Composition containing coloring agent

Abstract

The present invention relates to a laundry care composition comprising a laundry care ingredient and a polymeric thiophene coloring agent.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 983,880, filed on March 2, 2020, entitled “COMPOSITIONS CONTAINING COLORING AGENTS,” the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to a laundry care composition comprising a laundry care ingredient and a polymeric thiophene coloring agent. Background of the Invention

[0005] As consumers increasingly prefer lower temperatures and shorter wash cycles for laundry to save energy, the cleaning efficiency of laundry care compositions may not be as effective as at higher temperatures and longer wash times. Therefore, the use of coloring agents in laundry care compositions provides a technology for providing whitening effects to dirty textile products (e.g., clothes and other garments), making them look brighter and whiter even at lower wash temperatures and shorter wash cycles. The use of irritating bleaching chemicals is also undesirable because they shorten the service life of textile products and are environmentally unfriendly. In addition, in some cases, when covering up yellowing of fabrics, consumers prefer a reddish purple hue on clothes, which cannot be obtained with bleach formulations. Therefore, there is a need to improve the whitening effect of textile products treated with laundry care compositions containing coloring agents. The present invention provides a laundry care composition comprising a polymeric thiophene coloring agent, which has been shown to whiten textile products, such as cellulose-containing fabrics. Incorporating this coloring agent into a laundry care composition provides a possible and successful delivery mechanism for deposition onto a textile substrate. Each time the textile substrate is washed, the coloring agent is deposited on the textile substrate. As a result, the textile substrate continues to be whitened and the useful life of the textile article can be extended. Summary of the invention

[0006] In one aspect, the present invention is an aqueous laundry care composition comprising a laundry care ingredient and 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having a structure of Formula I:

[0007]

[0008] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; wherein each R1 is independently selected from H, C 1-4Alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2Cl, -CH=CH2, -CH2CH(OH)2 and salts thereof; wherein each R2 is independently selected from C 1-18 Alkyl, aryl, substituted aryl and substituted alkyl.

[0009] In another aspect, the present invention relates to an aqueous laundry care composition comprising a laundry care ingredient and 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having a structure of Formula I:

[0010]

[0011] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 5 polyethyleneoxy, polypropyleneoxy or polyethyleneoxy / polypropyleneoxy copolymer repeating units; wherein each R1 is independently selected from H and C 1-4 alkyl.

[0012] In yet another aspect, the present invention relates to an aqueous laundry care composition comprising a laundry care ingredient and 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having a structure of Formula II:

[0013]

[0014] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 5 polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer repeating units.

[0015] In yet another aspect, the present invention relates to a method for preparing an amide-containing polymeric thiophene colorant, wherein the amide is formed by hydrolysis of a nitrile under alkaline conditions, such as pH>9.

[0016] In another aspect, the present invention relates to a laundry care composition comprising: (1) a laundry care ingredient; (2) 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having a structure of Formula I:

[0017]

[0018] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; wherein each R1 is independently selected from H, C 1-4 Alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2Cl, -CH=CH2, -CH2CH(OH)2 and salts thereof; wherein each R2 is independently selected from C 1-18 Alkyl, aryl, substituted aryl and substituted alkyl; and (3) 0.0001 wt % to 1.0 wt % of a polymeric thiophene toner having a structure of Formula X:

[0019]

[0020] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; wherein each R1 is independently selected from H, C 1-4 Alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2Cl, -CH=CH2, -CH2CH(OH)2 and salts thereof; wherein each R2 is independently selected from C 1-18 Alkyl, aryl, substituted aryl and substituted alkyl.

[0021] In yet another aspect, the present invention relates to a laundry care composition comprising: (i) a laundry care ingredient; and (ii) 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having a structure of Formula I:

[0022]

[0023] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; wherein each R1 is independently selected from H, C 1-4Alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2Cl, -CH=CH2, -CH2CH(OH)2 and salts thereof; wherein each R2 is independently selected from C 1-18 Alkyl, aryl, substituted aryl and substituted alkyl; and wherein the laundry care composition imparts a measurable whitening effect to cellulose-containing textile articles than to polyester-containing textile articles treated with the laundry care composition, wherein the whitening effect is measured by a whiteness index on each textile article.

[0024] In another aspect, the present invention is directed to a method for measurably improving whitening effects on cellulose-containing textile articles, wherein the amount of improvement is greater than the amount observed on polyester-containing textile articles, wherein the method comprises the steps of: (a) providing a cellulose-containing textile substrate, (b) providing a polyester-containing textile substrate, (c) exposing the textile substrates of steps (a) and (b) to a laundry care composition, the laundry care composition comprising: (i) a laundry care ingredient; and (ii) 0.0001 wt% to 1.0 wt% of a polymeric thiophene coloring agent having a structure of Formula I:

[0025]

[0026] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; wherein each R1 is independently selected from H, C 1-4 Alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2Cl, -CH=CH2, -CH2CH(OH)2 and salts thereof; wherein each R2 is independently selected from C 1-18 alkyl, aryl, substituted aryl and substituted alkyl; and (d) measuring the whitening effect by evaluating the whiteness index of each textile product.

[0027] In another aspect, the present invention relates to a textile article, wherein the textile article comprises: (a) a majority by weight of cellulose fibers, and (b) a laundry care composition comprising: (i) a laundry care ingredient; and (ii) 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having a structure of Formula III:

[0028] DETAILED DESCRIPTION

[0029] The invention described herein is a laundry care composition comprising a laundry care ingredient and a polymeric thiophene coloring agent. In one aspect of the invention, the polymeric thiophene coloring agent is added to a textile article via the laundry care composition during a standard laundry wash process. The laundry care composition containing the polymeric thiophene coloring agent is added to a washing machine so that the molecules come into direct contact with the textile article. Thus, during the laundry wash process, the polymeric thiophene coloring agent is deposited on at least one surface of the textile article and improves the whitening of the treated textile article.

[0030] As used herein, the term "alkoxy" is intended to include C1-C8 alkoxy groups as well as alkoxy derivatives of polyols having repeating units such as butylene oxide, glycidyl oxide, ethylene oxide, or propylene oxide.

[0031] As used herein, unless otherwise indicated, the terms "alkyl" and "alkyl-terminated" are intended to include C2-C 100 Alkyl groups, C2-C 50 Alkyl groups, C5-C 25 Alkyl groups, or even C 10 -C 20 Alkyl group.

[0032] As used herein, unless otherwise specified, the term "aryl" is intended to include C6-C 12 Aryl group.

[0033] As used herein, unless otherwise specified, the term "arylalkyl" is intended to include C1-C 18 Alkyl groups, and in one aspect, include C1-C6 alkyl groups.

[0034] As used herein, unless otherwise indicated, the term "alkanoyl" refers to a radical of the formula -C(O)R a A monovalent group, where R a is an alkyl group, preferably C3-C 29 Alkyl group.

[0035] As used herein, unless otherwise specified, the term "alkenyl" refers to a monovalent group derived from an acyclic olefin by removing a hydrogen atom from any carbon atom. In the context of this definition, the term "acyclic olefin" refers to an acyclic hydrocarbon containing one or more carbon-carbon double bonds.

[0036] The terms "ethylene oxide," "propylene oxide," and "butylene oxide" may be referred to herein by their typical names "EO," "PO," and "BO," respectively.

[0037] 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.

[0038] The polymeric thiophene colorants suitable for use in the present invention may contain various groups, such as alkoxylated, acylated, alkylated, carbonylated, olefinated, etc., and their derivatives prepared by introducing these groups individually, alternately and / or in combination, including derivatives prepared by, for example, changing the order of adding these groups, by increasing the number and order of adding these groups, etc.

[0039] In one aspect, the present invention is an aqueous laundry care composition comprising a laundry care ingredient and 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having a structure of Formula I:

[0040]

[0041] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; wherein each R1 is independently selected from H, C 1-4 Alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2Cl, -CH=CH2, -CH2CH(OH)2 and salts thereof; wherein each R2 is independently selected from C 1-18 Alkyl, aryl, substituted aryl and substituted alkyl.

[0042] In yet another aspect, the present invention is an aqueous laundry care composition comprising a laundry care ingredient and 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having a structure of Formula I:

[0043]

[0044] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 5 polyethyleneoxy, polypropyleneoxy or polyethyleneoxy / polypropyleneoxy copolymer repeating units; wherein each R1 is independently selected from H and C 1-4 alkyl.

[0045] In yet another aspect, the present invention is an aqueous laundry care composition comprising a laundry care ingredient and 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having the structure of Formula II:

[0046]

[0047] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 5 polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer repeating units.

[0048] The polymeric thiophene hueing agent may be present in the laundry care composition in an amount from 1 ppm to 10000 ppm, or in an amount from 1 ppm to 500 ppm.

[0049] The laundry care composition may comprise water in an amount of 3% to 97% based on the total weight of the laundry care composition, or 10% to 90% based on the total weight of the laundry care composition, or even 25% to 75% based on the total weight of the laundry care composition.

[0050] The aqueous laundry care compositions of the present invention may be in liquid form, unit dose form or multi-compartment unit dose form.

[0051] Impurities may also be present in the coloring agent. Those skilled in the art will recognize that, when preparing azo dyes, impurities associated with positional isomers, incomplete reactions, or dual couplings of diazonium salts with coupling agents may be produced. Impurities may, for example, include carboxylic acids, bisamides, positional isomeric amides, or mixtures of carboxylic acids, esters, nitriles, and amides present in the thiophene portion. Therefore, the aqueous laundry care composition may also include at least one of the following structures, or a salt thereof:

[0052]

[0053] In one aspect of the present invention, the aqueous laundry care composition comprises a laundry care ingredient selected from the group consisting of cationic polymers, surfactants, builders, chelants, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, polymeric dispersants, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, pigments, colorants, perfumes, perfume delivery systems, structure elasticizers, fabric softeners, carriers, hydrotropes and processing aids.

[0054] The textile articles can be treated with the laundry care composition of the present invention. Thus, the treated textile articles can contain a polymeric thiophene coloring agent as described herein. In one aspect of the present invention, the textile articles contain cellulose-containing fibers. The textile articles can be in the form of fabrics. Thus, the present invention includes cellulose-containing fabrics containing a polymeric thiophene coloring agent as described herein.

[0055] A method of treating a textile article to improve the visual appearance of the article comprises the steps of: (1) providing a textile article, and (2) exposing the textile article to a laundry care composition comprising a polymeric thiophene coloring agent as described herein. The method of treating a textile article may also comprise the steps of: (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 of treating a textile article with the laundry care composition of the present invention, whether aqueous or non-aqueous, may be bleach-free.

[0056] A method for preparing the amide-containing polymeric thiophene toner of the present invention may include forming an amide by hydrolysis of a nitrile group under alkaline conditions, such as pH> 9. The alkaline 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.

[0057] The aqueous laundry care composition comprising the polymeric thiophene hue agent can impart a desired hue to the textile article with a relative hue angle > 270, or a relative hue angle of 270 to 310, or a relative hue angle of 290 to 310.

[0058] In yet another aspect, the present invention relates to a laundry care composition comprising: (1) a laundry care ingredient; and (2) 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having a structure of Formula I:

[0059]

[0060] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; wherein each R1 is independently selected from H, C 1-4 Alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2Cl, -CH=CH2, -CH2CH(OH)2 and salts thereof; wherein each R2 is independently selected from C 1-18 Alkyl, aryl, substituted aryl and substituted alkyl; and (3) 0.0001 wt % to 1.0 wt % of a polymeric thiophene toner having a structure of Formula X:

[0061]

[0062] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; wherein each R1 is independently selected from H, C 1-4 Alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2Cl, -CH=CH2, -CH2CH(OH)2 and salts thereof; wherein each R2 is independently selected from C 1-18 Alkyl, aryl, substituted aryl and substituted alkyl.

[0063] In yet another aspect, the present invention relates to a laundry care composition comprising: (1) a laundry care ingredient; (2) 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having a structure of Formula III:

[0064]

[0065] and (3) 0.0001 wt % to 1.0 wt % of a polymeric thiophene colorant having a structure of Formula Y:

[0066]

[0067] Each polymeric thiophene coloring agent is independently present in the laundry care composition in an amount of 1 ppm to 10000 ppm, or in an amount of 1 ppm to 500 ppm. The polymeric thiophene coloring agent of formula I and the polymeric thiophene coloring agent 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 present invention, the polymeric thiophene coloring agent of formula III and the polymeric thiophene coloring agent 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.

[0068] The laundry care composition may be in powder form, liquid form, unit dose form or multi-compartment unit dose form.

[0069] Impurities may also be present in the coloring agent. Impurities may, for example, include 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 also include at least one of the following structures, or a salt thereof:

[0070]

[0071] The laundry care ingredients may be selected from the group consisting of cationic polymers, surfactants, builders, chelants, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersants, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, pigments, colorants, perfumes, perfume delivery systems, structure elasticizers, fabric softeners, carriers, hydrotropes and processing aids.

[0072] The laundry care composition can impart a desired hue having a relative hue angle of 210 to 345, or 270 to 300, to textile articles treated therewith.

[0073] In yet another aspect of the present invention, the present invention includes a laundry care composition comprising: (i) a laundry care ingredient; and (ii) 0.0001 wt % to 1.0 wt % of a polymeric thiophene coloring agent having a structure of Formula I:

[0074]

[0075] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; wherein each R1 is independently selected from H, C 1-4 Alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2Cl, -CH=CH2, -CH2CH(OH)2 and salts thereof; wherein each R2 is independently selected from C 1-18 Alkyl, aryl, substituted aryl and substituted alkyl; and wherein the laundry care composition imparts a measurable whitening effect to cellulose-containing textile articles than to polyester-containing textile articles treated with the laundry care composition, wherein the whitening effect is measured by a whiteness index on each textile article.

[0076] The polymeric thiophene toner may be present in an amount of 1 ppm to 10000 ppm, or in an amount of 1 ppm to 500 ppm.

[0077] The cellulose-containing textile articles may exhibit at least two times the whitening effect of a polyester-containing textile substrate treated with the laundry care composition. The cellulose-containing textile articles may also exhibit at least five times the whitening effect of a polyester-containing textile substrate treated with the laundry care composition.

[0078] The polymeric thiophene coloring agent also provides a whitening deviation on cellulose-containing textile articles compared to polyester-containing textile articles, wherein the whitening deviation is measured by the following formula: Whitening Deviation = (whiteness change of cellulose-containing textile article / whiteness change of polyester-containing textile article), wherein the whitening effect is measured by the whiteness index of each textile article.

[0079] The cellulose-containing textile article may comprise fibers selected from the group consisting of cotton, linen, rayon, jute, hemp, bamboo, and blends thereof. The cellulose-containing textile article may comprise a majority by weight of cotton fibers. The cellulose-containing textile article may comprise 100% cotton fibers. The polyester-containing textile article may comprise a majority by weight of polyester fibers. The polyester-containing textile article may comprise 100% polyester fibers.

[0080] The presence of Formula I provides a hue to the cellulose-containing textile article, wherein the hue is determined by measurement of a relative hue angle. Cellulose-containing textile articles treated with the laundry care compositions of the present invention may exhibit a relative hue angle of from 280 to 345, or from 290 to 320.

[0081] Impurities may also be present in the coloring agent. Impurities may, for example, include 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 also include at least one of the following structures, or a salt thereof:

[0082]

[0083] 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 soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, pigments, colorants, perfumes, perfume delivery systems, structure elasticizers, fabric softeners, carriers, hydrotropes and processing aids.

[0084] The present invention also includes a method for increasing the whitening effect / index on a textile article, the method comprising the steps of: (i) treating the textile article with a laundry detergent 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] The present invention also includes a method for measurably improving whitening effects on cellulose-containing textile articles, wherein the amount of improvement is greater than the amount observed on polyester-containing textile articles, wherein the method comprises the steps of: (a) providing a cellulose-containing textile substrate, (b) providing a polyester-containing textile substrate, (c) exposing the textile substrates of steps (a) and (b) to a laundry care composition, the laundry care composition comprising: (i) a laundry care ingredient; and (ii) 0.0001 wt% to 1.0 wt% of a polymeric thiophene coloring agent having a structure of Formula I:

[0086]

[0087] wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; wherein each R1 is independently selected from H, C 1-4 Alkyl, alkoxyalkyl, halogen, aryl, substituted alkyl or substituted aryl, -COR2, -CH2COH, -COOR2, -COOH, -SO3H, -CH2COOH, -CH2CH2Cl, -CH=CH2, -CH2CH(OH)2 and salts thereof; wherein each R2 is independently selected from C 1-18 alkyl, aryl, substituted aryl and substituted alkyl; and (d) measuring the whitening effect by evaluating the whiteness index of each textile product.

[0088] In another aspect of the present invention, the present invention relates to a textile article, wherein the textile article comprises: (a) a majority of cellulose fibers by weight, and (b) a laundry care composition, the laundry care composition comprising: (i) a laundry care ingredient; and (ii) 0.0001 wt% to 1.0 wt% of a polymeric thiophene coloring agent having a structure of Formula III:

[0089]

[0090] In one aspect of the present invention, the polymeric thiophene toner may contain any suitable alkylene oxide group. Suitable alkylene oxide groups include those represented by the following formula (C):

[0091] (C)

[0092]

[0093] In the structure of formula (C) and the subsequent other alkyleneoxy structures, R 101 The carbon atom to which it is bonded is also bonded to the nitrogen atom of the amine group. 101 and R102 The groups are independently selected from hydrogen, alkyl, aryl, alkoxyalkyl and aryloxyalkyl. 105 is a terminal group of an oxyalkylene group and may be selected from hydrogen, an alkyl group (e.g., a C1-C4 alkyl group) and an aryl group, wherein hydrogen is preferred. Preferably, each R 101 and R 102 The groups are independently selected from hydrogen and alkyl (e.g., C1-C4 alkyl). The variable a is an integer equal to or greater than 1 (e.g., 1 to about 100). For each monomer unit in the alkyleneoxy group, R 101 and R 102 The group is independently selected from the group. Therefore, when the variable a is greater than 1, the alkylene oxide group may include two or more monomeric units, or even three or more monomeric units, covalently bonded to form the alkylene oxide group. When the alkylene oxide group includes two or more monomeric units (or even three or more monomeric units), these monomeric units may be arranged in a block configuration or a random configuration, but the block configuration is generally more preferred. In a preferred embodiment, the alkylene oxide group includes monomeric units independently selected from ethylene oxide, propylene oxide and butylene oxide. The suitable example of this alkylene oxide group is the following formula (CI):

[0094] (CI)

[0095]

[0096] In the structure of Formula (CI), the variables x, y and z are independently selected from zero and a positive integer (e.g., a positive integer 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 an oxyalkylene group and may be selected from hydrogen, alkyl (e.g., C1-C4 alkyl) and aryl, with hydrogen being preferred. In certain potentially preferred embodiments, the alkylene oxide group comprises ethylene oxide and propylene oxide monomer units arranged in a block configuration. Suitable examples of such alkylene oxide groups include those of the following formulae (CII) and (CIII):

[0097] (CII)

[0098]

[0099] (CIII)

[0100]

[0101] In the structures of Formula (CII) and (CIII), the variables t, u, v, q, r, and s are independently selected from zero and a positive integer (e.g., a positive integer from 1 to about 100). Preferably, the sum of t, u, and v, and the sum of 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 a terminal group of an oxyalkylene group, and may be selected from hydrogen, an alkyl group (eg, a C1-C4 alkyl group), and an aryl group, with hydrogen being preferred.

[0102] Alkoxylation is carried out by methods well known to those skilled in the art (see, for example, U.S. Pat. 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 suitable polyols having repeating units include oxyalkylenes. The oxyalkylenes may be selected from ethylene oxide, propylene oxide, butylene oxide and mixtures thereof. The oxyalkylene groups may be in the form of polymer chains known as polyalkylene oxide chains. As used herein, the term "polyalkylene oxide" generally refers to a molecular structure containing the following repeating units: -CH2CH2O-, CH2CH2CH2O-, -CH2CH2CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(CH2CH3)O-CH2CH2CH(CH3)O-, and any combination thereof. Typical of such groups are polymeric epoxides, such as polyoxyalkylenes and copolymers thereof. Typical polyoxyalkylenes and copolymers thereof include those prepared from oxyalkylene 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 the majority of the polymer substituents are polyethylene oxide, polypropylene oxide and / or polybutylene oxide. In addition, the average molecular weight of such polyalkylene oxide groups can be from about 132 to about 10,000, preferably from about 176 to about 5,000.

[0103] Typically, the alkoxy molecules form caps at the ends of the chains comprising the polymeric thiophene coloring agents. Thus, the resulting alkoxylated polymeric thiophene coloring agents may have an average degree of alkoxylation of 0.5 to 50, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 10, or 2 to 50, or 2 to 30, or 2 to 20, or 2 to 10, or 3 to 50, or 3 to 30, or 3 to 20, or 3 to 10, or 4 to 50, or 4 to 30, or 4 to 20, or 4 to 10.

[0104] The textile substrate treated with the laundry care composition comprising the polymeric thiophene coloring agent of the present invention may comprise synthetic fibers, natural fibers, or a combination of synthetic fibers and natural fibers. Synthetic fibers include, for example, polyesters, acrylics, polyamides, polyolefins, polyaramids, polyurethanes, regenerated cellulose (such as rayon) and blends thereof. The term "polyamide" is intended to describe any long-chain polymer having repeating amide groups (--NH—CO--) as components 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. "Polyaramids" include, for example, poly(p-phenylene terephthalamide) (e.g. ), polyisophthalamide (such as ) and combinations thereof. Natural fibers include, for example, wool, cotton, flax, and blends thereof.

[0105] The textile substrate can 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 denier of the fibers or yarns can be less than about 1 denier per filament to about 2000 denier per filament, or more preferably less than about 1 denier per filament to about 500 denier per filament, or even more preferably less than about 1 denier per filament to about 300 denier per filament.

[0106] In addition, the textile substrate may partially or completely comprise multicomponent or bicomponent fibers or yarns, which may be strippable or have been partially or completely stripped along its length by chemical or mechanical action. The textile substrate may comprise fibers, such as staple fibers, filament fibers, spun fibers, or combinations thereof.

[0107] The textile substrate can be of any kind, including but not limited to woven fabrics, knitted fabrics, nonwoven fabrics or combinations thereof. The textile substrate can optionally be colored by various dyeing techniques, such as high temperature jet dyeing with disperse dyes, vat dyeing, thermosol dyeing, pad dyeing, transfer printing, screen printing or any other common techniques used in the art for similar textile products. The yarns or fibers constituting the textile substrate can optionally be dyed by a suitable method before the fabric is formed, such as by packing dyeing or solution dyeing.

[0108] Textile substrates include, for example, articles of apparel such as outerwear (e.g., raincoats), workwear (e.g., uniforms), fashion apparel (e.g., shirts, pants, and other garments); draperies; tablecloths (e.g., tablecloths and napkins); residential interiors; commercial interiors; automotive interiors; wall coverings; floor covering products (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 dressings (e.g., fabrics for wound care); and any other article that can exhibit discoloration and for which it is desirable to control (e.g., prevent, remove, and / or ameliorate) the discoloration.

[0109] The polymeric thiophene coloring agent of the present invention can be incorporated into laundry care compositions, including but not limited to laundry detergents and fabric treatment compositions. As used herein, unless otherwise specified, the term "laundry care composition" includes granules, powders, liquids, gels, pastes, unit dose strip forms and / or sheet-type detergents and / or fabric treatment compositions. As used herein, unless otherwise specified, the term "fabric treatment composition" includes fabric softening compositions, fabric enhancing compositions, fabric refreshing compositions, and combinations thereof. Such compositions can be, but need not be, rinse agent addition compositions.

[0110] The laundry care composition of the present invention comprises one or more of a polymeric thiophene coloring agent and a laundry care ingredient. The polymeric thiophene coloring agent can be added to the article using various application techniques. In order to be applied to textile articles, the polymeric thiophene coloring agent is preferably included in a laundry detergent as an additive. Therefore, when a consumer adds laundry detergent to a washing machine, application to the textile article actually occurs. Similarly, rinse added fabric softening ("RAFS") compositions are typically added in the rinse cycle, which occurs after the detergent solution has been used and replaced with the rinse solution during a typical wash process.

[0111] The polymeric thiophene hueing agents may be present in the laundry care compositions (e.g., laundry detergent compositions) in an amount from about 0.0001 wt % to about 10 wt % of the composition, more preferably from about 0.0001 wt % to about 5 wt % of the composition, and even more preferably from about 0.0001 wt % to about 1 wt % of the composition.

[0112] The laundry detergent composition comprises a surfactant whose amount is enough to provide the desired cleaning properties. In one embodiment, the laundry detergent composition comprises a surfactant of about 5wt% to about 90wt%, and more specifically about 5wt% to about 70wt% of a surfactant, even more specifically about 5wt% to about 40wt% of a surfactant. The surfactant may include anionic, nonionic, cationic, zwitterionic and / or amphoteric surfactants. In a more specific embodiment, the detergent composition comprises anionic surfactants, nonionic surfactants or their mixtures.

[0113] Anionic surfactants suitable for use herein may include any of the conventional anionic surfactant types commonly used in liquid detergent products. These include alkylbenzene sulfonic acids and their salts, and alkoxylated or non-alkoxylated alkyl sulfate materials.

[0114] An exemplary anionic surfactant is C 10-16 Alkali metal salts of alkylbenzenesulfonic acids, preferably C 11-14 Alkali metal salts of alkylbenzene sulfonic acids. Preferably, the alkyl group is linear, and such linear alkylbenzene sulfonates are referred to as "LAS". Alkylbenzene sulfonates, particularly LAS, are well known in the art. Such surfactants and their preparation 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, wherein the average number of carbon atoms in the alkyl group is from about 11 to 14. C 11 -C 14 LAS sodium, such as C 12 Sodium LAS is a specific example of such a surfactant.

[0115] Another exemplary type of anionic surfactant includes ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylated sulfates, are those corresponding to the formula: R'--O--(C2H4O) n --SO3M, where R' is C8-C 20 alkyl group, n is about 1 to 20, and M is a salt-forming cation. In a specific embodiment, R' is C 10 -C 18 alkyl, n is about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. In more specific embodiments, R' is C12 -C 16 , n is about 1 to 6 or even about 1 to 3 or about 1 to 1.5, and M is sodium.

[0116] Alkyl ether sulfates are typically used in the form of mixtures comprising different R' chain lengths and different degrees of ethoxylation. Typically, such mixtures will inevitably also contain some non-ethoxylated alkyl sulfate material, i.e., ethoxylated alkyl sulfate surfactants of the above formula wherein n=0. Non-ethoxylated alkyl sulfates may also be added separately to the compositions of the present invention and used as or in any anionic surfactant component that may be present. Specific examples of non-alkoxylated, e.g., non-ethoxylated alkyl ether sulfate surfactants are prepared by high C8-C 20 Those produced by the sulfation of fatty alcohols. Traditional primary alkyl sulfate surfactants have the following general formula: ROSO3-M + , where R is usually a straight chain C8-C 20 A hydrocarbon group, which may be linear or branched, and M is a water-soluble cation. In a specific embodiment, R is C 10 -C 15 alkyl, M is an alkali metal, more specifically, R is C 12 -C 14 , M is sodium.

[0117] Specific non-limiting examples of anionic surfactants useful in the present invention include: a) C 11 -C 18 Alkylbenzene sulfonate (LAS); b) C 10 -C 20 Branched random primary 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) preferably C containing 1 to 5 ethoxy units 10 -C 186,060,443; g) mid-chain branched alkyl alkoxy sulfates as discussed in U.S. Pat. No. 6,008,181 and U.S. Pat. No. 6,020,303; h) modified alkylbenzene sulfonates (MLAS) as discussed in WO 99 / 05243, WO 99 / 05242, WO 99 / 05244, WO 99 / 05082, WO 99 / 05084, WO99 / 05241, WO 99 / 07656, WO 00 / 23549 and WO 00 / 23548; i) methyl ester sulfonates (MES); and j) alpha-olefin sulfonates (AOS).

[0118] Nonionic surfactants suitable for use in the present invention may include any conventional nonionic surfactant types commonly used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Preferred for use in the liquid detergent products described herein are those nonionic surfactants that are generally liquid.

[0119] Suitable nonionic surfactants for use in the present invention include alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are substances that conform to the following general formula: 1 (C m H 2m O) n OH, where R 1 For C8-C 16 An alkyl group, m is 2 to 4, and n is about 2 to 12. Preferably, R 1 The alkoxylated fatty alcohols will be ethoxylated materials containing from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule, or even from about 7 to 9 ethylene oxide moieties per molecule.

[0120] The alkoxylated fatty alcohol materials useful in the liquid detergent compositions of the present invention typically have a hydrophile-lipophile balance (HLB) of from about 3 to 17. More preferably, the material has an HLB of from about 6 to 15, most preferably from about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants are marketed by Shell Chemical Company under the trade names Neodol and Dobanol.

[0121] Another suitable type of nonionic surfactant that can be used in the present invention includes amine oxide surfactants. Amine oxides are what are generally referred to in the art as "semi-polar" nonionic materials. Amine oxides have the following formula: R(EO) x(PO) y (BO) z N(O)(CH2R')2.qH2O. In this formula, R is a relatively long chain hydrocarbon moiety, which may be saturated or unsaturated, linear or branched, and may contain 8 to 20, preferably 10 to 16 carbon atoms, and more preferably C 12 -C 16 R' is a short chain moiety, preferably selected from hydrogen, methyl and --CH2OH. When x+y+z is not 0, EO is ethyleneoxy, PO is propyleneoxy, and BO is butyleneoxy. Amine oxide surfactants are composed of C 12-14 Alkyl dimethyl amine oxides are exemplified.

[0122] Non-limiting examples of nonionic surfactants include: a) C 12 -C 18 Alkyl ethoxylates, such as those from Shell Nonionic surfactant; b) C6-C 12 Alkylphenol alkoxylate, wherein the alkoxylate units are a mixture of ethyleneoxy units and propyleneoxy units; c) C 12 -C 18 Alcohol and C6-C 12 Condensates of alkylphenols with ethylene oxide / propylene oxide block polymers, such as BASF d) C as discussed in U.S. Pat. No. 6,150,322 14 -C 22 Medium chain branched alcohol, BA; e) C as discussed 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 , wherein x is 1 to 30; f) alkyl polysaccharides as discussed in U.S. Pat. No. 4,565,647, issued Jan. 26, 1986 to Llenado; specifically alkyl glycosides as discussed in U.S. Pat. No. 4,483,780 and U.S. Pat. No. 4,483,779; g) polyhydroxy fatty acid amides as discussed in U.S. Pat. No. 5,332,528, WO 92 / 06162, WO 93 / 19146, WO 93 / 19038 and WO 94 / 09099; and h) ether-terminated poly(alkoxylated) alcohol surfactants as discussed in U.S. Pat. No. 6,482,994 and WO 01 / 42408.

[0123] In the laundry detergent composition herein, the cleaning surfactant component may include a combination of anionic surfactant materials and nonionic surfactant materials. In this case, the weight ratio of anionic surfactant to nonionic surfactant is typically 10:90 to 90:10, more typically 30:70 to 70:30.

[0124] Cationic surfactants are well known in the art, and non-limiting examples thereof include quaternary ammonium surfactants, which may have up to 26 carbon atoms. Other examples include: a) alkoxylated quaternary ammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b) dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No. 6,004,922; c) polyamine cationic surfactants as discussed in WO 98 / 35002, WO 98 / 35003, WO 98 / 35004, WO 98 / 35005 and WO 98 / 35006; d) cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042, 4,239,660, 4,260,529 and U.S. Pat. No. 6,022,844; and e) amino surfactants as discussed in U.S. Pat. No. 6,221,825 and WO 00 / 47708, particularly amidopropyl dimethylamine (APA).

[0125] 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. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin et al., at column 19, line 38 to column 22, line 48 for examples of zwitterionic surfactants; betaines, including alkyl dimethyl betaine and coconut dimethylamidopropyl betaine, C8-C 18 (Preferred C 12 -C 18 ) amine oxides and sulfonyl and hydroxy betaines, such as N-alkyl-N,N-dimethylamino-1-propane sulfonate, wherein the alkyl group can be C8-C 18 , preferably C 10 -C 14 .

[0126] The limiting examples of amphoteric surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and heterocyclic tertiary amines, wherein the aliphatic group can be straight or branched. One of the aliphatic substituents includes at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one includes anionic water-soluble groups, such as carboxyl, sulfonate, sulfate. The example of amphoteric surfactants is described in the 19th hurdle 18 to 35 rows of U.S. Patent No. 3,929,678, issued to Laughlin et al. on December 30, 1975.

[0127] As described, the composition can be in solid form (tablet or granular form), including but not limited to granules, flakes, etc., or the composition can be in liquid form. Liquid detergent compositions include an aqueous non-surface-active liquid carrier. Typically, the amount of the aqueous non-surface-active liquid carrier used in the composition herein will be effective for dissolving, suspending or dispersing the composition components. For example, the composition may include from about 5wt% to about 90wt%, more specifically from about 10wt% to about 70wt%, even more specifically from about 20wt% to about 70wt% of an aqueous non-surface-active liquid carrier.

[0128] Of course, the most cost-effective type of aqueous non-surface-active liquid carrier is water itself. Therefore, the aqueous non-surface-active liquid carrier component usually, if not completely, also mostly contains water. However, other types of water-miscible liquids, such as alkanols, glycols, other polyols, ethers, amines, etc., and mixtures thereof, can also be added to the liquid detergent composition as cosolvents or stabilizers to supplement or replace water. Therefore, the aqueous non-surface-active liquid carrier component of the liquid detergent composition is usually present in a concentration of about 5% to about 90%, more preferably about 20% to about 70%, by weight of the composition.

[0129] The detergent composition may also contain a bleaching agent. Suitable bleaching agents include, for example, hydrogen peroxide sources such as those described in detail in Kirk Othmer's Encyclopedia of Chemical Technology, 4th Edition (1992, John Wiley & Sons), Vol. 4, pp. 271-300, "Bleaching Agents (Survey)", incorporated herein. These hydrogen peroxide sources include various forms of sodium perborate and sodium percarbonate, including various coated and modified forms of these compounds.

[0130] Preferred sources of hydrogen peroxide used herein may be any convenient source, including hydrogen peroxide itself. For example, perborates such as sodium perborate (any hydrate, but preferably monohydrate or tetrahydrate), sodium peroxycarbonate hydrate or equivalent percarbonate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or sodium peroxide may be used herein. In addition, available oxygen sources are also available, such as persulfate bleach (e.g., OXONE manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Any convenient mixture of hydrogen peroxide sources may also be used.

[0131] Suitable percarbonate bleaching agents include dry particles having a mean particle size of about 500 microns to about 1000 microns, wherein the particles being no more than about 10wt% are less than about 200 microns, and the particles being no more than about 10wt% are greater than about 1250 microns. Optionally, the percarbonate can be coated with silicate, borate or a water-soluble surfactant. Percarbonate can be obtained from various commercial sources, such as FMC, Solvay and Tokai Denka.

[0132] The compositions of the present invention may also contain chlorine-type bleaching materials as bleaching agents. Such agents are well known in the art and include, for example, sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaching agents are less preferred for compositions containing enzymes.

[0133] (a) Bleach Activators -Preferably, the peroxygen bleach component in the composition is formulated with an activator (peracid precursor). The content of the activator is from about 0.01 wt %, preferably from about 0.5 wt %, more preferably from about 1 wt % to about 15 wt %, preferably about 10 wt %, more preferably about 8 wt % of the composition. The bleach activator used herein is any compound that, when used in combination with a hydrogen peroxide source, results in the in situ generation of a peracid corresponding to 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. Other typical bleaches and activators that can be used in the present invention can also be found in U.S. Pat. No. 4,634,551.

[0134] Preferred activators are selected from the group consisting of tetraacetylethylenediamine (TAED), benzoyl caprolactam (BzCL), 4-nitrobenzoyl caprolactam, 3-chlorobenzoyl caprolactam, benzoyloxybenzene sulfonate (BOBS), nonanoyloxybenzene sulfonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzene sulfonate (C 10-OBS), benzoyl valerolactam (BZVL), octanoyloxybenzene sulfonate (C8-OBS), perhydrolyzable esters and mixtures thereof, with benzoyl caprolactam and benzoyl valerolactam being most preferred. Particularly preferred bleach activators for a pH of about 8 to about 11 are those having an OBS or VL leaving group.

[0135] Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulfonate (NOBS); 4-[N-(nonanoyl)aminocaproyloxy]-benzenesulfonic acid 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 C 11 -OBS); and decanoyloxybenzoic acid (DOBA).

[0136] Preferred bleach activators are those described in: U.S. Pat. No. 5,998,350 to Burns et al.; U.S. Pat. No. 5,698,504 to Christie et al.; U.S. Pat. No. 5,695,679 to Christie et al.; U.S. Pat. No. 5,686,401 to Willey et al.; U.S. Pat. No. 5,686,014 to Hartshorn et al.; U.S. Pat. No. 5,405,412 to Willey et al.; U.S. Pat. No. 5,405,413 to Willey et al.; U.S. Pat. No. 5,130,045 to Mitchel et al.; and U.S. Pat. No. 4,412,934 to Chung et al., and co-pending patent application 08 / 064,564, all of which are incorporated herein by reference.

[0137] The molar ratio of peroxygen source (as AvO) to bleach activator herein is typically at least 1:1, preferably about 20:1, more preferably from about 10:1 to about 1:1, preferably to about 3:1.

[0138] Quaternary substituted bleach activators may also be included. The laundry detergent 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 the following patents: U.S. Pat. No. 5,686,015 to Willey et al.; U.S. Pat. No. 5,654,421 to Taylor et al.; U.S. Pat. No. 5,460,747 to Gosselink et al.; U.S. Pat. No. 5,584,888 to Miracle et al.; U.S. Pat. No. 5,578,136 to Taylor et al.; all of which are incorporated herein by reference.

[0139] Highly preferred bleach activators for use herein are amide substituted as described in U.S. Pat. Nos. 5,698,504, 5,695,679 and 5,686,014, all of which are cited above. Preferred examples of such bleach activators include: (6-octylaminocaproyl)oxybenzenesulfonate, (6-nonanoylaminocaproyl)oxybenzenesulfonate, (6-decanoylaminocaproyl)oxybenzenesulfonate and mixtures thereof.

[0140] Other useful activators are disclosed in U.S. Pat. Nos. 5,698,504, 5,695,679, and 5,686,014, each of which is cited herein above, and in U.S. Pat. No. 4,966,723 to Hodge et al. These activators include benzoxazine-type activators, such as those that react with --C(O)OC(R) at the 1,2-position. 1 ) = N-partially fused C6H4 ring.

[0141] Nitriles, such as acetonitrile and / or ammonium nitrile and other quaternary nitrogen-containing nitriles, are another class of activators useful in the present invention. Non-limiting examples of such nitrile bleach activators are described in the following patents: 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, 5,004,558; and European Patent Nos. 790 244, 775 127, 1 017 773, 1 017 776; and WO 99 / 14302, WO 99 / 14296, WO96 / 40661, all of which are incorporated herein by reference.

[0142] Depending on the activator and the precise application, good bleaching results can be obtained with a bleaching system having a pH of about 6 to about 13, preferably about 9.0 to about 10.5 when used. Typically, for example, activators having electron-withdrawing moieties are used in a pH range close to neutral or sub-neutral. Bases and buffers can be used to ensure such a pH.

[0143] Acyl lactam activators as described in U.S. Pat. Nos. 5,698,504, 5,695,679 and 5,686,014 (each cited herein above) are very useful in the present invention, especially acyl caprolactams (see, e.g., WO 94-28102 A) and acyl valerolactams (see U.S. Pat. No. 5,503,639 to Willey et al., which is incorporated herein by reference).

[0144] (b) Organic peroxides, especially diacyl peroxides - These are described in detail in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982, pp. 27 to 90, especially pp. 63 to 72, all of which is incorporated herein by reference. If a diacyl peroxide is used, it is preferably one that has the least adverse effect on fabric care, including color care.

[0145] (c) Metal-containing bleach catalysts - 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.

[0146] One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation having defined bleach catalytic activity (e.g., copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations), an auxiliary metal cation having little or no bleach catalytic activity (e.g., zinc or aluminum cations) and a chelating agent having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in Bragg, U.S. Pat. No. 4,430,243.

[0147] Manganese metal complex - If desired, the compositions herein may be catalyzed with the aid of manganese compounds. Such compounds and levels of use are well known in the art and include, for example, 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 Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1. Preferred examples of these catalysts include: Mn IV2(uO)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mn III 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. Pat. Nos. 4,430,243 and 5,114,611. The use of manganese with various complex ligands for enhancing bleaching has also been reported in the following patents: U.S. Pat. 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.

[0148] Cobalt metal complex - Cobalt bleach catalysts useful in the present invention are well known and are described, for example, in the following documents: U.S. Pat. Nos. 5,597,936, 5,595,967 and 5,703,030; and ML Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pp. 1-94. The most preferred cobalt catalyst useful in the present invention is a catalyst having the formula [Co(NH3)5OAc]T y The pentamine cobalt acetate salt, wherein "OAc" represents the acetate moiety, "T y " is an anion, particularly cobalt pentamine acetate chloride [Co(NH3)5OAc]Cl2; as well as [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").

[0149] These cobalt catalysts are readily prepared by known methods, such as taught 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's article and 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, WL Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg.Chem. ,18,1497-1502(1979); Inorg.Chem. ,21,2881-2885(1982); Inorg.Chem. ,18,2023-2025(1979);Inorg.Synthesis,173-176(1960); and Journal of Physical Chemistry,56 ,22-25(1952).

[0150] Macropolycyclic Transition Metal Complexes of Rigid Ligands - The compositions of the present invention may also suitably include transition metal complexes of polypolycyclic rigid ligands as bleach catalysts. The amount used is a catalytically effective amount, suitably about 1 ppb or more, such as up to about 99.9%, more typically about 0.001 ppm or more, preferably about 0.05 ppm to about 500 ppm (wherein "ppb" means parts per billion by weight and "ppm" means parts per million by weight).

[0151] Polymeric polycyclic rigid ligand transition metal bleach catalysts suitable for use in the compositions of the present invention may generally include known compounds meeting the definition of the present invention and, more preferably, any of a number of novel compounds specifically designed for the laundry or laundry detergent uses of the present invention, exemplified, but not limited to, by any of the following:

[0152] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0153] Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0154] 5,12-Dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II) hexafluorophosphate dihydrate

[0155] 5,12-Diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II) hexafluorophosphate dihydrate

[0156] Hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(III) hexafluorophosphate

[0157] 5,12-Dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II) tetrafluoroborate dihydrate

[0158] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(III) hexafluorophosphate

[0159] Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(III) hexafluorophosphate

[0160] Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0161] Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0162] Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0163] Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0164] Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II).

[0165] In practice and not as a limitation, the compositions and methods of the present invention can be adjusted to provide about at least one part per hundred million of active bleach catalyst material in a composition comprising a lipophilic fluid and a bleaching system, preferably 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 bleach catalyst material in the composition comprising a lipophilic fluid and a bleaching system.

[0166] (d) Bleach boosting compounds- The compositions of the present invention may contain one or more bleach boosting compounds. Bleach boosting compounds provide enhanced bleaching in low temperature applications. Bleach boosters work with traditional peroxygen bleaching sources to provide enhanced bleaching. This is usually achieved by in situ formation of active oxygen transfer agents such as dioxirane, oxaziridine or oxaziridinium. Alternatively, preformed dioxirane, oxaziridine and oxaziridinium salts may be used.

[0167] Suitable bleach boosting compounds for use according to the present invention are cationic imines, zwitterionic imines, anionic imines and / or polyionic imines having a net charge of about +3 to about -3, and mixtures thereof. These imine bleach boosting compounds of the present invention include those having the following general structure:

[0168]

[0169] Where R 1 -R 4 It may be hydrogen, or an unsubstituted or substituted group selected from phenyl, aryl, heterocycle, alkyl and cycloalkyl.

[0170] Preferred bleach boosting compounds are zwitterionic bleach boosters, which are described in U.S. Pat. Nos. 5,576,282 and 5,718,614. Other bleach boosting compounds include cationic bleach boosters as described in U.S. Pat. Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256; and WO 95 / 13351, WO 95 / 13352 and WO 95 / 13353.

[0171] Peroxygen sources are well known in the art, and the peroxygen sources used in the present invention may include any of these well known sources, including peroxygen compounds, and compounds that provide an effective amount of peroxygen in situ under consumer use conditions. The peroxygen source may include a hydrogen peroxide source that forms peracid anions in situ by reaction of the hydrogen peroxide source with a bleach activator, a preformed peracid compound, or a mixture of suitable peroxygen sources. Of course, one of ordinary skill in the art will recognize that other peroxygen sources may be used without departing from the scope of the present invention. When a bleach boosting compound is present, it is preferably used in conjunction with a peroxygen source in the bleaching system of the present invention.

[0172] (e) Pre-made peracid- Preformed peracids are also suitable for use as bleaching agents. Preformed peracid compounds as used herein are any convenient compounds that are stable and provide 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 salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof. Examples of these compounds are described in U.S. Pat. No. 5,576,282 to Miracle et al.

[0173] One class of suitable organic peroxycarboxylic acids has the general formula:

[0174]

[0175] wherein R is an alkylene or substituted alkylene group containing 1 to about 22 carbon atoms, or a phenylene or substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl, -C(O)OH, or -C(O)OOH.

[0176] Organic peroxyacids suitable for use in the present invention may contain one or two peroxy groups and may be aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the following general formula:

[0177]

[0178] wherein Y can be, for example, H, CH3, CH2Cl, C(O)OH or C(O)OOH; and n is an integer from 0 to 20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the following general formula:

[0179]

[0180] wherein Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C(O)OH or C(O)OOH.

[0181] Typical monoperoxyacids useful herein include the alkyl and aryl peroxyacids, for example:

[0182] (i) Peroxybenzoic acid and ring-substituted peroxybenzoic acids, for example peroxy-α-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate) and o-carboxybenzamidoperoxycaproic acid (sodium salt);

[0183] (ii) aliphatic monoperoxyacids, substituted aliphatic monoperoxyacids and arylalkyl monoperoxyacids, for example peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-(3-octylsuccinyl)aminoperoxycaproic acid (SAPA) and N,N-phthalamidoperoxycaproic acid (PAP);

[0184] (iii) Amide peroxyacids, for example the monononylamide of peroxysuccinic acid (NAPSA) or peroxyadipic acid (NAPAA).

[0185] Typical diperoxy acids useful herein include alkyl diperoxy acids and aryl diperoxy acids, for example:

[0186] (i) 1,12-diperoxydodecanedioic acid;

[0187] (ii) 1,9-diperoxyazelaic acid;

[0188] (iii) diperoxytridecanedioic acid, diperoxysebacic acid and diperoxyisophthalic acid;

[0189] (iv) 2-decyldiperoxybutane-1,4-dioic acid;

[0190] (v) 4,4′-Sulfonyldiperoxybenzoic acid.

[0191] Such bleaching agents are disclosed in the following patents: U.S. Pat. No. 4,483,781 to Hartman and U.S. Pat. No. 4,634,551 to Burns et al.; European Patent Application 0,133,354 to Banks et al.; and U.S. Pat. No. 4,412,934 to Chung et al. Sources also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No. 4,634,551 to Burns et al. Persulfate compounds, such as OXONE commercially produced by EI DuPont de Nemours of Wilmington (Wilmington, DE), can also be used as a suitable source of peroxymonosulfuric acid. PAP is disclosed, for example, in U.S. Pat. Nos. 5,487,818, 5,310,934, 5,246,620, 5,279,757 and 5,132,431.

[0192] (f) Photobleaching agents - Photobleaches suitable 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.

[0193] (g) Enzyme bleaching - Enzyme systems can be used as bleaching agents. Hydrogen peroxide can also be present by adding an enzyme system (i.e., enzyme and applied substrate) capable of generating hydrogen peroxide at the beginning or during the washing and / or rinsing operation. Such an enzyme system is disclosed in EP patent application 91202655.6 filed on October 9, 1991.

[0194] The compositions and methods of the present invention may utilize alternative bleaching systems such as ozone, chlorine dioxide, and the like. Bleaching using ozone may be accomplished by providing an ozone level of from about 20 to about 300 g / m 3The ozone-containing gas is introduced into the solution to be contacted with the fabric. The gas-liquid ratio in the solution should be maintained at about 1:2.5 to about 1:6. U.S. Patent No. 5,346,588 describes a method of using ozone as a replacement for traditional bleaching systems and is incorporated herein by reference.

[0195] The detergent composition of the present invention may also contain any number of other optional components. These components include conventional laundry detergent composition components, such as non-coloring dyes, detergent 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 regulators, chelating agents, montmorillonite clay, solvents, hydrotropes and phase stabilizers, structurants, dye transfer inhibitors, opacifiers, optical brighteners, perfumes and colorants. Various optional detergent composition components, if present in the composition of the present invention, should be used in concentrations conventionally used to produce the desired effect on the composition or washing operation. The total amount of such optional detergent composition components can often be from about 0.01 wt % to about 50 wt %, more preferably from about 0.1 wt % to about 30 wt % of the composition.

[0196] Liquid detergent compositions are in the form of aqueous solutions or uniform dispersions or suspensions of surfactants, polymeric thiophene coloring agents and certain optional other components (some of which may be in solid form) that have been combined with conventional liquid components of the composition, e.g., liquid alcohol ethoxylate nonionic materials, aqueous liquid carriers and any other optional components that are usually liquid. Such solutions, dispersions or suspensions will have acceptable phase stability, typically with a viscosity of about 100 cps to about 600 cps, more preferably about 150 cps to about 400 cps. For the purposes of the present invention, viscosity is measured using a Brookfield LVDV-II+ viscometer device with a #21 spindle.

[0197] Liquid detergent composition of the present invention can be prepared by combining its components in any convenient order, and by mixing, for example, stirring the resulting component composition to form a phase-stable liquid detergent composition. In the preferred method for preparing such compositions, a liquid matrix is ​​formed, which comprises at least a major part, preferably substantially all liquid ingredients, such as nonionic surfactant, non-surfactant liquid carrier and other optional liquid components, which are thoroughly mixed by shearing and stirring the liquid combination. For example, a mechanical stirrer can be generally used for rapid stirring. While maintaining shearing and stirring, substantially all components of any anionic surfactant and solid form can be added. The mixture is continuously stirred, and the stirring of the mixture can be increased at this time if necessary to form a solution or uniform dispersion of insoluble solid phase particles in the liquid phase. After some or all of the solid form materials are added to the stirred mixture, any particles of the enzyme material to be introduced, such as the pellet of the enzyme, are mixed. As a modification of the above-mentioned composition preparation process, one or more solid components can be added to the stirred mixture as a solution or slurry form of particles premixed with one or more liquid components of a smaller portion. After all the composition components have been added, stirring of the mixture is continued for a time sufficient to form a composition having the desired viscosity and phase stability characteristics. This time period involving stirring is usually about 30 minutes to 60 minutes.

[0198] In an alternative embodiment for forming a liquid detergent composition, the polymeric thiophene coloring agent is first combined with one or more liquid components to form a polymeric thiophene coloring agent premix, which is then added to a composition formulation containing a majority of the laundry detergent composition, for example, more than 50 wt%, more specifically more than 70 wt%, and more specifically more than 90 wt% of the remaining components. For example, in the above method, the polymeric thiophene coloring agent premix and the enzyme component are both added at the last stage of adding the components. In other embodiments, the polymeric thiophene coloring agent is encapsulated before being added to the detergent composition, the encapsulated polymeric thiophene coloring agent is suspended in a structured liquid, and then the suspension is added to a composition formulation containing a majority of the remaining components of the laundry detergent composition.

[0199] The composition of the present invention prepared as described above can be used to form an aqueous washing solution for washing textile substrates, for example, fabrics. Usually, an effective amount of the composition is added to the water, preferably in a traditional fully automatic washing machine for fabric washing, to form such an aqueous washing solution. Then the aqueous washing solution formed in this way is preferably contacted with the fabric to be washed by it under stirring. Here, the liquid detergent composition added in the water to form an effective amount of an aqueous washing solution can include an amount that is enough to form a composition of about 500ppm to 7000ppm in an aqueous washing liquid. More preferably, about 1000ppm to 3000ppm of detergent composition as described herein will be provided in an aqueous washing liquid.

[0200] Fabric treatment compositions / rinse added fabric softening compositions

[0201] In another embodiment, the polymeric thiophene coloring agent of the present invention may be included in a fabric treatment composition. The fabric treatment composition may include at least one polymeric thiophene coloring agent and a rinse-added fabric softening composition ("RAFS", also known as a rinse-added fabric conditioning composition). Examples of typical rinse-added softening compositions can be found in U.S. Provisional Patent Application Serial No. 60 / 687,582, filed on October 8, 2004. The rinse-added fabric softening composition of the present invention may include (a) a fabric softening active and (b) a polymeric thiophene coloring agent. The rinse-added fabric softening composition may include from about 1 wt % to about 90 wt % FSA, more preferably from about 5 wt % to about 50 wt % FSA. The polymeric thiophene coloring agent may be present in the rinse-added fabric softening 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.

[0202] In one embodiment of the invention, the fabric softening active is a quaternary ammonium compound suitable for softening fabrics in the rinse step. In one embodiment, the FSA is formed from the reaction product of a fatty acid and an amino alcohol to produce a mixture of monoester, diester 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 monoalkyl quaternary ammonium compounds, diamido quaternary ammonium compounds and diester quaternary ammonium compounds or combinations thereof.

[0203] In one aspect of the present invention, FSA comprises a diester quaternary ammonium compound (hereinafter referred to as "DQA") composition. In certain embodiments of the present invention, the DQA compound composition also includes descriptions of diamido FSA and FSA having mixed amide bonds and ester bonds as well as the aforementioned diester bonds, all referred to herein as DQA.

[0204] A first type of DQA ("DQA (1)") suitable for use as a FSA includes compounds having the formula:

[0205] {R 4-m -N + -[(CH2) n -YR 1 ] m}X -

[0206] Wherein each R substituent is hydrogen, a short chain C1-C6, preferably C1-C3 alkyl or hydroxyalkyl group, for example, methyl (most preferred), ethyl, propyl, hydroxyethyl, etc., poly (C 2-3 alkoxy), preferably polyethoxy, benzyl or a mixture 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; when Y is -O-(O)C- or -NR-C(O)-, each R 1 The sum of carbon in the body plus 1 is C 12 -C 22 , preferably C 14 -C 20 , where each R 1 is a hydrocarbon group or a substituted hydrocarbon group; it may accept R 1 is unsaturated or saturated, and is branched or linear, preferably linear; each R 1 are the same or different, and are preferably the same; X - It 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 usually prepared by reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Some materials usually obtained by this reaction include N, N-di(acyl-oxyethyl)-N, N-dimethylammonium chloride or N, N-di(acyl-oxyethyl)-N, N-methylhydroxyethyl methylammonium sulfate, wherein the acyl group is from animal fat, unsaturated and polyunsaturated fatty acids, such as tallow, hardened tallow, oleic acid, and / or partially hydrogenated fatty acids, from vegetable oils and / or partially hydrogenated vegetable oils, such as rapeseed oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, palm oil, etc.

[0207] Non-limiting examples of suitable fatty acids are listed in column 4, lines 45-66 of U.S. Pat. No. 5,759,990. In one embodiment, the FSA comprises other active substances in addition to DQA (1) or DQA. In another embodiment, the FSA comprises only DQA (1) or DQA and contains no or substantially no other quaternary ammonium compounds or other active substances. In yet another embodiment, the FSA comprises a precursor amine for preparing DQA.

[0208] In another aspect of the invention, the FSA comprises a compound identified as DTTMAC comprising the formula:

[0209] [R 4-m -N (+) -R 1 m ]A -

[0210] Where each m is 2 or 3, each R 1 C6-C 22 Hydrocarbyl, preferably C 14 -C 20 Hydrocarbyl, but not more than one having a carbon content of less than about C 12 and the others are at least about C 16 Hydrocarbyl, or substituted hydrocarbyl substituent, preferably C 10 -C 20 Alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, sometimes also referred to as "alkylene"), most preferably C 12 -C 18 alkyl or alkenyl, and it is branched or unbranched. In one embodiment, the iodine value (IV) of FSA is 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, hydroxyethyl, etc., benzyl or (R 2 O) 2-4 H, where each R 2 It is C 1-6 an alkylene group; and A - is a softener-compatible anion, preferably chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate or nitrate; more preferably chloride or methylsulfate.

[0211] Examples of these FSAs include dialkyldimethylammonium salts and dialkylenedimethylammonium salts, such as ditallowdimethylammonium and ditallowdimethylammonium methylsulfate. Examples of commercially available dialkylenedimethylammonium salts useful herein are available from Degussa under the trade names 442 and In one embodiment, the FSA comprises other active substances in addition to DTTMAC. In another embodiment, the FSA comprises only the compound of DTTMAC and contains no or substantially no other quaternary ammonium compounds or other active substances.

[0212] In one embodiment, the FSA comprises the FSA described in U.S. Patent Publication No. 2004 / 0204337A1, Corona et al., published October 14, 2004, paragraphs 30 to 79. In another embodiment, the FSA is the FSA described in U.S. Patent Publication No. 2004 / 0229769A1, Smith et al., published November 18, 2005, paragraphs 26 to 31, or in U.S. Patent No. 6,494,920, column 1, line 51 and described in detail below as "ester quaternary ammonium salts" or quaternized fatty acid triethanolamine ester salts.

[0213] In one embodiment, the FSA is selected from at least one of ditallowyloxyethyldimethylammonium chloride, dihydrogenated tallowyloxyethyldimethylammonium chloride, ditallowyldimethylammonium chloride, ditallowyloxyethyldimethylammonium methylsulfate, dihydrogenated tallowyloxyethyldimethylammonium chloride, dihydrogenated tallowyloxyethyldimethylammonium chloride, or a combination thereof.

[0214] In one embodiment, the FSA may also include a compound composition containing an amide. Examples of compounds containing diamides may include, but are not limited to, methyl-bis(tallowamidoethyl)-2-hydroxyethylammonium methyl sulfate (available from Degussa under the trade names 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.

[0215] Another specific embodiment of the present invention provides a rinse added fabric softening composition further comprising a cationic starch. Cationic starch is disclosed in US 2004 / 0204337 A1. In one embodiment, the rinse added fabric softening composition comprises from about 0.1 wt% to about 7 wt% of the fabric softening composition of the cationic starch. In one embodiment, the cationic starch is HCP401 from National Starch.

[0216] Proper clothing care ingredients

[0217] Although not necessary for the purposes of the present invention, the non-limiting list of laundry care ingredients shown below is suitable for use in laundry care compositions and may be ideally incorporated into certain embodiments of the present invention, for example, to assist or enhance the performance of treating the substrate to be cleaned, or to change the aesthetics of the composition in the case of using perfumes, colorants, dyes, etc. It should be understood that such ingredients are ingredients in addition to the components previously listed for any particular embodiment. The total amount of these adjuncts is from about 0.1 wt% to about 50 wt%, or even from about 1 wt% to about 30 wt% of the laundry care composition.

[0218] The precise nature of these other components and their incorporation amount will depend on the physical form of the composition and the nature of the operation in which it will be used. Suitable laundry care ingredients include, but are not limited to, polymers such as cationic polymers, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersants, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, other spices and spice delivery systems, structural elasticizers, fabric softeners, carriers, hydrotropes, processing aids and / or colorants. In addition to the following disclosure, suitable examples of such other adjuvants and use levels can be found in U.S. Patent Nos. 5,576,282, 6,306,812B1 and 6,326,348B1, which are incorporated herein by reference.

[0219] As mentioned above, laundry care ingredients are not essential to the applicant's laundry care compositions. Thus, certain embodiments of the applicant's compositions do not include 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 soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, other fragrances and fragrance delivery systems, structural elasticizers, fabric softeners, carriers, hydrotropes, processing aids and / or colorants. However, when one or more adjuncts are present, such one or more adjuncts may be as detailed below:

[0220] Surfactant - The composition according to the present invention may comprise a surfactant or surfactant system, wherein the surfactant 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 in an amount of about 0.1 wt%, about 1 wt%, even about 5 wt% to about 99.9 wt%, to about 80 wt%, to about 35 wt%, even to about 30 wt% of the cleaning composition.

[0221] Builders - The compositions of the present invention may contain one or more detergent builders or builder systems. If present, the composition typically contains at least about 1 wt % of a builder, or from about 5 wt % or 10 wt % to about 80 wt %, 50 wt % or even 30 wt % of said builder. Builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth metal and alkali metal carbonates, aluminosilicate builders, polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethylhydroxysuccinic acid, various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates such as mellitic acid, succinic acid, hydroxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof.

[0222] Chelating Agents - The compositions of the present invention may also optionally contain one or more copper, iron and / or manganese chelating agents. If used, chelating agents generally comprise from about 0.1 wt % to about 15 wt % of the compositions herein, or even from about 3.0 wt % to about 15 wt % of the compositions herein.

[0223] 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, polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinyl oxazolidones and polyvinylimidazoles, or mixtures thereof. When present in the compositions of the present invention, the dye transfer inhibitors are present in an amount of from about 0.0001 wt %, from about 0.01 wt %, from about 0.05 wt % to about 10 wt %, from about 2 wt %, or even about 1 wt % of the cleaning composition.

[0224] Dispersants - The compositions of the present invention may also contain dispersants. Suitable water-soluble organic materials are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid may comprise at least two carboxyl radicals separated from each other by not more than two carbon atoms.

[0225] Enzymes - The composition may 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, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, and amylases, or mixtures thereof. A typical combination is a conventionally applicable enzyme, such as a mixture of a protease, lipase, cutinase, and / or cellulase with an amylase.

[0226] Enzyme Stabilizers - Enzymes for use in compositions (eg, detergents) can be stabilized by various techniques. The enzymes employed herein can be stabilized by the presence of a water-soluble source of calcium and / or magnesium ions in the finished composition to provide such ions to the enzyme.

[0227] Catalytic Metal Complexes - Applicants' compositions may include catalytic metal complexes. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation having defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a chelating agent having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. These catalysts are disclosed in U.S. Pat. No. 4,430,243.

[0228] If desired, the compositions of the present invention may be catalyzed with the aid of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts described in U.S. Pat. No. 5,576,282.

[0229] Cobalt bleach catalysts useful herein are well known and are described, for example, in US Pat. Nos. 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known methods, such as taught in US Pat. Nos. 5,597,936 and 5,595,967.

[0230] The compositions of the present invention may also suitably contain transition metal complexes of macrocyclic polycyclic rigid ligands (abbreviated as "MRL"). In practice and without limitation, the compositions and methods of the present invention may be adjusted to provide about at least one part per hundred million of the benefit agent MRL material in the aqueous wash medium, and may provide 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 of MRL in the aqueous liquid.

[0231] Preferred transition metals in the transition metal bleach catalysts of the present invention include manganese, iron and chromium. Preferred MRLs of the present invention are special types of cross-linked ultra-rigid ligands, such as 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane. Suitable transition metal MRLs are readily prepared by known methods, such as those taught in WO 00 / 32601 and U.S. Pat. No. 6,225,464.

[0232] Exemplary laundry care composition formulations:

[0233] Liquid detergent formulations:

[0234] Table A provides examples of liquid detergent formulations comprising at least one polymeric thiophene hueing agent of the present invention.

[0235] Table A - Liquid detergent formulations containing polymeric thiophene coloring agents

[0236]

[0237]

[0238] 1 Diethylenetriaminepentaacetic acid sodium salt

[0239] 2 Diethylenetriaminepentamethylenephosphonic acid sodium salt

[0240] 3 Ethylenediaminetetraacetic acid sodium salt

[0241] 4 Packaged as a unit dose compacted preparation in polyvinyl alcohol film

[0242] Granular detergent formulations:

[0243] Table B provides examples of granular detergent formulations comprising at least one polymeric thiophene hueing agent of the present invention.

[0244] Table B - Granular detergent formulations containing polymeric thiophene coloring agents

[0245]

[0246]

[0247] Fabric treatment composition:

[0248] Table C provides examples of liquid fabric treatment compositions comprising at least one polymeric thiophene hueing agent of the present invention.

[0249] Table C - Liquid fabric treatment compositions containing polymeric thiophene hueing agents

[0250]

[0251]

[0252] a N,N-Di(tallowyloxyethyl)-N,N-dimethylammonium chloride

[0253] b Cationic starch based on ordinary corn starch or potato starch, containing 25% to 95% amylose, a degree of substitution of 0.02 to 0.09, and a viscosity value of 50 to 84 measured as water fluidity.

[0254] c A copolymer of ethylene oxide and terephthalate having the formula described in column 15, lines 1-5 of US 5,574,179, wherein each X is methyl, each n is 40, u is 4, each R 1 Mainly 1,4-phenylene moiety, each R 2 Mainly ethylene, 1,2-propylene moieties, or mixtures thereof.

[0255] d Diethylenetriaminepentaacetic acid

[0256] e Available from Rohm and Haas Co. CG

[0257] f Silicone defoamer available from Dow Corning Corp. under the trade name DC2310

[0258] g Disodium 4,4'-bis-(2-sulfostyryl)biphenyl available from Ciba Specialty Chemicals.

[0259] h Coconut methyl ethoxylated

[15] ammonium chloride available from Akzo Nobel

[0260] Example

[0261] The following examples further illustrate the above subject matter but, of course, should not be construed as limiting the scope thereof in any way.

[0262] Polymeric thiophene coloring agents of formula I were synthesized and tested for deposition at several concentrations in laundry detergent and fabric softening compositions during the wash cycle. Washing was performed on cotton and polyester fabrics. The detailed synthesis and test results are reported in detail below.

[0263] Testing process:

[0264] Method for determining relative hue angle (compared with AATCC) (reference: WO2019075142A1):

[0265] The relative hue angle delivered by the hue-coating agent to cotton fabric treated according to Method I described below was determined as follows:

[0266] a) Average the a* and b* values ​​from the 4 samples of each solution and determine Aa* and Ab* using the following formula:

[0267] Aa*=a* s –a*c and Ab*=b* s -b* c

[0268] Wherein the subscripts c and s refer to fabrics washed in an AATCC heavy-duty liquid detergent without brightener (control) and fabrics washed in a laundry care formulation containing a hueing agent (sample), respectively.

[0269] b) If the absolute values ​​of Aa* and Ab* are both < 0.25, the relative hue angle (RHA) is not calculated. If the absolute value of Aa* or Ab* is > 0.25, the RHA is determined using one of the following formulas:

[0270] For Ab*>0, RHA=ATAN2(Aa*,Ab*)

[0271] For Ab*<0, then RHA=360+ATAN2(Aa*,Ab*)

[0272] Determination method of ΔWI:

[0273] The WI CIE value for each wash solution sample was calculated using the following equation:

[0274] ΔWI=WI CIE (after washing)-WI CIE (before washing).

[0275] Calculation method of ΔE:

[0276] Take the L*, a*, b* values ​​and convert them to ΔE values ​​by calculating the difference in L, a and b between the washed measurements and the measurements of the same white cloth without washing with colorant and then applying the following equation:

[0277]

[0278] The deviation of cotton is determined by the following equation:

[0279]

[0280] Method I: Washing test method for determining whitening effect

[0281] Preparation of test fabrics:

[0282] The fabrics tested (purchased from Testfabrics, Inc.) included bleached cotton T-shirt fabric 60" open width pattern No. 437W-60, stretch polyester interlock knit fabric pattern No. 730, and elastic nylon 6,6 stretch fabric double knit pattern No. 314. Each sample was cut into a size of 16 cm x 16 cm. Prior to use, the fabrics were prepared by washing in a full cycle of AATCC liquid laundry detergent without brighteners, then rinsing the fabrics twice and drying.

[0283] Preparation of aqueous washing solution containing coloring dye:

[0284] By dissolving the detergent in tap water at room temperature with a concentration of 1 gram per liter, sufficient volumes of washing water containing liquid or powdered detergent and not containing brightener are prepared. Then comparative toner 1 and toner 1 of the present invention are added to the washing water in an amount that provides the same absorbance in each washing solution. The amount of toner in each experiment corresponds to about 3ppm in the washing water. For multiple washing experiments, toner is present in the washing water with 1ppm.

[0285] Washing procedures:

[0286] The washing test was completed using a tergotometer. Each wash used a fabric mixture consisting of 63% cotton, 25% polyester and 12% nylon. The total fabric in the wash water corresponded to a liquid: fabric ratio of 25:1. The fabric was stirred at a rate of 220rpm for 15 minutes. After washing, each group of fabrics 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 of each fabric type under each washing condition was used to calculate L*, a*, b* and WI-CIE values.

[0287] Example 1

[0288] The polymeric thiophene toner was prepared according to the following procedure.

[0289] Comparative toner 1 prepared with m-toluidine 5EO as described in Example 3 of U.S. Patent No. 4,912,203 was treated under alkaline conditions (pH>9) to form inventive toner 1. Surprisingly, no decomposition of the azo colorant was observed when the comparative toner was treated with alkali. Instead, selective hydrolysis of one nitrile bond to an amide was achieved to give inventive toner 1. For comparison purposes, these two toners were tested in comparison.

[0290]

[0291] A polyethylene glycol 200 solution containing 13 g of comparative colorant 1 (25 mmol) prepared according to Example 3 of U.S. Patent No. 4,912,203, water (33 mL) and 50% aqueous sodium hydroxide solution (25 mmol) were added to a round bottom flask. pH>9. The mixture was heated to 90°C for 1 hour, whereupon UPLC analysis showed that the reaction was complete. The solution was neutralized to pH 7 with acetic acid. A reddish purple solution containing 3.5 wt% of dissolved colorant 1 of the present invention was obtained.

[0292] Inventive Hue Agent 1 was compared to Comparative Hue Agent 1 using the test conditions listed above. Table 1 shows the improvement in whiteness and change in hue angle for cotton and polyester fabrics when treated with a composition containing Inventive Hue Agent 1 versus a composition containing Comparative Hue Agent 1 at a loading of 3 ppm in the wash water.

[0293] Table 1 - Whitening effect of coloring agent

[0294]

[0295] Test results on cotton fabrics show that Inventive Hueing Agent 1 provides almost 3 units of whitening performance improvement over Comparative Hueing Agent 1. In addition, the hue angle on fabrics treated with Inventive Hueing Agent 1 shifts toward a more reddish hue, which is preferred by consumers in some applications.

[0296] When the whitening deviation is calculated using the above equation, cotton treated with Inventive Hue Agent 1 shows a 5-fold improvement in whitening over polyester. In contrast, no actual deviation occurs when treated with Comparative Hue Agent 1. Since cotton fabrics tend to yellow more over time than synthetic fabrics when exposed to light, air, and pollutants, it is important to have a hue agent that targets cotton rather than polyester.

[0297] In addition, the composition comprising toner 1 of the present invention shows a leveling effect, wherein after multiple washes, the ΔE of the fabric does not change compared to fabrics washed without the coloring dye of the present invention. This result indicates that an equilibrium coloring point is reached, wherein the amount of dye deposited by subsequent washes is equal to the amount of dye removed from the fabric in these washes. Therefore, another advantage of the present invention is that an optimal shade level on the fabric is achieved without soiling the fabric. The test results are shown in Table 2.

[0298] Table 2 - Multiple wash data for cotton at 1 ppm in wash water

[0299]

[0300] The blend of toner is also used to evaluate the whitening effect. According to the washing method as described herein (under the total loading of the coloring dye of 3ppm), toner 1 of the present invention and toner 2 are used to wash fabrics in different ratios. Toner 2 is represented by formula Y. Test results are shown in Table 3 and Table 4. Test results have proved the change of relative hue angle on fabric, which may be desirable, because different regions of the world have different hue preferences for fabrics. Therefore, it is important to be able to regulate the perceived whitening effect by regulating the hue angle. Test results further illustrate that the ratio of these two toners (toner 1 of the present invention and toner 2) can be changed to reach the required hue angle between 270 and 300 on cotton fabric and polyester fabric. The range that the independent toner may obtain slightly exceeds the range of required hue angle (this depends on detergent and fabric).

[0301] Table 3 - Relative hue angles and colorant ratios on cotton at 3 ppm total loading in wash water

[0302]

[0303] Table 4 - Relative Hue Angles and Colorant Ratios on Polyester at 3 ppm Total Loading in Wash Water

[0304]

[0305]

[0306] Additional testing was performed to compare the performance of each of the inventive hueing agents 1 and 2 on cotton fabric at a 1 ppm loading level. The test results are shown in Table 5. The test results show that both hueing agents accumulate on the fabric, as determined by ΔE, but are stable after a certain number of washes. This is advantageous because the hueing agents do not stain the fabric, but give enough tint to eliminate yellowing of soiled fabrics.

[0307] Table 5 - Multiple wash data for fabrics at 1 ppm dye in wash water

[0308]

[0309] It should be noted that, unlike many traditional dyes, the polymeric thiophene coloring agents of the present invention and laundry care compositions containing the polymeric thiophene coloring agents do not need to contain bleach to remove excess due to over-coloring of fabrics. The coloring agents and compositions of the present invention naturally accumulate and stabilize on fabrics in the required amounts to impart the whitening effect desired by consumers without staining (e.g., over-coloring) the fabrics.

[0310] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0311] The terms "one" and "a kind of" and "said" and similar indicators used in the context of describing the subject matter of the present application (especially in the context of the attached claims) should be understood to include the singular and the plural, unless otherwise specified herein or clearly contradicted by the context. Unless otherwise specified, the terms "comprising", "having", "including" and "containing" should be interpreted as open terms (i.e., meaning "including but not limited to"). Unless otherwise specified herein, the description of the numerical range herein is intended only to be used as a shorthand method for individually referring to each individual value falling within the range, and each individual value is incorporated into this specification as if it is individually described herein. All methods described herein can be performed in any suitable order, unless otherwise specified herein or clearly contradicted by the context. The use of any and all examples or exemplary language (e.g., "for example") provided herein is intended only to better illustrate the subject matter of the present application, without limiting the scope of the subject matter, unless otherwise specified. Any language in the specification should not be interpreted as indicating that any unclaimed element is essential to the practice of the subject matter described herein.

[0312] Preferred embodiments of the subject matter of the present application are described herein, including the best mode known to the inventor for realizing the claimed subject matter. After reading the foregoing description, variations of those preferred embodiments are obvious to those of ordinary skill in the art. The inventor expects that such variations will be appropriately adopted by those skilled in the art, and the inventor intends to practice the subject matter described herein in a manner different from that specifically described herein. Therefore, the present disclosure includes all modifications and equivalents to the subject matter recorded in the attached claims when permitted by applicable law. In addition, unless otherwise stated herein or clearly contradictory to the context, the present disclosure covers any combination of the above-mentioned elements in all possible variations thereof.

Claims

1. A laundry care composition comprising: (i) a laundry care ingredient; and (2) 1 ppm to 500 ppm of a polymeric thiophene coloring agent having a structure of Formula I: wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 5 repeating units of polyethyleneoxy, polypropyleneoxy, or polyethyleneoxy / polypropyleneoxy copolymer; Wherein each R1 is independently selected from H, C 1-4 Alkyl; and wherein the laundry care composition imparts measurably greater whitening benefits to cellulose-containing textile articles than to polyester-containing textile articles treated with the laundry care composition, wherein the whitening benefits are measured by a Whiteness Index on each textile article.

2. A laundry care composition according to claim 1, wherein the cellulose-containing textile article exhibits at least twice the whitening effect as a polyester-containing textile substrate treated with the laundry care composition.

3. A laundry care composition according to claim 1, wherein said cellulose-containing textile article exhibits at least five times greater whitening performance than a polyester-containing textile substrate treated with said laundry care composition.

4. A laundry care composition according to claim 1, wherein the polymeric thiophene colorant provides a whitening deviation on a cellulose-containing textile article compared to a polyester-containing textile substrate, wherein the whitening deviation is measured by the following formula: Whitening Deviation = (whiteness change of cellulose-containing textile article / whiteness change of polyester-containing textile article), wherein the whitening effect is measured by the whiteness index of each textile article.

5. The laundry care composition of claim 1, wherein the cellulose-containing textile article comprises fibers selected from the group consisting of cotton, linen, rayon, jute, hemp, bamboo, and blends thereof.

6. A laundry care composition according to claim 5, wherein the cellulose-containing textile article comprises cotton fibers.

7. A laundry care composition according to claim 6, wherein the cellulose-containing textile article comprises a majority by weight of cotton fibers.

8. A laundry care composition according to claim 7, wherein the cellulose-containing textile article comprises 100% cotton fibers.

9. A laundry care composition according to claim 4, wherein the polyester-containing textile article comprises a majority by weight of polyester fibers.

10. A laundry care composition according to claim 9, wherein the polyester-containing textile article comprises 100% polyester fibers.

11. A laundry care composition according to claim 1, wherein the cellulose containing textile article exhibits a relative hue angle of 280 to 345.

12. A laundry care composition according to claim 1, wherein the cellulose containing textile article exhibits a relative hue angle of 290 to 320.

13. A laundry care composition according to claim 1, wherein the presence of Formula I provides a hue to the cellulose-containing textile article, wherein the hue is determined by measurement of relative hue angle.

14. The laundry care composition of claim 1, wherein the laundry care composition further comprises at least one of the following structures or a salt thereof:

15. The laundry care composition of claim 1, wherein the laundry care ingredients are selected from the group consisting of cationic polymers, surfactants, builders, chelants, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, pigments, colorants, perfumes, perfume delivery systems, structure elasticizers, fabric softeners, carriers, hydrotropes, and processing aids.

16. A method for improving the whitening effect / index on a textile product, the method comprising the following steps: (i) treating the textile article with a laundry care composition according to claim 1, and (ii) rinsing and drying the treated textile article.

17. The method of claim 16, wherein the step of treating the textile article is bleach-free.

18. A method for measurably improving whitening performance on a cellulose-containing textile article, wherein the amount of improvement is greater than that observed on a polyester-containing textile article, wherein the method comprises the steps of: (a) providing a cellulose-containing textile substrate, (b) providing a textile substrate comprising polyester, (c) exposing the textile substrate of steps (a) and (b) to a laundry care composition comprising: (i) a laundry care ingredient; and (ii) 1 ppm to 500 ppm of a polymeric thiophene coloring agent having a structure of Formula I: wherein each A is independently selected from polyethyleneoxy, polypropyleneoxy, and polyethyleneoxy / polypropyleneoxy copolymer, and wherein each A is independently present in 1 to 5 repeating units of polyethyleneoxy, polypropyleneoxy or polyethyleneoxy / polypropyleneoxy copolymer; wherein each R1 is independently selected from H, C 1-4 Alkyl; and (d) measuring the whitening effect by evaluating the whiteness index of each textile product.

19. A textile article, wherein the textile article comprises: (a) a majority by weight of cellulose fibers, and (b) a laundry care composition comprising: (i) a laundry care ingredient; and (ii) 1 ppm to 500 ppm of a polymeric thiophene coloring agent having a structure of Formula III:

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