4 independently selected from alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2Cl, -CH=CH2, -CH2CH(OH)2, and salts thereof; Each R2 is C 1~18 independently selected from alkyl, aryl, substituted aryl, and substituted alkyl. and (3) 0.0001 wt % to 1.0 wt % of a polymeric thiophene hue modifier having the structure:

[0015] [ka]

[0016] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 20 repeat units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Each R1 is H, C 1~4 independently selected from alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, —COR 2 , —CH 2 COH, —COOR 2 , —COOH, —SO 3 H, —CH 2 COOH, —CH 2 CH 2 Cl, —CH═CH 2 , —CH 2 CH(OH) 2 , and salts thereof; each R 2 is independently selected from C 1~18 independently selected from alkyl, aryl, substituted aryl, and substituted alkyl. and a polymeric thiophene hue adjuster having the structure:

[0017] In a further aspect, the present invention provides a composition comprising: (i) a laundry care ingredient; and (ii) 0.0001% to 1.0% by weight of a compound of formula I:

[0018] [ka]

[0019] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 20 repeat units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Each R1 is H, C 1~4 independently selected from alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, —COR 2 , —CH 2 COH, —COOR 2 , —COOH, —SO 3 H, —CH 2 COOH, —CH 2 CH 2 Cl, —CH═CH 2 , —CH 2 CH(OH) 2 , and salts thereof; each R 2 is independently selected from C 1~18 independently selected from alkyl, aryl, substituted aryl, and substituted alkyl. and a polymeric thiophene hue modifier having the structure:

[0020] In another aspect, the present invention provides a method for measurably improving the whitening effect on cellulose-containing textile articles, wherein the improvement is present in an amount greater than that observed in polyester-containing textile articles, the method comprising the steps of: (a) providing a cellulose-containing textile substrate; (b) providing a polyester-containing textile substrate; and treating the textile substrate of steps (a) and (b) with: (i) laundry care ingredients; and (ii) from 0.0001% to 1.0% by weight of a component of Formula I:

[0021] [ka]

[0022] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 20 repeat units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Each R1 is H, C 1~4 independently selected from alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, —COR 2 , —CH 2 COH, —COOR 2 , —COOH, —SO 3 H, —CH 2 COOH, —CH 2 CH 2 Cl, —CH═CH 2 , —CH 2 CH(OH) 2 , and salts thereof; each R 2 is independently selected from C 1~18 independently selected from alkyl, aryl, substituted aryl, and substituted alkyl. and (d) measuring the whitening effect by rating the whiteness index of each textile article.

[0023] In another aspect, the present invention provides a composition comprising: (a) a majority by weight of cellulosic fibers; and (b) (i) a laundry care ingredient; and (ii) 0.0001% to 1.0% by weight of a compound of formula III:

[0024] [ka]

[0025] and a laundry care composition comprising a polymeric thiophene hue adjuster having the structure: Detailed Description The invention described herein is a laundry care composition comprising a laundry care ingredient and a polymeric thiophene hue modifier. In one aspect of the invention, the polymeric thiophene hue modifier is added to textile articles via the laundry care composition during a standard laundry cycle. The laundry care composition containing the polymeric thiophene hue modifier is added to a washing machine, thereby allowing the molecules to directly contact the textile articles. Thus, the polymeric thiophene hue modifier is deposited on at least one surface of the textile article during the laundry cycle, providing improved whitening to the treated textile article.

[0026]

[0013] As used herein, the term "alkoxy" is intended to include C1-C8 alkoxy and alkoxy derivatives of polyols having repeating units, for example, butylene oxide, glycidol oxide, ethylene oxide, or propylene oxide.

[0027] As used herein, unless otherwise specified, the terms "alkyl" and "alkyl-capped" refer to C to C 100 Alkyl groups, C2-C 50 Alkyl groups, C5-C 25 Alkyl groups, or even C 10 ~C 20 Alkyl groups are intended to be included.

[0028] As used herein, unless otherwise specified, the term "aryl" refers to a C-C 12 Aryl groups are intended to be included.

[0029] As used herein, unless otherwise specified, the term "arylalkyl" refers to a C1-C 18 It is intended to include alkyl groups and, in one aspect, C1 to C6 alkyl groups.

[0030] As used herein, unless otherwise specified, the term "alkanoyl" refers to a group of the formula -C(O)R a (In the formula, R a is an alkyl group, preferably C3 to C 29 refers to a monovalent group that is an alkyl.

[0031] As used herein, unless otherwise specified, the term "alkenyl" refers to a monovalent group obtained by removing a hydrogen atom from any carbon atom of an acyclic olefinic hydrocarbon. In the context of this definition, the term "acyclic olefinic hydrocarbon" refers to an acyclic hydrocarbon containing one or more carbon-carbon double bonds.

[0032]

[0019] The terms "ethylene oxide," "propylene oxide," and "butylene oxide" may be referred to herein by their typical names, "EO," "PO," and "BO," respectively.

[0033]

[0020] Unless otherwise indicated, all percentages and ratios are calculated by weight. Unless otherwise indicated, all percentages and ratios are calculated based on the total composition.

[0034]

[0021] Polymeric thiophene hue modifiers suitable for use in the present invention may contain a variety of groups, such as oxyalkylated, acylated, alkylated, carbonylated, and olefinated derivatives thereof (prepared by introducing such groups individually, selectively, and / or in combination, including derivatives prepared by, for example, varying the order in which such groups are added, and increasing the number and order in which such groups are added).

[0035] In one aspect, the present invention provides a laundry care ingredient comprising 0.0001% to 1.0% by weight of a compound of formula I:

[0036] [ka]

[0037] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 20 repeat units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Each R1 is H, C 1~4 independently selected from alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, —COR 2 , —CH 2 COH, —COOR 2 , —COOH, —SO 3 H, —CH 2 COOH, —CH 2 CH 2 Cl, —CH═CH 2 , —CH 2 CH(OH) 2 , and salts thereof; each R 2 is independently selected from C 1~18 independently selected from alkyl, aryl, substituted aryl, and substituted alkyl. and a polymeric thiophene hue adjuster having the structure:

[0038] In a further aspect, the present invention provides a laundry care ingredient comprising from 0.0001% to 1.0% by weight of a compound of formula I:

[0039] [ka]

[0040] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 5 polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer repeat units; Each R1 is H and C 1~4 alkyl] and a polymeric thiophene hue adjuster having the structure:

[0041] In yet a further aspect, the present invention provides a laundry care ingredient comprising from 0.0001% to 1.0% by weight of a compound of formula II:

[0042] [ka]

[0043] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 5 polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer repeat units. and a polymeric thiophene hue adjuster having the structure:

[0044] The polymeric thiophene hue modifier may be present in the laundry care composition in an amount ranging from 1 ppm to 10,000 ppm, or from 1 ppm to 500 ppm.

[0045]

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

[0046] The aqueous laundry care compositions of the present invention may be in liquid form, in unit dose packages, or in multi-compartment unit dose packages.

[0047]

[0028] Impurities in the hue adjuster may also be present. Those skilled in the art will recognize that impurities associated with positional isomers, incomplete reactions, or double coupling of the diazonium salt to the coupling agent may occur when preparing the azo dye. Impurities may include, for example, carboxylic acids, bisamides, positional isomeric amides, or mixtures of carboxylic acids, esters, nitriles, and amides present in the thiophene moiety. Thus, the aqueous laundry care composition may comprise a compound having the following structure:

[0048] [ka]

[0049] or a salt thereof.

[0050] In one aspect of the present invention, the aqueous laundry care composition contains laundry care ingredients selected from the group consisting of cationic polymers, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersants, clay and earth soil removers / anti-redeposition agents, brighteners, suds suppressors, dyes, pigments, colorants, fragrances, fragrance delivery systems, structural plasticizers, fabric softeners, carriers, hydrotropes, and processing aids.

[0051] Textile articles may be treated with the laundry care compositions of the present invention. As a result, the treated textile articles may contain a polymeric thiophene hue modifier as described herein. In one aspect of the present invention, the textile articles are comprised of cellulose-containing fibers. The textile articles may be in the form of fabrics. Thus, the present invention includes cellulose-containing fabrics containing a polymeric thiophene hue modifier as described herein.

[0052] A method for treating a textile article to improve its appearance includes (1) providing a textile article and (2) exposing the textile article to a laundry care composition containing a polymeric thiophene hue adjuster as described herein. The method for treating the textile article may further include (i) treating the textile article with an aqueous or non-aqueous laundry care composition as described herein, and (ii) rinsing and drying the treated textile article. The method for treating textile articles with the laundry care composition of the present invention may be aqueous or non-aqueous and may be bleach-free.

[0053]

[0032] The method for making the amide-containing polymeric thiophene hue modifier of the present invention may include forming an amide by hydrolysis of a nitrile under basic conditions, for example, conditions where the pH is greater than 9. The basic conditions may be formed in the presence of at least one of a carbonate, a bicarbonate, an amine, a hydroxide, an alkoxide, and mixtures thereof.

[0054] Aqueous laundry care compositions containing polymeric thiophene hue adjusters may impart desired hues to textile articles with relative hue angles greater than 270, or with relative hue angles in the range of 270 to 310, or with relative hue angles in the range of 290 to 310.

[0055] In yet another aspect of the present invention, (1) a laundry care ingredient; and (2) 0.0001% to 1.0% by weight of a compound of Formula I:

[0056] [ka]

[0057] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 20 repeat units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Each R1 is H, C 1~4 independently selected from alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, —COR 2 , —CH 2 COH, —COOR 2 , —COOH, —SO 3 H, —CH 2 COOH, —CH 2 CH 2 Cl, —CH═CH 2 , —CH 2 CH(OH) 2 , and salts thereof; each R 2 is independently selected from C 1~18 independently selected from alkyl, aryl, substituted aryl, and substituted alkyl. and (3) 0.0001 wt % to 1.0 wt % of a polymeric thiophene hue modifier having the structure:

[0058] [ka]

[0059] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 20 repeat units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Each R1 is H, C 1~4 independently selected from alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, —COR 2 , —CH 2 COH, —COOR 2 , —COOH, —SO 3 H, —CH 2 COOH, —CH 2 CH 2 Cl, —CH═CH 2 , —CH 2 CH(OH) 2 , and salts thereof; each R 2 is independently selected from C 1~18 independently selected from alkyl, aryl, substituted aryl, and substituted alkyl. and a polymeric thiophene hue adjuster having the structure:

[0060] In a further aspect of the present invention, (1) a laundry care ingredient; and (2) 0.0001% to 1.0% by weight of a compound of formula III:

[0061] [ka]

[0062] and (3) 0.0001 wt % to 1.0 wt % of a polymeric thiophene hue modifier having the structure:

[0063] [ka]

[0064] and a polymeric thiophene hue adjuster having the structure:

[0065] Each polymeric thiophene hue modifier is independently present in the composition in an amount ranging from 1 ppm to 10,000 ppm, or even in an amount ranging from 1 ppm to 500 ppm. The polymeric thiophene hue modifier of Formula I and the polymeric thiophene hue modifier of Formula X are present in a ratio of 1:200 to 200:1, a ratio of 1:100 to 100:1, or even a ratio of 1:3 to 3:1. In another aspect of the invention, the polymeric thiophene hue modifier of Formula III and the polymeric thiophene hue modifier of Formula Y are present in a ratio of 1:200 to 200:1, a ratio of 1:100 to 100:1, or even a ratio of 1:3 to 3:1.

[0066] The laundry care composition may be in powder form, liquid form, unit dose package form, or multi-compartment unit dose package form.

[0067]

[0038] Impurities in the hue adjuster may also be present. Impurities may include, for example, carboxylic acids, bisamides, regioisomeric amides, or mixtures of carboxylic acids, esters, nitriles, and amides present in the thiophene moiety. Thus, the aqueous laundry care composition may comprise a compound having the following structure:

[0068] [ka]

[0069] or a salt thereof.

[0070]

[0039] The laundry care ingredients may be selected from the group consisting of cationic polymers, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersants, clay and soil removers / anti-redeposition agents, brighteners, suds suppressors, dyes, pigments, colorants, fragrances, fragrance delivery systems, structural plasticizers, fabric softeners, carriers, hydrotropes, and processing aids.

[0071] The laundry care composition may have a relative hue angle in the range of 210 to 345, or in the range of 270 to 300, thereby imparting the desired hue to treated textile articles.

[0072] A further aspect of the present invention is a composition comprising (i) a laundry care ingredient; and (ii) 0.0001% to 1.0% by weight of Formula I:

[0073] [ka]

[0074] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 20 repeat units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Each R1 is H, C 1~4 independently selected from alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, —COR 2 , —CH 2 COH, —COOR 2 , —COOH, —SO 3 H, —CH 2 COOH, —CH 2 CH 2 Cl, —CH═CH 2 , —CH 2 CH(OH) 2 , and salts thereof; each R 2 is independently selected from C 1~18 independently selected from alkyl, aryl, substituted aryl, and substituted alkyl. and a polymeric thiophene hue modifier having the structure:

[0075] The polymeric thiophene hue modifier may be present in an amount ranging from 1 ppm to 10,000 ppm, or from 1 ppm to 500 ppm.

[0076] The cellulose-containing textile article may exhibit at least two times greater whitening effectiveness than a polyester-containing textile substrate treated with the laundry care composition. The cellulose-containing textile article may further exhibit at least five times greater whitening effectiveness than a polyester-containing textile substrate treated with the laundry care composition.

[0077] Polymeric thiophene hue modifiers also exhibit a higher hue than polyester-containing textiles than cellulose-containing textiles, as shown by the formula: Brightening bias = (change in whiteness of cellulose-containing textile article / change in whiteness of polyester-containing textile article) and the whitening effect is measured by the whiteness index of each textile article.

[0078] The cellulose-containing textile article may be composed of fibers selected from the group consisting of cotton, linen, rayon, jute, hemp, bamboo, and blends thereof. The cellulose-containing textile article may be composed of cotton fibers that make up a majority of its weight. The cellulose-containing textile article may be composed of 100% cotton fibers. The polyester-containing textile article may be composed of polyester fibers that make up a majority of its weight. The polyester-containing textile article may be composed of 100% polyester fibers.

[0079] The presence of Formula I imparts a hue to cellulose-containing textile articles, the hue being determined by measuring the relative hue angle. Cellulose-containing textile articles treated with the laundry care compositions of the present invention may exhibit a relative hue angle in the range of 280 to 345, or in the range of 290 to 320.

[0080] Impurities in the hue adjuster may also be present. Impurities may include, for example, carboxylic acids, bisamides, regioisomeric amides, or mixtures of carboxylic acids, esters, nitriles, and amides present in the thiophene moiety. Thus, the aqueous laundry care composition may comprise a compound having the following structure:

[0081] [ka]

[0082] or a salt thereof.

[0083]

[0048] The laundry care ingredients may be selected from the group consisting of cationic polymers, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersants, clay and soil removers / anti-redeposition agents, brighteners, suds suppressors, dyes, pigments, colorants, fragrances, fragrance delivery systems, structural plasticizers, fabric softeners, carriers, hydrotropes, and processing aids.

[0084] The present invention also encompasses a method for increasing the whitening effect / index of a textile article, comprising the steps of (i) treating the textile article with a laundry care composition as described herein, and (ii) rinsing and drying the treated textile article. The step of treating the textile article may be bleach-free.

[0085] A method for measurably improving the whitening effect on cellulose-containing textile articles, wherein the improvement is present in an amount greater than that observed in polyester-containing textile articles, the method comprising the steps of: (a) providing a cellulose-containing textile substrate; (b) providing a polyester-containing textile substrate; and treating the textile substrate of steps (a) and (b) with: (i) laundry care ingredients; and (ii) 0.0001% to 1.0% by weight of a compound of Formula I:

[0086] [ka]

[0087] [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 20 repeat units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Each R1 is H, C 1~4independently selected from alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, —COR 2 , —CH 2 COH, —COOR 2 , —COOH, —SO 3 H, —CH 2 COOH, —CH 2 CH 2 Cl, —CH═CH 2 , —CH 2 CH(OH) 2 , and salts thereof; each R 2 is independently selected from C 1~18 independently selected from alkyl, aryl, substituted aryl, and substituted alkyl. and (d) measuring the whitening effect by rating the whiteness index of each textile article.

[0088] In another aspect of the invention, a composition comprising: (a) a majority by weight of cellulosic fibers; and (b) (i) laundry care ingredients; and (ii) 0.0001% to 1.0% by weight of a composition of formula III:

[0089] [ka]

[0090] and a laundry care composition comprising a polymeric thiophene hue adjuster having the structure:

[0091] In one aspect of the present invention, the polymeric thiophene color modifier can comprise any suitable alkyleneoxy group. Suitable alkyleneoxy groups include those of the following formula (C):

[0092] [ka]

[0093] Examples include:

[0094] In the structure of formula (C) and the alkyleneoxy structure below, R 101 The carbon atom bonded to is also bonded to the nitrogen atom of the amine group.101 and R 102 The R groups are independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyalkyl, and aryloxyalkyl. 105 is the terminal group of the oxyalkylene and can be selected from the group consisting of hydrogen, alkyl groups (e.g., C1-C4 alkyl groups), and aryl groups, with hydrogen being preferred. Preferably, each R 101 and R 102 The groups are independently selected from the group consisting of hydrogen and alkyl (e.g., C1-C4 alkyl). The variable a is an integer equal to or greater than 1 (e.g., 1-100). For each monomer unit in the alkyleneoxy group, R 101 and R 102 The groups are independently selected from the mentioned groups. Thus, when the variable a is greater than 1, the alkyleneoxy group can be composed of two or more monomer units, or even three or more monomer units, covalently bonded to form the alkyleneoxy group. When the alkyleneoxy group comprises two or more monomer units (or even three or more monomer units), these monomer units can be arranged in either a block configuration or a random configuration, although a block configuration is generally more preferred. In a preferred embodiment, the alkyleneoxy group comprises monomer units independently selected from the group consisting of ethyleneoxy, propyleneoxy, and butyleneoxy. A suitable example of such an alkyleneoxy group is represented by the following formula (CI):

[0095] [ka]

[0096] is.

[0097] In the structure of formula (CI), the variables x, y, and z are independently selected from the group consisting of 0 and positive integers (e.g., positive integers from 1 to about 100). Preferably, the sum of x, y, and z is 2 or greater or 3 or greater (e.g., 2 to about 300, 3 to about 300, 2 to about 200, 3 to about 200, 2 to about 100, 3 to about 100, 2 to about 50, 3 to about 50, 2 to about 30, 3 to about 30, 2 to about 25, 3 to about 25, 2 to about 20, 3 to about 20, 2 to about 15, 3 to about 15, 2 to about 10, or 3 to about 10). R 105 is the terminal group of the oxyalkylene and can be selected from the group consisting of hydrogen, alkyl groups (e.g., C1-C4 alkyl groups), and aryl groups, with hydrogen being preferred. In certain potentially preferred embodiments, the alkyleneoxy group comprises ethyleneoxy and propyleneoxy monomer units arranged in a block configuration. Suitable examples of such alkyleneoxy groups include those of the following formulae (CII) and (CIII):

[0098] [ka]

[0099] Examples include:

[0100] In the structures of formulae (CII) and (CIII), the variables t, u, v, q, r, and s are independently selected from the group consisting of 0 and positive integers (e.g., positive integers from 1 to about 100). Preferably, the sum of t, u, and v and q, r, and s is 2 or greater or 3 or greater (e.g., 2 to about 300, 3 to about 300, 2 to about 200, 3 to about 200, 2 to about 100, 3 to about 100, 2 to about 50, 3 to about 50, 2 to about 30, 3 to about 30, 2 to about 25, 3 to about 25, 2 to about 20, 3 to about 20, 2 to about 15, 3 to about 15, 2 to about 10, or 3 to about 10). R 105 is the terminal group of the oxyalkylene and can be selected from the group consisting of hydrogen, alkyl groups (eg, C1-C4 alkyl groups), and aryl groups, with hydrogen being preferred.

[0101] 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 C1-C8 alkoxy or alkoxy derivatives of polyols having repeating units include alkylene oxides. The alkylene oxide may be selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. The alkylene oxide group may also be in the form of a polymeric chain known as a polyalkyleneoxy chain. The term "polyalkyleneoxy," as used herein, generally refers to a molecular structure containing the following repeating units: -CHCHO-, CHCHCHO-, -CHCHCHCHO-, -CHCH(CH)O-, -CHCH(CHCH)O-, CHCHCH(CH)O-, and any combination thereof. Exemplary of such groups are polymeric epoxides, such as polyalkylene oxides and their copolymers. Typical polyalkylene oxides and copolymers include those made from alkylene oxide monomers containing 2 to 20 carbon atoms, or more preferably 2 to 6 carbon atoms. Examples include polyethylene oxide; polypropylene oxide; polybutylene oxide; oxetane; tetrahydrofuran; copolymers of polyethylene oxide, polypropylene oxide, and polybutylene oxide; and other copolymers, including block copolymers, in which a majority of the polymer substituents are polyethylene oxide, polypropylene oxide, and / or polybutylene oxide. Furthermore, such polyalkyleneoxy groups may have an average molecular weight ranging from about 132 to about 10,000, preferably from about 176 to about 5,000.

[0102] Typically, the alkoxy moieties cap the ends of the chains that make up the polymeric thiophene hue modifier. Thus, the resulting alkoxylated polymeric thiophene hue modifier may have an average degree of alkoxylation of from 0.5 to 50, or from 1 to 50, or from 1 to 30, or from 1 to 20, or from 1 to 10, or from 2 to 50, or from 2 to 30, or from 2 to 20, or from 2 to 10, or from 3 to 50, or from 3 to 30, or from 3 to 20, or from 3 to 10, or from 4 to 50, or from 4 to 30, or from 4 to 20, or from 4 to 10.

[0103] The textile substrates treated with the laundry care composition(s) comprised of the polymeric thiophene hue adjuster(s) of the present invention may be comprised of synthetic fibers, natural fibers, or a combination 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 repeating 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 repeating ester groups (-C(O)-O-). 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. "Polyamides" include, for example, poly-p-phenylene teraphthalamide (i.e., Kevlar®), poly-m-phenylene teraphthalamide (i.e., Nomex®), and combinations thereof. Natural fibers include, for example, wool, cotton, flax, and blends thereof.

[0104] The textile substrate may be formed from fibers or yarns of any size, including microdenier fibers and yarns (fibers or yarns having less than 1 denier per filament). The fibers or yarns may have a denier ranging from less than about 1 denier per filament to about 2000 denier per filament, or more preferably from less than about 1 denier per filament to about 500 denier per filament, or even more preferably from less than about 1 denier per filament to about 300 denier per filament.

[0105] Additionally, the textile substrate may be composed partially or entirely of multicomponent or bicomponent fibers or yarns, which may be separable or partially or completely separated along their length by chemical or mechanical action. The textile substrate may be composed of fibers, such as staple fibers, filaments, spun fibers, or combinations thereof.

[0106] The textile substrate may be of any type, including, but not limited to, woven, knitted, nonwoven, or a combination thereof. The textile substrate may optionally be colored by various dyeing techniques, such as hot jet dyeing with disperse dyes, vat dyeing, thermosol dyeing, pad dyeing, transfer printing, silk screening, or any other technique common in the art for equivalent textile products. The yarns or fibers comprising the textile substrate may optionally be dyed by a suitable method, such as package dyeing or solution dyeing, prior to forming the fabric.

[0107]

[0062] Examples of textile substrates include articles of apparel, such as outerwear (e.g., rain gear), workwear (e.g., uniforms), fashion apparel (e.g., shirts, pants, and other garments); draperies; household linens (e.g., table linens and napkins); residential upholstery; commercial upholstery; automotive interiors; wallpaper; floor coverings (e.g., carpets, rugs, and mats); human bedding (e.g., mattresses, mattress covers, etc.); pet bedding; outdoor fabrics (e.g., outdoor furniture, awnings, boat covers, and grill covers); medical bandages (e.g., fabrics for use in wound care); and any other article that can be treated for discoloration, where it is desirable to control (e.g., prevent, remove, and / or ameliorate) said discoloration.

[0108] The polymeric thiophene hue adjusters of the present invention may be incorporated into laundry care compositions, including, but not limited to, laundry detergents and fabric treatment compositions. As used herein, the term "laundry care composition" includes, unless otherwise indicated, cleaning and / or fabric treatment compositions in granular, powder, liquid, gel, paste, single-serving bar, and / or flake form. As used herein, the term "fabric treatment composition" includes, unless otherwise indicated, fabric softener compositions, fabric strengthening compositions, fabric regenerating compositions, and combinations thereof. Such compositions may, but need not, be rinse additive compositions.

[0109] The laundry care compositions of the present invention comprise one or more polymeric thiophene hue modifiers and laundry care ingredients. The polymeric thiophene hue modifiers may be applied to articles using a variety of application techniques. For application to textile articles, the polymeric thiophene hue modifiers are preferably included as additives in laundry detergents. Thus, application to textile articles actually occurs when the consumer adds laundry detergent to the washing machine. Similarly, in a typical laundry process, rinse-added fabric softening ("RAFS") compositions are commonly added during the rinse cycle after the detergent solution has been used and replaced with the rinse solution.

[0110] The polymeric thiophene hue modifier may be present in the laundry care composition (e.g., laundry detergent composition) in an amount from about 0.0001% to about 10% by weight of the composition, more preferably from about 0.0001% to about 5% by weight of the composition, and even more preferably from about 0.0001% to about 1% by weight of the composition.

[0111] Laundry detergent compositions contain a sufficient amount of surfactant to provide the desired cleaning characteristics. In one embodiment, the laundry detergent composition contains from about 5% to about 90% by weight, more specifically from about 5% to about 70% by weight, and even more specifically from about 5% to about 40% by weight of surfactant. The surfactant may include anionic, nonionic, cationic, zwitterionic, and / or amphoteric surfactants. In a more specific embodiment, the detergent composition contains anionic surfactants, nonionic surfactants, or mixtures thereof.

[0112] Suitable anionic surfactants useful herein can include any of the conventional anionic surfactant classes typically used in liquid detergent products, including alkyl benzene sulfonic acids and their salts, and alkoxylated or non-alkoxylated alkyl sulfate materials.

[0113]

[0068] Representative anionic surfactants include C 10~16Alkylbenzene sulfonic acid, preferably C 11~14 These are alkali metal salts of alkylbenzene sulfonates. Preferably, the alkyl group is linear, and such linear alkylbenzene sulfonates are known as "LAS." Alkylbenzene sulfonates, particularly LAS, are well known in the art. Such surfactants and their preparations are described, for example, in U.S. Pat. Nos. 2,220,099 and 2,477,383. Particularly preferred are sodium and potassium linear alkylbenzene sulfonates, in which the average number of carbon atoms in the alkyl group is about 11 to 14. 11 ~C 14 , for example, C 12、 Sodium LAS is an example of such a surfactant.

[0114] Another representative class of anionic surfactants includes the ethoxylated alkyl sulfate surfactants. Such materials are also known as alkyl ether sulfates or alkyl polyethoxylate sulfates and have the formula R'-O-(C2H4O) n -SO3M (wherein R' is C8 to C 20 wherein n is an alkyl group, n is about 1 to 20, and M is a salt-forming cation. 10 ~C 18 In a more specific embodiment, R' is C alkyl, n is about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. 12 ~C 16 where n is about 1 to 6, or even about 1 to 3 or about 1 to 1.5, and M is sodium.

[0115]

[0070] Alkyl ether sulfates are generally used in the form of mixtures containing various R' chain lengths and various degrees of ethoxylation. Often, such mixtures will inevitably also contain some non-ethoxylated alkyl sulfate materials, i.e., surfactants where n=0 in the above ethoxylated alkyl sulfate formula. Non-ethoxylated alkyl sulfates may also be added separately to the compositions of the present invention and used as or within any anionic surfactant component that may be present. Specific examples of non-alkoxylated, e.g., non-ethoxylated, alkyl ether sulfate surfactants include higher C8-C 20 They are produced by the sulfation of fatty alcohols. Typical primary alkyl sulfate surfactants have the general formula: ROSO3-M + (wherein R is typically a linear C8-C 20 In a specific embodiment, R is a C 10 ~C 15 alkyl, M is an alkali metal, and more specifically, R is C 12 ~C 14 and M is sodium.

[0116] Specific, non-limiting examples of anionic surfactants useful herein include: a) C 11 ~C 18 Alkylbenzene sulfonate (LAS); b) C 10 ~C 20 Primary branched random alkyl sulfate (AS); c) C 10 ~C 18 Secondary (2,3) alkyl sulfate; d) C 10 ~C 18 Alkyl alkoxy sulfate (AE x S) (wherein x is preferably 1 to 30); e) C preferably containing 1 to 5 ethoxy units 10 ~C 18f) mid-chain branched alkyl sulfates, such as those described in U.S. Pat. Nos. 6,020,303 and 6,060,443; g) mid-chain branched alkyl alkoxy sulfates, such as those described in U.S. Pat. Nos. 6,008,181 and 6,020,303; h) modified alkyl benzene sulfonates (MLAS), such as those 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 sulfonates (MES); and j) alpha-olefin sulfonates (AOS).

[0117] Suitable nonionic surfactants useful herein can include any of the common nonionic surfactant types typically used in liquid detergent products, including alkoxylated fatty alcohol and amine oxide surfactants. Preferred for use in liquid detergent products herein are the normally liquid nonionic surfactants.

[0118] Suitable nonionic surfactants for use herein include alcohol alkoxylate nonionic surfactants, which have the general formula: R 1 (C m H 2m O) n OH (in the formula, R 1 is C8~C 16 alkyl group, m is 2 to 4, and n is in the range of about 2 to 12. 1 is an alkyl group containing about 9 to 15 carbon atoms, more preferably about 10 to 14 carbon atoms, which may be primary or secondary. In one embodiment, the alkoxylated fatty alcohol is also an ethoxylated material containing about 2 to 12 ethylene oxide moieties per molecule, more preferably about 3 to 10 or even about 7 to 9 ethylene oxide moieties per molecule.

[0119] Alkoxylated fatty alcohol materials useful in the liquid detergent products herein often have a hydrophile-lipophile ratio (HLB) in the range of about 3 to 17. More preferably, the HLB of the materials is in the range of about 6 to 15, more preferably in the range of about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants are sold by Shell Chemical Company under the trade names Neodol and Dobanol.

[0120] Another suitable class of nonionic surfactants useful herein comprises amine oxide surfactants. Amine oxides are often referred to in the art as "semi-polar" nonionics. Amine oxides have the formula: R(EO) x (PO) y (BO) z N(O)(CH2R')2·qH2O, where R can be saturated or unsaturated, linear or branched, and can contain 8 to 20, preferably 10 to 16, carbon atoms, more preferably C 12 ~C 16 R' is a relatively long-chain hydrocarbon moiety, preferably a primary alkyl. R' is a short-chain moiety, preferably selected from hydrogen, methyl, and --CH2OH. When x + y + z is different from 0, EO is ethyleneoxy, PO is propyleneoxy, and BO is butyleneoxy. Amine oxide surfactants include C 12~14 Examples include alkyldimethylamine oxides.

[0121] Non-limiting examples of nonionic surfactants include: a) C 12 ~C 18 alkyl ethoxylates, e.g., NEODOL® nonionic surfactants by Shell; b) alkoxylate units are mixtures of ethyleneoxy and propyleneoxy units, C 6~12 Alkylphenol alkoxylates; c) C with ethylene oxide / propylene oxide block polymers 12 ~C 18Alcohols and C6-C 12 Alkylphenol condensates, such as Pluronic® by BASF; d) C phenols, as described in U.S. Pat. No. 6,150,322; 14 ~C 22 e) medium chain branched alcohols, BA; e) C, as described in U.S. Pat. No. 6,153,577, U.S. Pat. No. 6,020,303, and U.S. Pat. No. 6,093,856. 14 ~C 22 Medium Chain Branched Alkyl Alkoxylate, BAE x where x is 1 to 30; f) alkyl polysaccharides, as described in U.S. Pat. No. 4,565,647, issued Jan. 26, 1986 to Llenado; specifically, alkyl polyglycosides, as described in U.S. Pat. Nos. 4,483,780 and 4,483,779; g) polyhydroxy fatty acid amides, as described in U.S. Pat. No. 5,332,528, WO 92 / 06162, WO 93 / 19146, WO 93 / 19038, and WO 94 / 09099; and h) ether-capped poly(oxyalkylated) alcohol surfactants, as described in U.S. Pat. No. 6,482,994 and WO 01 / 42408.

[0122] In the laundry detergent compositions herein, the detersive surfactant component may comprise a combination of anionic and nonionic surfactant materials, wherein the weight ratio of anionic to nonionic materials is typically from 10:90 to 90:10, more typically from 30:70 to 70:30.

[0123] Cationic surfactants are well known in the art, non-limiting examples of which include quaternary ammonium surfactants, which may have up to 26 carbon atoms. Further examples include a) alkoxylated quaternary ammonium (AQA) surfactants, such as those described in U.S. Pat. No. 6,136,769; b) dimethylhydroxyethyl quaternary ammonium surfactants, such as those described in U.S. Pat. No. 6,004,922; c) polyamine cationic surfactants, such as those described in WO 98 / 35002, WO 98 / 35003, WO 98 / 35004, WO 98 / 35005, and WO 98 / 35006; d) cationic ester surfactants, such as those described in U.S. Pat. Nos. 4,228,042, 4,239,660, 4,260,529, and U.S. Pat. No. 6,022,844; and e) amino surfactants, specifically amidopropyldimethylamine (APA), such as those described in U.S. Pat. No. 6,221,825 and WO 00 / 47708.

[0124] Non-limiting examples of zwitterionic surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678, issued December 30, 1975, to Laughlin et al., column 19, line 38 to column 22, line 48, for example, Zwitterionic Surfactants; alkyl dimethyl betaines and coco dimethyl amidopropyl betaines, C8-C9 18 (Preferably C 12 ~C 18 ) Amine oxides, as well as sulfo and hydroxybetaines, for example, those in which the alkyl group is C8 to C 18 , preferably C 10 ~C 14 Betaines, including N-alkyl-N,N-dimethylamino-1-propanesulfonates, which may be

[0125] Non-limiting examples of zwitterionic surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, where the aliphatic radical can be straight or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678, issued December 30, 1975, Laughlin et al., column 19, lines 18-35, under "Zwitterionic Surfactants."

[0126] As noted, the compositions may be in solid form, either in the form of a tablet or particulate form, including, but not limited to, particles, flakes, etc., or the compositions may be in liquid form. Liquid detergent compositions include an aqueous, non-surface-active liquid carrier. Generally, the amount of aqueous, non-surface-active liquid carrier utilized in the compositions herein is effective to solubilize, suspend, or disperse the components of the composition. For example, the compositions may contain from about 5% to about 90% by weight, more specifically from about 10% to about 70% by weight, and even more specifically from about 20% to about 70% by weight of the aqueous, non-surface-active liquid carrier.

[0127] The most cost-effective type of aqueous, non-surface-active liquid carrier is, of course, water itself. Thus, typically, the aqueous, non-surface-active liquid carrier component will be composed mostly, 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 cosolvents or stabilizers, in addition to or instead of water. Thus, typically, the aqueous, non-surface-active liquid carrier component of a liquid detergent composition will be present in a concentration 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.

[0128] The detergent compositions may also contain bleaching agents. Suitable bleaching agents include, for example, sources of hydrogen peroxide, such as those described in detail in "Bleaching Agents (Survey)," Kirk Othmer's Encyclopedia of Chemical Technology, Fourth Edition (1992, John Wiley & Sons), Vol. 4, pp. 271-300, incorporated herein by reference. These hydrogen peroxide sources include various forms of sodium perborate and sodium percarbonate, including coated and modified forms of these compounds.

[0129] The preferred hydrogen peroxide source used herein can be any convenient source, including hydrogen peroxide itself. For example, perborates, such as sodium perborate (any hydrate, but preferably the mono- or tetrahydrate), sodium carbonate perhydrogenate or an equivalent percarbonate, sodium pyrophosphate perhydrogenate, urea perhydrogenate, or sodium peroxide, can be used herein. Sources of available oxygen, such as persulfate bleach (e.g., OXONE manufactured by DuPont), are also useful. Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.

[0130] Suitable percarbonate bleaching agents comprise dry particles having an average particle size ranging from about 500 micrometers to about 1,000 micrometers, with no more than about 10% by weight of the particles being smaller than about 200 micrometers and no more than about 10% by weight of the particles being greater than about 1,250 micrometers. The percarbonate can optionally be coated with silicates, borates, or water-soluble surfactants. Percarbonates are available from a variety of suppliers, including FMC, Solvay, and Tokai Denka.

[0131] The compositions of the present invention may also contain a chlorine bleaching material as the bleaching agent. Such agents are well known in the art and include, for example, sodium dichloroisocyanurate ("NaDCC"). However, chlorine bleaches are less preferred in compositions containing enzymes.

[0132]

[0087] (a) bleaching activator Preferably, the peroxygen bleach component in the composition is combined with an activator (peracid precursor). The activator is present at a level of from about 0.01% by weight of the composition, preferably from about 0.5% by weight, more preferably from about 1% to about 15% by weight, preferably up to about 10% by weight, more preferably up to about 8% by weight. A bleach activator, as used herein, is any compound that, when used with hydrogen peroxide, results in the in situ generation of a peracid corresponding to the source of the bleach activator. Various non-limiting examples of activators are disclosed in U.S. Pat. Nos. 5,576,282; 4,915,854; and 4,412,934. See also U.S. Pat. No. 4,634,551 for other exemplary bleaches and activators useful herein.

[0133]

[0088] Preferred activators are tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulfonate (C 10 Preferably, the bleach activator is selected from the group consisting of benzoyl caprolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS), perhydrolyzable esters, and mixtures thereof, most preferably benzoyl caprolactam and benzoyl valerolactam. Particularly preferred bleach activators in the pH range of about 8 to about 11 are selected from those having an OBS or VL leaving group.

[0134] Preferred hydrophobic bleach activators include nonanoyloxybenzenesulfonate (NOBS); 4-[N-(nonanoyl)aminohexanoyloxy]-benzenesulfonate sodium salt (NACA-OBS), an example of which is described in U.S. Pat. No. 5,523,434; dodecanoyloxybenzenesulfonate (LOBS or C 12 -OBS); 10-undecenoyloxybenzenesulfonate (UDOBS or C11-OBS with unsaturation at the 10 position); and decanoyloxybenzoic acid (DOBA).

[0135]

[0090] Preferred bleach 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 Mitchel et al.; and U.S. Patent No. 4,412,934 to Chung et al., and co-pending patent application Ser. No. 08 / 064,564, all of which are incorporated herein by reference.

[0136]

[0091] The molar ratio of peroxygen source (as AvO) to bleach activator in the present invention generally ranges from at least 1:1, preferably from about 20:1, more preferably from about 10:1, to about 1:1, preferably to about 3:1.

[0137] Quaternary-substituted bleach activators may also be included. The laundry compositions of the present invention preferably contain a quaternary-substituted bleach activator (QSBA) or a quaternary-substituted peracid (QSP, preferably a quaternary-substituted percarboxylic acid or a quaternary-substituted peroxyimidic acid); more preferably, the former. Preferred QSBA structures are further described 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.

[0138] Highly preferred bleach activators useful herein are amide-substituted, as described in U.S. Patent Nos. 5,698,504; 5,695,679; and 5,686,014, each of which is herein above-cited. Preferred examples of such bleach activators include (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decaneamidocaproyl)oxybenzenesulfonate, and mixtures thereof.

[0139] Other useful activators are disclosed in U.S. Pat. Nos. 5,698,504; 5,695,679; and 5,686,014, each of which is herein cited above, and U.S. Pat. No. 4,966,723 to Hodge et al. These activators include benzoxazine-type activators, such as those having a 1,2-position bond to -C(O)OC(R 1 )=N-moiety fused to a C6H4 ring.

[0140] Nitriles, such as acetonitrile and / or ammonium nitriles and other quaternary nitrogen-containing nitriles, are another class of activating agents useful herein. Non-limiting examples of such nitrile bleach activators are described in U.S. Pat. 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; and 5,004,558; as well as European Patent Nos. 790 244, 775 127, 1 017 773, and 1 017 776; and WO 99 / 14302, WO 99 / 14296, and WO 96 / 40661, all of which are incorporated herein by reference.

[0141] Depending on the activator and the specific application, good bleaching results can be obtained from bleaching systems having an in-use pH of about 6 to about 13, preferably about 9.0 to about 10.5. For example, for pH ranges near or below neutral, activators with electron-withdrawing moieties are typically used. Alkalis and buffers can be used to ensure such a pH.

[0142] Acyl lactam activators, particularly acyl caprolactams (see, for example, WO 94-28102A) and acyl valerolactams (see U.S. Patent No. 5,503,639 to Willey et al., incorporated herein by reference), as described in U.S. Patent Nos. 5,698,504; 5,695,679; and 5,686,014, each of which is cited herein above, are very useful herein.

[0143]

[0098] (b) Organic peroxides, especially diacyl peroxidesThese are extensively described in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982, pp. 27-90, especially pp. 63-72, all of which are incorporated herein by reference. If a diacyl peroxide is used, it is preferably one that has minimal adverse effects on fabric care, including color care.

[0144]

[0099] (c) Metal-containing bleach catalyst The compositions and methods of the present invention may also optionally include a metal-containing bleach catalyst, preferably a manganese- and cobalt-containing bleach catalyst.

[0145] One type of metal-containing bleach catalyst is a catalyst system containing a transition metal cation having a defined bleach catalytic activity (e.g., copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cation), an auxiliary metal cation having little or no bleach catalytic activity (e.g., zinc or aluminum cation), and a sequestering agent having a defined stability constant for the catalyst and auxiliary metal cation, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid), and water-soluble salts thereof. Such catalysts are disclosed in U.S. Patent No. 4,430,243 to Bragg.

[0146]

[0101] Manganese Metal Complexes If desired, the compositions herein can be catalyzed by a manganese compound. Such compounds and their extent of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Patent Application Publication Nos. 549,271A1; 549,272A1; 544,440A2; and 544,490A1. Preferred examples of these catalysts include Mn IV 2(uO)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII 2(uO)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(ClO4)2, Mn IV 4(uO)6(1,4,7-triazacyclononane)4(ClO4)4, Mn III Mn IV 4(uO)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2(ClO4)3, Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Patent Nos. 4,430,243 and 5,114,611. The use of manganese with various complexing ligands to enhance bleaching has also been reported in 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.

[0147]

[0102] Cobalt metal complexes Cobalt bleach catalysts useful herein are known and are described, for example, in U.S. Pat. Nos. 5,597,936; 5,595,967; and 5,703,030; and M.L. Tobe, "Base Hydrolysis of Transition-Metal Complexes," Adv. Inorg. Bioinorg. Mech., (1983), 2, pp. 1-94. The most preferred cobalt catalysts useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc]Ty (where "OAc" represents the acetate moiety and "Ty" represents the anion), especially cobalt pentaamine acetate chloride [Co(NH3)5OAc]Cl2; and [Co(NH3)5OAc](OAc)2; [Co(NH3)5OAc](PF6)2; [Co(NH3)5OAc](SO4); [Co(NH3)5OAc](BF4)2; and [Co(NH3)5OAc](NO3)2 (herein "PAC").

[0148] These cobalt catalysts can be prepared by known procedures, e.g., as described in U.S. Pat. Nos. 6,302,921; 6,287,580; 6,140,294; 5,597,936; 5,595,967; and 5,703,030; Tobe and the references cited therein; and U.S. Pat. No. 4,810,410; J. Chem., ed. (1989), 66(12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. 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, pp. 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952).

[0149]

[0104] Transition metal complexes of macropolycyclic rigid ligands The compositions herein may also suitably include a transition metal complex of a macropolycyclic rigid ligand as a bleach catalyst, preferably in a catalytically effective amount, preferably at least about 1 ppb, e.g., up to about 99.9%, more typically at least about 0.001 ppm, and preferably from about 0.05 ppm to about 500 ppm ("ppb" means parts per billion by weight, and "ppm" means parts per million by weight).

[0150] Suitable macrocyclic rigid ligand transition metal bleach catalysts for use in the compositions of the present invention include generally known compounds, but are more preferably any of the numerous novel compounds specifically designed for the laundry or laundry applications of the present invention, including, but not limited to, any of the following: Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) Diaqua-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) hexafluorophosphate Diaqua-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) hexafluorophosphate Aqua-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(III) hexafluorophosphate Diaqua-5,12-dimethyl-1,5,8,12-tetraazabicyclo[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) hexafluorophosphate Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane manganese(II) Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane manganese(II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane manganese(II)

[0106] As a practical matter, and not by way of limitation, the compositions and methods herein can be adjusted to provide active bleach catalyst species in a composition comprising a lipophilic fluid and a bleaching system on the order of at least parts per million, preferably resulting in 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 active bleach catalyst species in a composition comprising a lipophilic fluid and a bleaching system.

[0151]

[0107] (d) bleaching-enhancing compounds The compositions herein may also include one or more bleach boosting compounds. The bleach boosting compounds increase bleaching effectiveness in low temperature applications. The bleach boosting compounds work in conjunction with conventional peroxygen bleaching sources to increase bleaching effectiveness. Typically, this is achieved by in situ generation of an active oxygen transfer agent, such as a dioxirane, oxaziridine, or oxaziridinium. Alternatively, preformed dioxiranes, oxaziridines, and oxaziridiniums may be used.

[0152] Included among the bleach boost compounds suitable for use in accordance with the present invention are cationic imines, zwitterionic imines, anionic imines, and / or polyionic imines, and mixtures thereof, having a net charge of from about +3 to about -3. These imine bleach boost compounds of the present invention include compounds having the general structural formula:

[0153] [ka]

[0154] [In the formula, R 1 ~R 4 may be hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic, alkyl, and cycloalkyl radicals. Examples include:

[0155]

[0109] Among the preferred bleach boosting compounds are zwitterionic bleach boosters, which are described in U.S. Patent Nos. 5,576,282 and 5,718,614. Other bleach boosting compounds include cationic bleach boosters, which are described in U.S. Patent Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 5,482,515; and 5,550,256; and WO 95 / 13351, WO 95 / 13352, and WO 95 / 13353.

[0156]

[0110] Peroxygen sources are well known in the art, and the peroxygen source utilized in the present invention may include any of these well-known peroxygen sources, including peroxygen source compounds as well as compounds that generate effective amounts of peroxygen in situ under consumer use conditions. The peroxygen source may include a source of hydrogen peroxide, in situ generation of peroxygen anion by reaction of a hydrogen peroxide source with a bleach activator, a preformed peroxygen compound, or a mixture of suitable peroxygen sources. Of course, those skilled in the art will recognize that other peroxygen sources may be utilized without departing from the scope of the present invention. A bleach boosting compound, when present, is preferably utilized in conjunction with the peroxygen source in the bleaching systems of the present invention.

[0157]

[0111] (e) Preformed peracid Preformed peracids are also suitable as bleaching agents. As used herein, a preformed peracid compound is any convenient compound that is stable and generates an effective amount of peracid or peracid anion under consumer use conditions. The preformed peracid compound may be selected from the group consisting of percarboxylic acids and their salts, percarbonic acids and their salts, perimidic acids and their salts, peroxymonosulfuric acids and their salts, and mixtures thereof. Examples of these compounds are described in U.S. Patent No. 5,576,282 to Miracle et al.

[0158] One class of suitable organic peroxycarboxylic acids has the general formula:

[0159] [ka]

[0160] [In the formula, R is an alkylene or substituted alkylene group containing 1 to about 22 carbon atoms, or a phenylene or substituted phenylene group; Y is hydrogen, halogen, alkyl, aryl, —C(O)OH, or —C(O)OOH. It has.

[0161] Organic peroxyacids suitable for use in the present invention can contain one or two peroxy groups and can be aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula:

[0162] [ka]

[0163] [In the formula, Y can be, for example, H, CH, CHCl, C(O)OH, or C(O)OOH; n is an integer between 0 and 20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

[0164] [ka]

[0165] [In the formula, Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C(O)OH, or C(O)OOH. It has.

[0166] Typical monoperoxyacids useful herein include alkyl and aryl peroxyacids, such as: (i) Peroxybenzoic acid and ring-substituted peroxybenzoic acids, such as peroxy-α-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o-carboxybenzamidoperoxyhexanoic acid (sodium salt); (ii) aliphatic, substituted aliphatic, and arylalkyl monoperoxyacids, such as peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-(3-octyl succinoyl) aminoperoxycaproic acid (SAPA), and N,N-phthaloylaminoperoxycaproic acid (PAP); (iii) amidoperoxyacids, such as monononylamides of peroxysuccinic acid (NAPSA) or peroxyadipic acid (NAPAA) Examples include:

[0167] Typical diperoxyacids useful herein include alkyl diperoxyacids and aryl diperoxyacids, such as: (i) 1,12-diperoxydodecanedioic acid; (ii) 1,9-diperoxyazelaic acid; (iii) diperoxybrassylic acid; diperoxysebacic acid, and diperoxyisophthalic acid; (iv) 2-decyldiperoxybutane-1,4-dioic acid; (v) 4,4'-sulfonylbisperoxybenzoic acid Examples include:

[0168] Such bleaching agents are disclosed 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 6-nonylamino-6-oxoperoxycaproic acid, as described in U.S. Patent No. 4,634,551 to Burns et al. Persulfate compounds, such as OXONE, manufactured and sold by EI DuPont de Nemours of Wilmington, Del., can also be used as a suitable source of peroxymonosulfuric acid. PAP is disclosed, for example, in U.S. Patent Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757; and 5,132,431.

[0169]

[0116] (f) Photobleaching agent Suitable photobleaches for use in treating the compositions of the present invention include, but are not limited to, those described in US Pat. Nos. 4,217,105 and 5,916,481.

[0170]

[0117] (g) Enzyme bleaching Enzyme systems may be used as bleaching agents. Hydrogen peroxide may also be present by adding an enzyme system (i.e., an enzyme and its substrate) capable of producing hydrogen peroxide at the beginning or during the washing and / or rinsing process. Such enzyme systems are disclosed in European Patent Application No. 91202655.6, filed October 9, 1991.

[0171] The compositions and methods of the present invention may utilize other bleaching systems, such as ozone and chlorine dioxide. Bleaching with ozone involves adding about 20 to about 300 g / m of bleach to the solution contacting the fabric. 3This may be achieved by introducing an ozone-containing gas having an ozone content of 1:2.5 to about 1:6. The gas:liquid ratio in the solution should be maintained at 1:2.5 to about 1:6. U.S. Patent No. 5,346,588 describes a method for utilizing ozone as a replacement for conventional bleaching systems and is incorporated herein by reference.

[0172] The detergent compositions of the present invention may also contain any number of additional optional ingredients, including conventional laundry detergent composition ingredients such as non-tinting dyes, detergency builders, enzymes, enzyme stabilizers (e.g., propylene glycol, boric acid, and / or borax), suds suppressors, soil suspending agents, soil release agents, other fabric care benefit agents, pH adjusters, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structurants, dye transfer inhibitors, opacifying agents, optical brighteners, fragrances, and colorants. The various optional detergent composition ingredients, when present in the compositions herein, should be utilized at concentrations typically utilized to provide their desired contribution to the composition or laundry operation. Often, the total amount of such optional detergent composition ingredients can range from about 0.01% to about 50%, more preferably from about 0.1% to about 30%, by weight of the composition.

[0173] Liquid detergent compositions are in the form of aqueous solutions or homogeneous dispersions or suspensions of surfactants, polymeric thiophene hue modifiers, and certain other optional ingredients (some of which may be in normally solid form) in combination with the normally liquid components of the composition, such as liquid alcohol ethoxylate nonionics, aqueous liquid carriers, and any other normally liquid optional ingredients. Such solutions, dispersions, or suspensions are acceptably phase stable and typically have viscosities in the range of about 100 to 600 cps, more preferably about 150 to 400 cps. For purposes of this invention, viscosity is measured using a Brookfield LVDV-II+ viscometer using a #21 spindle.

[0174] The liquid detergent compositions herein can be prepared by combining these ingredients in any convenient order and mixing, e.g., stirring, the resulting combination of ingredients to form a phase-stable liquid detergent composition. A preferred process for preparing such compositions involves forming a liquid matrix containing at least a majority, and preferably substantially all, of the liquid components, e.g., nonionic surfactant, non-surface-active liquid carrier, and any other optional liquid components, and thoroughly mixing these liquid components by applying shear agitation to the liquid combination. For example, rapid stirring using a mechanical stirrer can be effectively utilized. While shear agitation is maintained, any anionic surfactant and substantially all of the solid ingredients can be added. Agitation of the mixture continues, and if necessary, can be intensified at this point to form a solution or uniform dispersion of insoluble solid particles in the liquid phase. After some or all of the solid ingredients have been added to the stirred mixture, particles of any enzymatic material, e.g., enzyme globules, to be included are incorporated. As a variation of the composition preparation procedure described above, one or more of the solid components may be added to an agitated mixture that is a solution or slurry of particles premixed with a minor portion of one or more of the liquid components. After all of the composition components have been added, agitation of the mixture is continued for a time sufficient to form a composition having the desired viscosity and phase stability characteristics. This often involves agitation for about 30 to 60 minutes.

[0175] In an alternative embodiment for forming a liquid detergent composition, the polymeric thiophene hue modifier is first combined with one or more liquid ingredients to form a polymeric thiophene hue modifier premix, and this premix is ​​added to a composition formulation containing a substantial portion, e.g., greater than 50% by weight, more specifically greater than 70% by weight, and even more specifically greater than 90% by weight, of the remaining components of the laundry detergent composition. For example, in the methodology described above, both the polymeric thiophene hue modifier premix and the enzyme component are added at the final stage of ingredient addition. In a further embodiment, the polymeric thiophene hue modifier is encapsulated prior to addition to the detergent composition, the encapsulated polymeric thiophene hue modifier 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.

[0176] The compositions of the present invention, prepared as described above, can be used to form aqueous wash solutions for use in laundering textile substrates, such as fabrics. Generally, an effective amount of such a composition is added to water, preferably in a conventional automatic fabric washing machine, to form such an aqueous wash solution. The aqueous wash solution thus formed is then contacted with fabrics, preferably under agitation, thereby laundering the fabrics. The effective amount of the liquid detergent composition herein added to water to form the wash solution can include an amount sufficient to form about 500 to 7,000 ppm of the composition in the wash solution. More preferably, about 1,000 to about 3,000 ppm of the detergent composition herein results in the wash solution.

[0177]

[0124] Fabric Treatment Composition / Rinse-Additive Fabric Softener Composition In another specific embodiment, the polymeric thiophene hue adjusters of the present invention may be included in a fabric treatment composition. The fabric treatment composition may be comprised of at least one polymeric thiophene hue adjuster and a rinse-added fabric softening composition (also known as a "RAFS" or "rinse-added fabric softening composition"), a rinse-added fabric softening composition, or a rinse-added fabric conditioning composition. Examples of typical rinse-added fabric softening compositions can be found in U.S. Provisional Patent Application No. 60 / 687,582, filed October 8, 2004. The rinse-added fabric softening composition of the present invention may include (a) a fabric softening active ("FSA") and (b) a polymeric thiophene hue adjuster. The rinse-added fabric softening composition may include from about 1% to about 90% by weight of the FSA, more preferably from about 5% to about 50% by weight of the FSA. The polymeric thiophene hue modifier may be present in the rinse aid fabric softener composition in an amount of from about 0.5 ppb to about 50 ppm, more preferably from about 0.5 ppm to about 30 ppm.

[0178] In one embodiment of the present invention, the fabric softener active is a quaternary ammonium compound suitable for softening fabrics during the rinse step. In one embodiment, the FSA is formed from the reaction product of a fatty acid and an amino alcohol to yield a mixture of mono-, di-, and, in one embodiment, triester compounds. In another embodiment, the FSA comprises one or more softener quaternary ammonium compounds, such as, but not limited to, monoalkoxy quaternary ammonium compounds, diamide quaternary compounds, and diester quaternary ammonium compounds, or combinations thereof.

[0179] In one aspect of the invention, the FSA comprises a diester quaternary ammonium (hereinafter "DQA") compound composition. In certain embodiments of the invention, the DQA compound composition encompasses the description of diamide FSAs and FSAs with mixed amide and ester linkages as well as the diester linkages described above, all of which are referred to as DQAs.

[0180]

[0128] A first type of DQA suitable as an FSA ("DQA(1)") includes compounds of the formula: {R 4-m -N + -[(CH2) n -YR 1 ] m}X - [In the formula, Each R substituent may be hydrogen, a short chain C1-C6, preferably C1-C3 alkyl, or hydroxyalkyl group, such as methyl (most preferred), ethyl, propyl, hydroxyethyl, etc., or a poly(C 2~3 alkoxy), preferably polyethoxy, benzyl, or mixtures thereof; each m is 2 or 3; each n is 1 to about 4, preferably 2; each Y is -O-(O)C-, -C(O)-O-, -NR-C(O)-, or -C(O)-NR-, and each Y may be the same or different; Each R 1 The sum of carbons in (add 1 if Y is -O-(O)C- or -NR-C(O)-) is C 12 ~C 22 , preferably C 14 ~C 20 and each R 1 is a hydrocarbyl or substituted hydrocarbyl group; R 1 may be unsaturated or saturated, branched or linear, preferably linear; each R 1 may be the same or different, preferably they are the same; X - can be any softener compatible anion, preferably chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, phosphate, and nitrate, more preferably chloride or methyl sulfate. Preferred DQA compounds are typically made by reacting alkanolamines, such as MDEA (methyldiethanolamine) and TEA (triethanolamine), with fatty acids. Some materials typically obtained from such reactions include N,N-di(acyloxyethyl)-N,N-dimethylammonium chloride or N,N-di(acyloxyethyl)-N,N-methylhydroxyethylammonium methyl sulfate, where the acyl groups are derived from animal fats, unsaturated and polyunsaturated fatty acids, such as tallow, hydrogenated tallow, oleic acid, and / or partially hydrogenated fatty acids and / or partially hydrogenated vegetable oils, such as canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice oil, palm oil, and the like.

[0181] Non-limiting examples of suitable fatty acids are listed in U.S. Patent No. 5,759,990, column 4, lines 45-66. In one embodiment, the FSA comprises DQA (1) or other activators in addition to DQA. In yet another embodiment, the FSA comprises only DQA (1) or DQA, and is free or essentially free of any other quaternary ammonium compounds or other activators. In yet another embodiment, the FSA comprises the precursor amine used to produce DQA.

[0182] In another aspect of the invention, the FSA has the formula: [R 4-m -N (+) -R 1 m ]A - [In the formula, each m is 2 or 3, Each R 1 is C6~C 22 (Preferably C 14 ~C 20 However, less than one is about C 12 and the other is at least about 16) hydrocarbyl or substituted hydrocarbyl substituents, preferably C 10 ~C 20Alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, sometimes referred to as "alkylene"), most preferably C 12 ~C 18 alkyl or alkenyl, branched or unbranched] In one embodiment, the FSA has an iodine value (IV) of about 1 to 70; each R is H or a short chain C1-C6, preferably C1-C3 alkyl or hydroxyalkyl group, such as methyl (most preferred), ethyl, propyl, and hydroxyethyl, benzyl, or (R 2 O) 2~4 H (wherein each R 2 is C 1~6 an alkylene group; A - is a softener compatible anion, preferably chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, phosphate, or nitrate; more preferably chloride or methyl sulfate.

[0183] Examples of these FSAs include dialkydimethylammonium salts and dialkylenedimethylammonium salts, such as ditallowdimethylammonium and ditallowdimethylammonium methyl sulfate. Examples of commercially available dialkylenedimethylammonium salts that can be used in the present invention are dihydrogenated tallowdimethylammonium chloride and ditallowdimethylammonium chloride, available from Degussa under the tradenames Adogen® 442 and Adogen® 470, respectively. In one embodiment, the FSA contains other active agents in addition to DTTMAC. In yet another embodiment, the FSA contains only the compound DTTMAC and is free or essentially free of any other quaternary ammonium compounds or other active agents.

[0184] In one embodiment, the FSA includes those described in U.S. Patent Application Publication No. 2004 / 0204337A1 to Corona et al., published October 14, 2004, paragraphs 30-79. In another embodiment, the FSA is one described in U.S. Patent Application Publication No. 2004 / 0229769A1 to Smith et al., published November 18, 2005, paragraphs 26-31; or U.S. Patent No. 6,494,920, column 1, line 51 (see details on "esterquat," i.e., quaternized fatty acid triethanolamine ester salts).

[0185] In one embodiment, the FSA is selected from at least one of the following: ditallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated tallowoyloxyethyl dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methyl sulfate, dihydrogenated tallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated tallowoyloxyethyl dimethyl ammonium chloride, or combinations thereof.

[0186] In one embodiment, the FSA may also include an amide-containing compound composition. An example of a diamide-containing compound includes, but is not limited to, methyl-bis(tallowamidoethyl)-2-hydroxyethylammonium methyl sulfate (available from Degussa under the tradenames Varisoft 110 and Varisoft 222). An example of an amide-ester-containing compound is N-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl]-N-methylamine.

[0187] Another specific embodiment of the present invention provides a rinse-aid fabric softener composition further comprising a cationic starch. Cationic starches are disclosed in US 2004 / 0204337 A1. In one embodiment, the rinse-aid fabric softener composition comprises from about 0.1% to about 7%, by weight of the fabric softener composition, of the cationic starch. In one embodiment, the cationic starch is HCP401 by National Starch.

[0188]

[0136] Suitable laundry care ingredients Although not required for purposes of the present invention, the following non-limiting list of laundry care ingredients are suitable for use in laundry care compositions and may desirably be incorporated in certain embodiments of the present invention to, for example, supplement or enhance performance for treating the substrate being cleaned, or to modify the aesthetic appearance of the composition, as with perfumes, colorants, or dyes. It is understood that such ingredients are in addition to the compounds listed above for any particular embodiment. The total amount of such adjuncts may range from about 0.1% to about 50%, or even from about 1% to about 30%, by weight of the laundry care composition.

[0189] The exact nature of these additional ingredients and the extent to which they are incorporated will depend on the physical form of the composition and the nature of the operation in which it is used. Suitable laundry care ingredients include, but are not limited to, polymers, e.g., cationic polymers, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersants, clay and soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structural plasticizers, fabric softeners, carriers, hydrotropes, processing aids, and / or colorants. In addition to the disclosure below, suitable examples of such other adjuncts and their extent of use can be found in U.S. Patent Nos. 5,576,282, 6,306,812 B1, and 6,326,348 B1, which are incorporated by reference.

[0190] As noted, laundry care ingredients are not essential to Applicants' laundry care compositions. Accordingly, certain embodiments of Applicants' compositions do not contain one or more of the following adjunct materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, clay and earth soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structural plasticizers, fabric softeners, carriers, hydrotropes, processing aids, and / or colorants. However, if one or more adjuncts are present, such one or more adjuncts may be present as detailed below.

[0191] Surfactants - The compositions of the present invention may comprise a surfactant or surfactant system, which may be selected from nonionic and / or anionic and / or cationic surfactants and / or amphoteric and / or zwitterionic and / or semi-polar nonionic surfactants. The surfactant is typically present at a level of from about 0.1%, about 1%, or even about 5% by weight of the cleaning composition to about 99.9%, about 80%, about 35%, or even about 30% by weight of the cleaning composition.

[0192] Builders—The compositions of the present invention can include one or more detergent builders or builder systems. When present, the compositions typically include at least about 1% by weight of builder, or from about 5% or 10% by weight up to about 80%, 50%, or even 30% by weight of builder. Builders include, but are not limited to, alkali metal, ammonium, and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builder polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, various alkali metal, ammonium, and substituted ammonium salts of polyacetic acid, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

[0193] Chelating Agents—The compositions herein may also optionally include one or more copper, iron, and / or manganese chelating agents. If utilized, the chelating agents generally comprise from about 0.1% to about 15% by weight of the compositions herein, or even from about 3.0% to about 15% by weight of the compositions herein.

[0194] Dye Transfer Inhibitors—The compositions of the present invention may also contain one or more dye transfer inhibitors. Suitable polymeric dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidone and polyvinylimidazole, or mixtures thereof. When present in the compositions herein, the dye transfer inhibitors are present at levels from about 0.0001%, about 0.01%, or about 0.05% by weight of the cleaning composition to about 10%, about 2%, or even about 1% by weight of the cleaning composition.

[0195] Dispersants - The compositions of the present invention can also contain a dispersant. Suitable water-soluble organic materials are homopolymeric or copolymeric acids or salts thereof, where the polycarboxylic acid may contain at least two carboxyl radicals separated from each other by not more than two carbon atoms.

[0196] Enzymes—The compositions can include 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, hyaluronidases, chondroitinases, laccases, and amylases, or combinations thereof. A typical combination is a cocktail of commonly applicable enzymes such as proteases, lipases, cutinases, and / or cellulases, combined with amylases.

[0197] Enzyme Stabilizers—Enzymes for use in compositions, such as detergents, can be stabilized by a variety of techniques. The enzymes utilized herein can be stabilized by the presence in the finished composition of a water-soluble source of calcium and / or magnesium ions, with the finished composition donating these ions to the enzyme.

[0198] Catalytic Metal Complexes—Applicants' compositions may contain catalytic metal complexes. One type of metal-containing bleach catalyst is a catalyst system containing a transition metal cation having a defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cation, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cation, and a sequestering agent having a defined stability constant for the catalyst and auxiliary metal cation, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid), and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.

[0199] If desired, the compositions herein can be catalyzed by manganese compounds. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent No. 5,576,282.

[0200] Cobalt bleach catalysts useful herein are known and are described, for example, in U.S. Patent Nos. 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known procedures, for example, as taught in U.S. Patent Nos. 5,597,936 and 5,595,967.

[0201] The compositions herein may also suitably include a transition metal complex of a macropolycyclic rigid ligand (abbreviated as "MRL"). As a practical matter, and not by way of limitation, the compositions and cleaning processes herein may be tailored to provide benefit agent MRL species in the aqueous cleaning medium on the order of at least 1 part per billion, resulting in about 0.005 ppm to about 25 ppm, about 0.05 ppm to about 10 ppm, or even about 0.1 ppm to about 5 ppm MRL in the cleaning liquor.

[0202]

[0151] Preferred transition metals in the transition metal bleach catalyst include manganese, iron, and chromium. Preferred MRLs herein are special types of bridged superrigid ligands, such as 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane. Suitable transition metal MRLs are readily prepared by known procedures, for example, as taught in WO 00 / 32601 and U.S. Pat. No. 6,225,464.

[0203]

[0152] Exemplary Laundry Care Composition Formulations: Liquid detergent formulations: Table A shows examples of liquid detergent formulations containing at least one polymeric thiophene hue adjuster of the present invention.

[0204] [Table 1]

[0205] Granular detergent formulations: Table B shows examples of granular detergent formulations containing at least one polymeric thiophene hue adjuster of the present invention.

[0206] [Table 2]

[0207] Dough treatment composition: Table C shows examples of liquid fabric treatment compositions containing at least one polymeric thiophene hue adjuster of the present invention.

[0208] [Table 3]

[0209] [example]

[0153] The following examples further illustrate the above-described subject matter but, of course, should not be construed as in any way limiting its scope.

[0210] Polymeric thiophene hue adjusters of Formula I were synthesized and tested at several concentrations in laundry detergent and fabric softener compositions for their deposition during the wash cycle. Washing was performed on cotton and polyester-containing fabrics. Details of the synthesis and test results are reported in more detail below.

[0211] Test Procedure: Method for determining relative hue angle (vs. AATCC control) (Reference: WO2019075142A1): The relative hue angles imparted by the hue adjusters to cotton fabric treated according to Method I, described below, were determined as follows: a) Four swatches obtained from each solution * and b * Average the values ​​and calculate Aa using the following formula: * and Ab * We have decided: Aa * =a * s -a * c and Ab * =b * s -b * c [In the formula, The subscripts c and s refer to fabrics washed with a brightener-free AATCC heavy-duty liquid detergent (control) and fabrics washed in a laundry care composition containing a hue adjuster (sample), respectively.]; b) Aa * and Ab * If the absolute values ​​of both A and B were <0.25, the relative hue angle (RHA) was calculated. * or Ab * If the absolute value of either was >0.25, then RHA was determined using one of the following formulas: Ab * If >0, RHA = ATAN2(Aa * ,Ab * ) Ab * If <0, RHA = 360 + ATAN2(Aa * ,Ab * ) Method for determining ΔWI: For each wash solution, the WI CIE value of the swatches was calculated using the following equation: ΔWI = WI CIE (after cleaning) - WI CIE (before cleaning) Method for calculating ΔE:

[0161] L * , a * , b * values ​​and calculate the difference in L, a, and b between the measurements after washing and the measurements on the same white fabric that has not been washed with the hue adjuster, then use the equation:

[0212]

number

[0213] The values ​​were converted to Delta E values ​​by applying

[0214]

[0162] The bias for cotton is determined by the following equation:

[0215]

[0163]

[0216]

number

[0217] Method I: Wash Test Method for Determining Whitening Preparation of test fabric: Test fabrics (purchased from Testfabrics, Inc.) included bleached cotton t-shirt fabric, 60" open weave, model number 437W-60; polyester smooth knit weave, model number 730; and nylon 6,6 stretch fabric, double knit weave, model number 314. Each sample was cut to a size of 16 cm x 16 cm. Prior to use, the fabrics were conditioned by washing them in one complete cycle in a brightener-free AATCC liquid laundry detergent, followed by two rinses before drying.

[0218] Preparation of a Wash Solution Containing a Hue-Adjusting Dye A sufficient volume of wash water containing a liquid or powdered, non-brightener-containing detergent was prepared by dissolving the detergent in tap water at room temperature at a concentration of 1 gram per liter. Both Comparative Hue Adjuster 1 and Hue Adjuster 1 of the present invention were then added to the wash water in amounts to provide the same absorbance in each wash solution. This amount of hue adjuster in each experiment corresponded to approximately 3 ppm in the wash water. For multiple wash experiments, the hue adjuster was present in the wash water at 1 ppm.

[0219] Washing Procedure: Wash tests were completed using a Tergotometer. A fabric blend consisting of 63% cotton, 25% polyester, and 12% nylon was used for each wash. The total fabric in the wash water corresponded to a 25:1 liquor:fabric ratio. The fabrics were agitated at 220 rpm for 15 minutes. After washing, each fabric set was rinsed twice with tap water. After rinsing, all fabrics were dried in a dryer for 1 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 at each wash condition was used to calculate the L * , a* , b * , and WI-CIE values ​​were calculated.

[0220] Example 1

[0171] Polymeric thiophene hue adjusters were prepared according to the procedure described below.

[0221] Comparative hue modifier 1, prepared using m-toluidine 5EO according to Example 3 of U.S. Pat. No. 4,912,203, was treated under basic conditions (pH >9) to form inventive hue modifier 1. Surprisingly, when the comparative hue modifier was treated with base, no decomposition of the azo colorant was observed. Instead, selective hydrolysis of one nitrile bond to an amide may have been achieved to yield inventive hue modifier 1. These two hue modifiers were tested for the purpose of comparing them with each other.

[0222] [ka]

[0223] A round-bottom flask was charged with 13 g of comparative hue modifier 1 (25 mmol), prepared according to Example 3 of U.S. Pat. No. 4,912,203, water (33 mL), and a polyethylene glycol 200 solution containing 50% aqueous sodium hydroxide (25 mmol). The pH was >9. The mixture was heated to 90° C. for 1 hour, at which point UPLC indicated the reaction was complete. The solution was neutralized to pH 7 with acetic acid. A reddish-blue-purple solution was obtained, containing 3.5 wt. % of dissolved inventive hue modifier 1.

[0224] Using the test conditions listed above, Inventive Hue Adjuster 1 was compared to Comparative Hue Adjuster 1. Table 1 shows the improvement in whitening and change in hue angle on both cotton and polyester fabrics when treated with compositions containing Inventive Hue Adjuster 1 versus Comparative Hue Adjuster 1 on cotton fabric at 3 ppm in wash water loading.

[0225] [Table 4]

[0226] Test results on cotton fabric show an approximately 3 unit improvement in whitening performance of Inventive Hue Adjuster 1 over Comparative Hue Adjuster 1. In addition, the hue angle on fabric treated with Inventive Hue Adjuster 1 was shifted to a redder shade, which is preferred by consumers in some applications.

[0227] Using the above equation to calculate the whitening bias, the improvement in whitening on cotton treated with Inventive Hue Adjuster 1 was five times greater than on polyester fabric. In comparison, there was virtually no bias when treated with Comparative Hue Adjuster 1. The need for a hue adjuster that targets cotton rather than polyester is significant because cotton fabrics tend to yellow more over time than synthetic fabrics when exposed to light, air, and pollutants.

[0228] Furthermore, the composition containing the inventive hue adjuster 1 exhibited a leveling effect, with no change in the ΔE of the fabric after multiple washes compared to fabric washed without the inventive hue adjuster dye. This result indicates that an equilibrium hue adjustment point was reached, where the amount of dye deposited through subsequent washes equaled the dye removed from the fabric during that wash. Therefore, another advantage of the present invention is that an optimal level of hue adjustment was achieved on the fabric without staining the fabric. The test results are shown in Table 2.

[0229] [Table 5]

[0230] The whitening effect was also evaluated using mixtures of hue adjusters. Fabrics were washed according to the wash method described herein (3 ppm total hue-adjusting dye loading) while varying the ratio of inventive hue adjuster 1 to hue adjuster 2. Hue adjuster 2 is represented by the formula Y. The test results are presented in Tables 3 and 4. The test results show variation in the relative hue angle on the fabric, which may be desirable because different hues are preferred on fabrics in different regions of the world. Therefore, being able to tailor the perceived whitening benefit by adjusting the hue angle is important. The results further demonstrate that varying the ratio of the two hue adjusters (inventive hue adjuster 1 and hue adjuster 2) can target a desired hue angle of 270 to 300 on both cotton and polyester fabrics. The hue adjusters alone may result in a slightly outside-range hue angle (depending on the detergent and fabric).

[0231] [Table 6]

[0232] [Table 7]

[0233] Further testing was conducted to compare the effectiveness of each of the inventive hue adjusters 1 and 2 on cotton fabric at a dosage level of 1 ppm. The test results are presented in Table 5. The test results show that both hue adjusters develop on the fabric, but plateau after a certain number of washes, as measured by ΔE. This is advantageous in that the hue adjusters do not stain the fabric, but provide sufficient hue adjustment to remove yellowing from stained fabrics.

[0234]

[0180]

[0235] [Table 8]

[0236] It should be noted that, unlike many conventional dyes, the polymeric thiophene hue adjusters of the present invention and laundry care compositions containing same do not require the inclusion of bleach to remove excess due to over-toning of the fabric. The hue adjusters and compositions of the present invention naturally develop and plateau on the fabric in the desired amount, providing the consumer with the desired whitening effect without staining (e.g., over-toning) the fabric.

[0237]

[0182] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0238]

[0183] The use of the terms "a," "an," and "the," and similar referents in the context of describing the subject matter of this application (particularly in the context of the claims below), are to be construed as including both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise noted. References herein to ranges of values ​​are merely intended to serve as a shorthand method of referring individually to each separate value falling within that range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually referred to herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted otherwise by context. Any and all examples, or exemplary language (e.g., "such as") presented herein, is intended merely to further clarify the subject matter of this application and does not pose a limitation on the scope of the subject matter unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the subject matter described herein.

[0239] Preferred embodiments of the subject matter of this application are described herein, including the best mode known to the inventors for carrying out the claimed subject matter. Variations of these preferred embodiments will become apparent to those of skill in the art upon reading the foregoing description. The inventors anticipate that skilled artisans will utilize such variations as appropriate, and the inventors intend that the subject matter described herein may be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, this disclosure encompasses all combinations of the above-described elements in all possible variations thereof unless otherwise indicated herein or otherwise clearly contradicted by context.

Claims

[Claim 1] 1. A method for improving the whitening effect on cellulose-containing textile articles, wherein the improvement is present in an amount greater than that observed in polyester-containing textile articles, as measured by a spectrophotometer, said method comprising: (a) providing a cellulose-containing textile substrate; (b) providing a polyester-containing textile substrate; (c) treating the textile substrate of steps (a) and (b) with: (i) laundry care ingredients; and (ii) 0.0001% to 1.0% by weight of Formula I: 【Chemistry 1】 [In the formula, each A is independently selected from the group consisting of polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and each A is independently present in the range of 1 to 20 repeat units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Each R １ is H, C １～４ Alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, —COR ２ , -CH ２ COH, -COOR ２ , -COOH, -SO ３ H, —CH ２ COOH, -CH ２ CH ２ Cl, -CH=CH ２ , -CH ２ CH(OH) ２ and salts thereof; each R ２ is C １～１８ independently selected from alkyl, aryl, substituted aryl, and substituted alkyl. to a laundry care composition comprising a polymeric thiophene hue adjuster having the structure (d) measuring the whitening effect of each textile article by spectrophotometer; A method comprising:

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