TECHNICAL FIELD

[0001] This invention relates to polymeric colorants that do not stain clothing, plastic or metal when used in consumer products, such as laundry detergents, fabric softeners and dish detergents. The polymeric colorants contain at least one carboxymethyl capped alkyleneoxy chain to improve the fugitivity and staining properties.

BACKGROUND

[0002] A wide variety of fugitive, or non-permanent, colorants have been used to color code textiles during production and/or finishing operations to identify certain synthetic or natural fibers. Such fugitive colorants may be water fugitive, solvent fugitive or both water and solvent fugitive. Colorants containing one or more polyethyleneoxy groups wherein the polyethyleneoxy group contains at least 2 repeating ethyleneoxy units in the molecule are generally considered water fugitive colorants; whereas colorants containing one or more propyleneoxy groups having similar repeating propyleneoxy units in the molecule are considered solvent fugitive.

[0003] Fugitive colorants which include polyethylene oxide colorants are described in

U.S. Patent No. 3,157,663 to Kuhn. Such colorants are a combination of a dyestuff radical and one or more polyethyleneoxy groups. Dyestuff radicals disclosed in the patent include nitroso, nitro, azo, diphenylmethane, triphenylmethane, xanthene, acridine, methine, thiazole, indamine, azine, oxazine, or anthraquinone radicals. Preferably, such radicals are attached to the polymeric constituents of the colorant compositions by an amino nitrogen. [0004] Another type of fugitive colorant includes the alkaline-stable fugitive colorant of the triphenylmethane type as described in U.S. Patent No. 3,927,044 to Foster et al. These colorants are alkaline stable due to the use of aromatic aldehydes containing an electron withdrawing substituent in the ortho position. They are considered alkaline stable if the colorant is capable of retaining its color in an alkaline solution, such as in a solution of sodium hydroxide at a pH of 11. U.S. Patent No. 2598660 to Glickman discloses polyalkeneoxy-based triphenylmethane dyes with unusually high water solubility.

[0005] Yet another category of fugitive colorants are the ester capped alkyleneoxy fugitive colorants disclosed in U.S. Patent No. 4,167,510 to Brendle. Such fugitive colorants comprise an organic dyestuff molecule having from 1 to 5 capped alkyleneoxy units wherein the total alkyleneoxy capped units in the molecule are from 2 to about 300. The alkylene moiety of the alkyleneoxy units contains from about 2 to 4 carbon atoms and the colorants of the invention can be made water and/or organic solvent soluble depending upon the particular capping moiety employed, the presence or absence of at least one ionic group and the total number of alkyleneoxy units present in the colorant molecule. The solubility, and thus the fugitivity of the colorants may be achieved irrespective of whether the relatively large dyestuff molecule is hydrophobic or hydrophilic.

[0006] Still another category of fugitive colorants includes those disclosed in U.S.

Patent No. 4,400,320 to Keller et al. These colorants are made from an aromatic compound containing between 6 and 20 carbon atoms and a linking moiety which are converted into a hydroxyalkylated compound. A further step includes the addition of a diazo compound to the hydroxyalkylated compound to form the final product. These colorants are red or purple in nature.

[0007] U.S. Patent No. 5, 520,943 to Brendle discusses the utilization of alkyleneoxy-substituted fugitive colorants for use as spray pattern indicators. These fugitive colorants are an improvement over permanent dyes in that they are washable from most surfaces including skin, textiles, and equipment. Additionally, these water soluble polyoxyalkylene substituted colorants are remarkably less toxic than dyes to aquatic organisms. However, on exposure to porous surfaces, such as concrete or brick, spray pattern indicators of this class can leave highly visible stains than may require days or weeks to fade. The presence of visual stains on these porous surfaces is unsightly and serves no purpose after the spray has been applied.

[0008] U.S. Patent No. 7632682 to Hong et al. discloses anthraquinone colorants with improved impurity levels and staining for use in consumer products. U.S. Patent No. 8735533 to Hong et al. discloses polymeric violet anthraquinone colorants with non-staining properties for use in coloring consumer products.

[0009] None of the above patents disclose the use of a carboxymethyl capped alkyleneoxy chain to improve the fugitivity and staining properties. It is believed that the incorporation of a carboxymethyl cap on the end of the alkyleneoxy chain of polymeric colorants further increases the water solubility, while not decreasing the color strength of the colorant. This functionality reduces staining on clothing and plastics, which is a problem associated with some polymeric colorants and/or dyes. Thus, the polymeric colorants of the present invention represent a useful advancement over the prior art.

BRIEF SUMMARY

[0010] In one aspect, the invention relates to a polymeric colorant of the formula: wherein:

A is a chromophore selected from nitro, nitroso, monazo, bisazo, diarylmethane, triarylmethane, acridine, ethine, thiazole, indamine, oxazine, pthalocyanine, or anthraquinone;

Ri is selected from nitrogen, oxygen, or sulfur;

R2 is hydrogen;

R3 is a methyl or ethyl group; a is an integer of from 0-40, or from 0-10, or even 0-5; b is an integer of from 0-40, or from 0-10, or even 0-5; c is one when Ri is oxygen or sulfur and two when Ri is nitrogen; and B is — CH2COOH and its salt forms.

DETAILED DESCRIPTION

[0011] The invention described herein is a polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain which provides improvement in fugitivity and non staining properties.

[0012] The term “non-staining” as used herein, generally refers to a colorant composition that may be washed or removed from substrate surfaces (e.g. skin, fabric, wood, concrete) with relatively little effort and without staining the substrate to an appreciable extent.

[0013] The term “non-bleeding,” as used herein, generally refers to a colorant composition that does not substantially color the material surrounding the colorant composition under conditions wherein the material is not intended to be colored. For example, the colorant composition may be present in a powdered laundry detergent as a colored speckle (i.e. a colored particle that is not chemically a part of the detergent particles during storage). The colorant composition will be considered to be “non-bleeding” if it fails to substantially color the surrounding powdered detergent in its unused state (i.e. while it remains in the package).

[0014] The phrase “relatively high color strength,” as used herein, generally refers to a colored product having a color value of at least 5.0. Color strength, or color value, is determined using a modified version of AATCC Test Method 182-2000 wherein the color value is determined and calculated on the absorbance of a 1 gram per liter through a one centimeter cell length of the colorant, in the appropriate solvent, by UV-vis spectroscopy. [0015] For the purposes of this invention the term “fugitive” means a temporary colorant that can be removed easily by the processes of light exposure, exposure to rain or watering, or time.

[0016] As used herein, the term “alkoxy” is intended to include C Cs alkoxy and alkoxy derivatives of polyols having repeating units such as butylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

[0017] As used herein, unless otherwise specified, the terms “alkyl” and “alkyl capped” are intended to include C ₂ to Cioo alkyl groups, C ₂ to C50 alkyl groups, Cs-C ₂ 5 alkyl groups, or even Cio-C ₂ o alkyl groups.

[0018] As used herein, unless otherwise specified, the term “aryl” is intended to include C ₆ -Ci ₂ aryl groups.

[0019] As used herein, unless otherwise specified, the term “arylalkyl” is intended to include C1-C18 alkyl groups and, in one aspect, C1-C6 alkyl groups.

[0020] As used herein, unless otherwise specified, the term “alkanoyl” refers to univalent groups of the formula — C(0)R ^a , where R ^a is an alkyl group, preferably a C3-C _2g alkyl group.

[0021] As used herein, unless otherwise specified, the term “alkenyl” refers to univalent groups derived from acyclic olefinic hydrocarbons by removal of a hydrogen atom from any carbon atom. In the context of this definition, the term “acyclic olefinic hydrocarbons” refers to acyclic hydrocarbons containing one or more carbon-carbon double bonds.

[0022] A used herein, unless otherwise specified, the term “alkenoyl” refers to univalent groups of the formula — C(0)R ^b , where R ^b is an alkenyl group, preferably a C3-C _2g alkenyl group.

[0023] A used herein, unless otherwise specified, the term “aroyl” refers to univalent groups of the formula — C(0)R ^c , where R ^c is an aryl group, preferably a C6-C10 aryl group. [0024] The terms “ethylene oxide,” “propylene oxide” and “butylene oxide” may be shown herein by their typical designation of “EO,” “PO” and “BO,” respectively.

[0025] All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated.

[0026] The term “polymeric colorant” generally refers to a colorant having at least one chromophore portion attached to at least one oligomeric or polymeric chain, wherein the chain has at least three repeating units. The oligomeric or polymeric constituent can be bound to the chromophore via any suitable means, such as a covalent bond, an ionic bond, or suitable electrostatic interaction. Generally, the polymeric colorant may be characterized by having an absorbance in the range of between about 300 nanometers and about 900 nanometers, as measured by UV-vis spectroscopy.

[0027] As a function of its manufacturing process, the polymeric colorant has a molecular weight that is typically represented as a molecular weight distribution.

Accordingly, the molecular weight of the polymeric colorant is generally reported as an average molecular weight, as determined by its molecular weight distribution.

[0028] The chromophore group of the colorant may vary widely and may include compounds characterized in the art as dyestuffs or as pigments. The actual group used will depend to a large extent upon, for instance, the desired color and colorfastness characteristics. The chromophore group may be attached to at least one polyalkyleneoxy- substituent through a suitable linking moiety of nitrogen, oxygen, sulfur, etc.

[0029] Examples of chromophore groups include nitroso, nitro, azo (including monoazo, disazo, trisazo, tetrakisazo, polyazo, formazan, azomethine and metal complexes thereof), stilbene, diarylmethane, triarylmethane, xanthene acridine, quinoline, methine (including polymethine), thiazole, indamine, indophenol, azine, thiazine, oxazine, aminoketone, hydroxyketone, anthraquinone (including anthrapyrazolines, anthrone, anthrapyridone, anthrapyrimidine, flavanthrone, pyranthrone, benzanthrone, perylene, perinone, naphthalimide and other structures formally related to anthraquinone), indigoid (including thioindigoid), and phthalocyanine chromophore groups. Particularly useful in the preparation of the colorants used in the compositions of the invention may be the azo, anthraquinone, triarylmethane and methine dyestuff radicals.

[0030] Examples of suitable polymeric chains are polyalkyleneoxy chains. The term

“polyalkyleneoxy,” as used herein, generally refers to molecular structures containing the following repeating units: -CH ₂ CH ₂ 0-, CH ₂ CH ₂ CH ₂ 0-, -CH ₂ CH ₂ CH ₂ CH ₂ 0-, -CH ₂ CH(CH ₃ )0-, -CH ₂ CH(CH ₂ CH ₃ )0- CH ₂ CH ₂ CH(CH ₃ )0-, and any combinations thereof.

[0031] Typical of such groups which may be attached to the chromophore group are the polymeric epoxides, such as the polyalkylene oxides and copolymers thereof. Typical polyalkylene oxides and copolymers of same which may be employed to provide the colorants include those made from alkylene oxide monomers containing from two to twenty carbon atoms, or more preferably, from two to six carbon atoms. Examples include: polyethylene oxides; polypropylene oxides; polybutylene oxides; oxetanes; tetrahydrafurans; copolymers of polyethylene oxides, polypropylene oxides and polybutylene oxides; and other copolymers including block copolymers, in which a majority of the polymeric substituent is polyethylene oxide, polypropylene oxide and/or polybutylene oxide. Further, such polyalkyleneoxy group may have an average molecular weight in the range of from about 132 to about 10,000, preferably from about 176 to about 5000.

[0032] It is to be understood that because the colorants may not ordinarily be chemically bound to the carrier particles, the precise chemical identity of the end group on the polyalkyleneoxy group may not be critical insofar as the proper functioning of the colorant is concerned in the composition. With this consideration in mind certain most preferred colorants will be defined where certain end groups will be identified. Such recitation of end groups is not to be construed as limiting the invention in its broader embodiments in any way. According to such a most preferred embodiment the colorants may be characterized as follows: wherein:

A is a chromophore selected from nitro, nitroso, monazo, bisazo, diarylmethane, triarylmethane, acridine, methine, thiazole, indamine, oxazine, pthalocyanine, or anthraquinone;

Ri is selected from nitrogen, oxygen, or sulfur;

R2 is hydrogen;

R3 is a methyl or ethyl group; a is an integer of from 0-40; b is an integer of from 0-40; c is one when Ri is oxygen or sulfur and two when Ri is nitrogen; and B is — CH2COOH and its salt forms.

[0033] Salt forms of B could consist of a cation moiety of an alkali metal, an alkali earth metal, a transition metal or ammonium. In addition, it is well known to those skilled in the art of colorant synthesis that the process(es) for making the colorants often result in the synthesis of certain impurities of various amounts. As such, the processes and colorants made therefrom as described herein may contain one or more impurities. Typical impurities that may be present could be terminal aldehydes that result from autoxidation of the terminal hydroxyl of the polyalkyleneoxy chain. Additionally, displacement of the terminal hydroxyl of the polyoxyalkylene chain by halogens such as chlorine and bromine may occur during reaction conditions. Sulfation of the terminal oxidation can occur as an impurity as well. [0034] The oligomeric constituent can be any suitable constituent including, but not limited to, oligomeric constituents selected from the group consisting of (i) oligomers comprising at least three monomers, or repeating units, selected from the group consisting of C2-C20 alkyleneoxy groups, glycidol groups, and glycidyl groups, (ii) aliphatic oligomeric esters conforming to structure (I) and (iii) combinations of (i) and (ii). In structure (I), R2 and R3 are independently selected from the group consisting of hydrogen and C1-C10 alkyl groups, f is an integer between and including 1 and 10, and g is any positive integer or fraction between and including 1 and 20. As will be understood by those of ordinary skill in the art, suitable values for g include both integers and fractions because the length of the oligomeric constituent on the individual polymeric colorant molecules may vary. Thus, the value for g represents an average length of the ester chain for a given sample or collection of polymeric colorant molecules. In certain embodiments, the polymeric colorant can comprise one or more oligomeric constituents consisting of three or more ethylene oxide monomer groups.

[0035] The polymeric colorant can comprise any suitable alkyleneoxy group.

Suitable alkyleneoxy groups include those of Formula (C) below:

[0036] In the structure of Formula (C) and the other alkyleneoxy structures that follow, the carbon atom bonded to R ¹⁰¹ is also bonded to the nitrogen atom of the amine group. In the structure of Formula (C), each R ¹⁰¹ and R ¹⁰² group is independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyalkyl, and aryloxyalkyl. R ¹⁰⁵ is a terminal group for the oxyalkylene and can be selected from the group consisting of hydrogen, alkyl groups (e.g., C1-C4 alkyl groups), and aryl groups, with hydrogen being preferred. Preferably, each R ¹⁰¹ and R ¹⁰² group is independently selected from the group consisting of hydrogen and alkyl (e.g., C1-C4 alkyl). The variable a is an integer equal to or greater than 1 (e.g., from 1 to about 100). For each monomer unit in the alkyleneoxy group, the R ¹⁰¹ and R ¹⁰² groups are independently selected from the recited group. Thus, when the variable a is greater than 1 , the alkyleneoxy group can be comprised of two or more monomer units covalently bonded to form the alkyleneoxy group, or even three or more monomer units. When the alkyleneoxy group comprises two or more monomer units (or even three or more monomer units), these monomer units can be arranged in either a block configuration or in a random configuration, but a block configuration generally is more preferred. In a preferred embodiment, the alkyleneoxy group comprises monomer units independently selected from the group consisting of ethyleneoxy, propyleneoxy, and butyleneoxy. A suitable example of such an alkyleneoxy group is Formula (Cl) below:

[0037] In the structure of Formula (Cl), the variables x, y, and z are independently selected from the group consisting of zero and positive integers (e.g., positive integers from 1 to about 100). Preferably, the sum of x, y, and z is 2 or more or 3 or more (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 for the oxyalkylene and can be selected from the group consisting of hydrogen, alkyl groups (e.g., C1-C4 alkyl groups), and aryl groups, with hydrogen being preferred. In certain possibly preferred embodiments, the alkyleneoxy group comprises ethyleneoxy and propyleneoxy monomer units arranged in a block configuration. Suitable examples of such alkyleneoxy groups include those of Formulae (CM) and (Cl II) below

[0038] In the structures of Formulae (CM) and (Cl 11), the variables, t, u, v, q, r, and s are independently selected from the group consisting of zero and positive integers (e.g., positive integers from 1 to about 100). Preferably, the sum of t, u, and v and q, r, and s is 2 or more or 3 or more (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 for the oxyalkylene and can be selected from the group consisting of hydrogen, alkyl groups (e.g., C1-C4 alkyl groups), and aryl groups, with hydrogen being preferred.

[0039] A method for preparing the polymeric colorant of the present invention is comprised of the following steps: reacting an alkoxylated intermediate with a reagent, such as sodium chloroacetate or other means in the literature, to introduce a carboxymethyl group to the end of the polyalkyleneoxy chain. If an intermediate, the intermediate can then be reacted to obtain the polymeric dyes or interest.

[0040] At least one polymeric colorant as described herein may be added to a laundry care composition. As a result, the invention also encompasses a textile substrate containing at least one polymeric colorant that contains at least one carboxymethyl capped alkyleneoxy chain.

[0041] Alkoxylation is carried out by procedures well-known to those skilled in the art

(see, for example, USPNs 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 CrCs alkoxy or alkoxy derivative of polyol having repeating units include alkylene oxides. Alkylene oxides may be selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. Alkylene oxide groups may be in the form of polymeric chains known as polyalkyleneoxy chains. The term “polyalkyleneoxy,” as used herein, generally refers to molecular structures containing the following repeating units: -CH ₂ CH ₂ 0-, CH ₂ CH ₂ CH ₂ 0-, -CH ₂ CH ₂ CH ₂ CH ₂ 0-, - CH ₂ CH(CH ₃ )0-, -CH ₂ CH(CH ₂ CH ₃ )0- CH ₂ CH ₂ CH(CH ₃ )0-, and any combinations thereof. Typical of such groups are the polymeric epoxides, such as the polyalkylene oxides and copolymers thereof. Typical polyalkylene oxides and copolymers of same include those made from alkylene oxide monomers containing from two to twenty carbon atoms, or more preferably, from two to six carbon atoms. Examples include: polyethylene oxides; polypropylene oxides; polybutylene oxides; oxetanes; tetrahydrafurans; copolymers of polyethylene oxides, polypropylene oxides and polybutylene oxides; and other copolymers including block copolymers, in which a majority of the polymeric substituent is polyethylene oxide, polypropylene oxide and/or polybutylene oxide. Further, such polyalkyleneoxy group may have an average molecular weight in the range of from about 132 to about 10,000, preferably from about 176 to about 5000.

[0042] Typically, the alkoxy molecules form caps for the ends of the chains comprising the polymeric colorant. Thus, the resulting alkoxylated polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain substituted compound may have an average degree of alkoxylation of from 0.5 to 50, or from 1 to 50, or from 1 to 30, or from 1 to 20, or from 1 to 10, or from 2 to 50, or from 2 to 30, or from 2 to 20, or from 2 to 10, or from 3 to 50 or from 3 to 30, or from 3 to 20, or from 3 to 10, or from 4 to 50, or from 4 to 30, or from 4 to 20, or from 4 to 10.

[0043] The polymeric colorant of the present invention may be incorporated into a hard surface cleaner. Hard surface cleaners include, for example, compositions ideally suited for cleaning flooring (such as ceramic tile, vinyl tile, and the like), toilets, bathtubs, showers, faucets, countertops, glass (such as windows), and the like. The hard surface cleaner may contain at least one polymeric colorant as described herein and at least one hard surface ingredient. Hard surface ingredients may include, without limitation, surfactants; antibacterial/antimicrobial agents; aqueous, non-surface active liquid carriers; bleaching agents; non-tinting dyes; detersive builders; enzymes; enzyme stabilizers (such as propylene glycol, boric acid and/or borax); suds suppressors, soil suspending agents; soil release agents; other fabric care benefit agents; pH adjusting agents; chelating agents; smectite clays; solvents; hydrotropes and phase stabilizers; structuring agents; opacifying agents; optical brighteners; perfumes/fragrances; and coloring agents.

[0044] The polymeric colorant of the present invention may be incorporated into a laundry care composition including but not limited to laundry detergents and fabric treatment compositions. As used herein, the term “laundry care composition” includes, unless otherwise indicated, granular, powder, liquid, gel, paste, unit dose bar form and/or flake type washing agents and/or fabric treatment compositions. As used herein, the term “fabric treatment composition” includes, unless otherwise indicated, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, and combinations thereof. Such compositions may be, but need not be, rinse added compositions.

[0045] Laundry care compositions of the present invention comprise one or more of said polymeric colorants containing at least one carboxymethyl capped alkyleneoxy chain and a laundry care ingredient. The polymeric colorant may be added to substrates using a variety of application techniques. For application to textile substrates, the polymeric colorant is preferably included as an additive in laundry detergent. Thus, application to the textile substrate actually occurs when a consumer adds laundry detergent to a washing machine. Similarly, rinse added fabric softening (“RAFS”) compositions are typically added in the rinse cycle, which is after the detergent solution has been used and replaced with the rinsing solution in typical laundering processes.

[0046] The laundry care compositions including laundry detergents may be in solid or liquid form, including a gel form. The laundry care compositions including laundry detergents may also be in a unit dose pouch. The laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties.

[0047] The polymeric colorant may be present in the laundry care composition (such as the laundry detergent composition) in an amount from about 0.0001% to about 10% by weight of the composition, more preferably from about 0.0001% to about 5% by weight of the composition, and even more preferably from about 0.0001% to about 1% by weight of the composition.

[0048] The laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties. In one embodiment, the laundry detergent composition comprises, by weight, from about 5% to about 90% of the surfactant, and more specifically from about 5% to about 70% of the surfactant, and even more specifically from about 5% to about 40%. The surfactant may comprise anionic, nonionic, cationic, zwitterionic and/or amphoteric surfactants. In a more specific embodiment, the detergent composition comprises anionic surfactant, nonionic surfactant, or mixtures thereof.

[0049] Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or non- alkoxylated alkyl sulfate materials. [0050] Exemplary anionic surfactants are the alkali metal salts of C10-16 alkyl benzene sulfonic acids, preferably C _U.M alkyl benzene sulfonic acids. Preferably the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS". Alkyl benzene sulfonates, and 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.

Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium C _H -C _M , e.g., C12, LAS is a specific example of such surfactants.

[0051] Another exemplary type of anionic surfactant comprises ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'--0--(C2H40) _n --SC>3M wherein R' is a C8-C20 alkyl group, n is from about 1 to 20, and M is a salt-forming cation. In a specific embodiment, R' is C10-C18 alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In more specific embodiments, R' is a C12-C16, n is from about 1 to 6 or even from about 1 to 3 or from about 1 to 1.5 and M is sodium.

[0052] The alkyl ether sulfates will generally be used in the form of mixtures comprising varying R' chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some non-ethoxylated alkyl sulfate materials, i.e., surfactants of the above ethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkyl sulfates may also be added separately to the compositions of this invention and used as or in any anionic surfactant component which may be present. Specific examples of non- alkoxylated, e.g., non-ethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C8-C20 fatty alcohols. Conventional primary alkyl sulfate surfactants have the general formula: ROSC>3-M ⁺ wherein R is typically a linear C8-C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation. In specific embodiments, R is a C10-C15 alkyl, and M is alkali metal, more specifically R is C12- Ci4 and M is sodium.

[0053] Specific, non-limiting examples of anionic surfactants useful herein include: a)

C11-C18 alkyl benzene sulfonates (LAS); b) C10-C20 primary, branched-chain and random alkyl sulfates (AS); c) C10-C18 secondary (2,3) alkyl sulfates; d) C10-C18 alkyl alkoxy sulfates (AE _x S) wherein preferably x is from 1-30; e) C10-C18 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443; 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 sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; i) methyl ester sulfonate (MES); and j) alpha-olefin sulfonate (AOS).

[0054] Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Preferred for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid.

[0055] Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials which correspond to the general formula: R ¹ (C _m H _2m O) _n OH wherein R ¹ is a Cs-Ci ₆ alkyl group, m is from 2 to 4, and n ranges from about 2 to 12. Preferably R ¹ is an alkyl group, which may be primary or secondary, that comprises from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. In one embodiment, the alkoxylated fatty alcohols will also be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 or even from about 7 to 9 ethylene oxide moieties per molecule.

[0056] The alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have been marketed under the tradenames Neodol and Dobanol by the Shell Chemical Company. [0057] Another suitable type of nonionic surfactant useful herein comprises the amine oxide surfactants. Amine oxides are materials which are often referred to in the art as "semi-polar" nonionics. Amine oxides have the formula:

R(E0) _x (P0) _y (B0) _z N(0)(CH ₂ R') ₂ .qH ₂ 0. In this formula, R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more preferably C12-C16 primary alkyl. R' is a short-chain moiety, preferably selected from hydrogen, methyl and -- CH2OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by Ci2-i4alkyldimethyl amine oxide. [0058] Non-limiting examples of nonionic surfactants include: a) C12-C18 alkyl ethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C6-C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; d) C14-C22 mid-chain branched alcohols, BA, as discussed in U.S. Pat. No. 6,150,322; e) C14-C22 mid-chain branched alkyl alkoxylates, BAE _X , wherein x if from 1-30, 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; f) Alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647 to Llenado, issued Jan. 26, 1986; specifically alkylpolyglycosides 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 capped poly(oxyalkylated) alcohol surfactants as discussed in U.S. Pat. No. 6,482,994 and WO 01/42408.

[0059] In the laundry detergent compositions herein, the detersive surfactant component may comprise combinations of anionic and nonionic surfactant materials. When this is the case, the weight ratio of anionic to nonionic will typically range from 10:90 to 90:10, more typically from 30:70 to 70:30.

[0060] Cationic surfactants are well known in the art and non-limiting examples of these include quaternary ammonium surfactants, which can have up to 26 carbon atoms. Additional examples include a) alkoxylate quaternary ammonium (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, 4,239,6604,260,529 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, specifically amido propyldimethyl amine (APA).

[0061] 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 to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants; betaine, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, Cs to Cis (preferably Ci2 to Cis) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N- dimethylammino-1-propane sulfonate where the alkyl group can be Cs to Cis, preferably Cio to CM.

[0062] Non-limiting examples of ampholytic surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents comprises at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one comprises an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.

[0063] As noted, the compositions may be in the form of a solid, either in tablet or particulate form, including, but not limited to particles, flakes, or the like, or the compositions may be in the form of a liquid. The liquid detergent compositions comprise an aqueous, non surface active liquid carrier. Generally, the amount of the aqueous, non-surface active liquid carrier employed in the compositions herein will be effective to solubilize, suspend or disperse the composition components. For example, the compositions may comprise, by weight, from about 5% to about 90%, more specifically from about 10% to about 70%, and even more specifically from about 20% to about 70% of the aqueous, non-surface active liquid carrier.

[0064] The most cost-effective type of aqueous, non-surface active liquid carrier is, of course, water itself. Accordingly, the aqueous, non-surface active liquid carrier component will generally be mostly, if not completely, comprised of water. However, other types of water-miscible liquids, such alkanols, diols, other polyols, ethers, amines, and the like, and mixtures thereof, may also be added to liquid detergent compositions as co solvents or stabilizers in addition to or in place of water. Accordingly, the aqueous non surface active liquid carrier component of the liquid detergent composition will generally be present in concentrations ranging from about 5% to about 90% by weight of the composition, more preferably from about 20% to about 70% by weight of the composition.

[0065] Detergent compositions may also contain bleaching agents. Suitable bleaching agents include, for example, hydrogen peroxide sources, such as those described in detail in the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)." These hydrogen peroxide sources include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms of these compounds.

[0066] The preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide can be used herein. Also useful are sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.

[0067] A suitable percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with a silicate, borate or water- soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

[0068] Compositions of the present invention may also comprise as the bleaching agent a chlorine-type bleaching material. Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are less preferred for compositions which comprise enzymes.

[0069] (a) Bleach Activators - Preferably, the peroxygen bleach component in the composition is formulated with an activator (peracid precursor). The activator is present at levels of from about 0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%, preferably to about 10%, more preferably to about 8%, by weight of the composition. A bleach activator as used herein is any compound which, when used in conjunction with a hydrogen peroxide, source leads to the in situ production of the peracid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S. Patent Nos. 5,576,282; 4,915,854 and 4,412,934. See also U.S. Patent No. 4,634,551 for other typical bleaches and activators useful herein.

[0070] Preferred activators are selected from the group consisting of tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3- chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzene- sulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C-io-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cs-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range from about 8 to about 11 are those selected having an OBS or VL leaving group.

[0071] Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulphonate (NOBS); 4-[N-(nonanoyl) amino hexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS), an example of which is described in U.S. Patent No. 5,523,434; dodecanoyloxybenzenesulphonate (LOBS or C^-OBS); 10- undecenoyloxybenzenesulfonate (UDOBS or Cn-OBS with unsaturation in the 10 position); and decanoyloxybenzoic acid (DOBA).

[0072] Preferred bleach activators are those described in U.S. Patent No. 5,998,350 to Burns et al.; U.S. Patent No. 5,698,504 to Christie et al.; U.S. Patent No. 5,695,679 to Christie et al.; U.S. Patent No. 5,686,401 to Willey et al.; U.S. Patent No. 5,686,014 to Hartshorn et al.; U.S. Patent No. 5,405,412 to Wiley et al.; U.S. Patent No. 5,405,413 to Wiley et al.; U.S. Patent No. 5,130,045 to Mitchel et al.; and U.S. Patent No. 4,412,934 to Chung et al. , and copending Patent Application Serial No. 08/064,564, all of which are incorporated herein by reference.

[0073] The mole ratio of peroxygen source (as AvO) to bleach activator in the present invention generally ranges from at least 1:1, preferably from about 20:1, more preferably from about 10:1 to about 1:1, preferably to about 3:1.

[0074] Quaternary substituted bleach activators may also be included. The present laundry compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP, preferably a quaternary substituted percarboxylic acid or a quaternary substituted peroxyimidic acid); more preferably, the former. Preferred QSBA structures are further described in U.S. Patent No. 5,686,015 to Willey et al.; U.S. Patent No. 5,654,421 to Taylor et al.; U.S. Patent No. 5,460,747 to Gosselink et al.; U.S. Patent No. 5,584,888 to Miracle et al.; U.S. Patent No. 5,578,136 to Taylor et al.; all of which are incorporated herein by reference.

[0075] Highly preferred bleach activators useful herein are amide-substituted as described in U.S. Patent Nos. 5,698,504; 5,695,679; and 5,686,014, each of which are cited herein above. Preferred examples of such bleach activators include: (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof.

[0076] Other useful activators are disclosed in U.S. Patent Nos. 5,698,504;

5,695,679; and 5,686,014, each of which is cited herein above, and in U.S. Patent No. 4,966,723 to Hodge et al. These activators include benzoxazin-type activators, such as a

C6H4 ring to which is fused in the 1,2-positions a moiety --C(0)OC(R1)=N-.

[0077] Nitriles, such as acetonitriles and/or ammonium nitriles and other quaternary nitrogen containing nitriles, are another class of activators that are useful herein. Non limiting examples of such nitrile bleach activators are described in U.S. Patent Nos. 6,133,216; 3,986,972; 6,063,750; 6,017,464; 5,958,289; 5,877,315; 5,741,437; 5,739,327;

5,004,558; and in EP Nos. 790244, 775 127, 1 017 773, 1 017776; and in WO 99/14302,

WO 99/14296, WO96/40661, all of which are incorporated herein by reference.

[0078] Depending on the activator and precise application, good bleaching results can be obtained from bleaching systems having an in-use pH of from about 6 to about 13, and preferably from about 9.0 to about 10.5. Typically, for example, activators with electron- withdrawing moieties are used for near-neutral or sub-neutral pH ranges. Alkalis and buffering agents can be used to secure such pH.

[0079] Acyl lactam activators, as described in U.S. Patent Nos. 5,698,504; 5,695,679 and 5,686,014, each of which is cited herein above, are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S. Patent No. 5,503,639 to Willey et al. incorporated herein by reference).

[0080] (b) Organic Peroxides, especially Diacyl Peroxides - These are extensively illustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982 at pages 27-90 and especially at pages 63-72, all incorporated herein by reference. If a diacyl peroxide is used, it will preferably be one which exerts minimal adverse impact on fabric care, including color care.

[0081] (c) Metal-Containing Bleach Catalysts - The compositions and methods of the present invention can also optionally include metal-containing bleach catalysts, preferably manganese and cobalt-containing bleach catalysts.

[0082] One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of 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 sequestrate 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 U.S. Patent No. 4,430,243 to Bragg.

[0083] Manganese Metal Complexes - If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Pat. App. Pub. Nos. 549,271 A1; 549,272 A1; 544,440 A2; and 544,490 A1. Preferred examples of these catalysts include Mn^2(u-0)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2- (PFQ)2, Mn^2( ^u -0)i(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2 (CI04)2, Mn'V^u- 0) _Q (1,4,7-triazacyclononane)4(CIC>4)4, Mn^Mn^4(u-0) _'| (u-0Ac)2-(1.4,7-trimethyl-1,4,7- triazacyclononane)2(CIC>4)3, Mn^(i ,4,7-trimethyl-1 ,4,7-triazacyclononane)- (OCH3)3(PFQ), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Patent Nos. 4,430,243 and 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following: U.S. Patent Nos. 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

[0084] Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; and M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5<0Ac] Ty, wherein "OAc" represents an acetate moiety and "Ty" is an anion, and especially cobalt pentaamine acetate chloride, [CO(NH3) ₅ OAC]CI ₂ ; as well as [Co(NH ₃ ) ₅ OAc](OAc) ₂ ; [Co(NH ₃ ) ₅ OAc](PF ₆ ) ₂ ;

[Co( N H ₃ ) ₅ OAC] (S0 ₄ ) ; [Co(NH ₃ ) ₅ OAc](BF ₄ ) ₂ ; and [Co(NH ₃ ) ₅ OAc](N0 ₃ ) ₂ (herein "PAC").

[0085] These cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. Patent Nos. 6,302,921; 6,287,580; 6,140,294; 5,597,936; 5,595,967; and 5,703,030; in the Tobe article and the references cited therein; and in U.S. Patent No. 4,810,410; J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorq. Chem.. 18, 1497-1502 (1979); Inorq. Chem.. 21, 2881-2885 (1982); Inorq. Chem.. 18, 2023- 2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952).

[0086] Transition Metal Complexes of Macropolycyclic Rigid Ligands - Compositions herein may also suitably include as bleach catalyst a transition metal complex of a macropolycyclic rigid ligand. The amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (wherein "ppb" denotes parts per billion by weight and "ppm" denotes parts per million by weight).

[0087] Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which are suitable for use in the invention compositions can in general include known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or laundry uses, and are non-limitingly illustrated by any of the following:

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hex adecane Manganese(ll) Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadec ane Manganese(ll) Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadeca neManganese(ll) Hexafluorophosphate

Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexade caneManganese(ll)

Hexafluorophosphate

Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2 ]hexadecane Manganese(lll) Hexafluorophosphate

Diaquo-5, 12-dimethyl- 1 ,5,8, 12-tetraazabicyclo[6.6.2]hexadecaneManganese(l I) Tetrafluoroborate

Dichloro-5,12-dimethyl-1,5,8,12 tetraazabicyclo[6.6.2]hexadecane Manganese(lll) Hexafluorophosphate

Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa decaneManganese(lll)

Hexafluorophosphate

Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza bicyclo[6.6.2]hexadecane Manganese(ll)

Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hex adecaneManganese(ll)

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6. 6.2]hexadecane

Manganese(ll)

Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6. 6.2]hexadecane

Manganese(ll)

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6. 6.2]hexadecane

Manganese(ll).

[0088] As a practical matter, and not by way of limitation, the compositions and methods herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the composition comprising a lipophilic fluid and a bleach system, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the composition comprising a lipophilic fluid and a bleach system.

[0089] (d) Bleach Boosting Compounds - The compositions herein may comprise one or more bleach boosting compounds. Bleach boosting compounds provide increased bleaching effectiveness in lower temperature applications. The bleach boosters act in conjunction with conventional peroxygen bleaching sources to provide increased bleaching effectiveness. This is normally accomplished through in situ formation of an active oxygen transfer agent such as a dioxirane, an oxaziridine, or an oxaziridinium. Alternatively, preformed dioxiranes, oxaziridines and oxaziridiniums may be used.

[0090] Among suitable bleach boosting compounds for use in accordance with the present invention are cationic imines, zwitterionic imines, anionic imines and/or polyionic imines having a net charge of from about +3 to about -3, and mixtures thereof. These imine bleach boosting compounds of the present invention include those of the general structure: [A] where may be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl radicals. [0091] Among preferred bleach boosting compounds are zwitterionic bleach boosters, which are described in U.S. Patent Nos. 5,576,282 and 5,718,614. Other bleach boosting compounds include cationic bleach boosters described in U.S. Patent Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO 95/13351, WO 95/13352, and WO 95/13353.

[0092] Peroxygen sources are well-known in the art and the peroxygen source employed in the present invention may comprise any of these well known sources, including peroxygen compounds as well as compounds, which under consumer use conditions, provide an effective amount of peroxygen in situ. The peroxygen source may include a hydrogen peroxide source, the in situ formation of a peracid anion through the reaction of a hydrogen peroxide source and a bleach activator, preformed peracid compounds or mixtures of suitable peroxygen sources. Of course, one of ordinary skill in the art will recognize that other sources of peroxygen may be employed without departing from the scope of the invention. The bleach boosting compounds, when present, are preferably employed in conjunction with a peroxygen source in the bleaching systems of the present invention. [0093] (e) Preformed Peracids - Also suitable as bleaching agents are preformed peracids. The preformed peracid compound as used herein is any convenient compound which is stable and which under consumer use conditions provides an effective amount of peracid or peracid anion. The preformed peracid compound may be selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof. Examples of these compounds are described in U.S. Patent No. 5,576,282 to Miracle et al.

[0094] One class of suitable organic peroxycarboxylic acids have the general formula:

O

Y— R— C— O— OH wherein R is an alkylene or substituted alkylene group containing from 1 to about 22 carbon atoms or a phenylene or substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl, -C(0)OH or -C(0)OOH. Organic peroxyacids suitable for use in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula: wherein Y can be, for example, H, CH3, CH2CI, C(0)OH, or C(0)OOH; and n is an integer from 0 to 20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

O

Y-C6H4-C— o— OH wherein Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C(0)0H or C(0)00H.

[0095] Typical monoperoxy acids useful herein include alkyl and aryl peroxyacids such as:

(i) peroxybenzoic acid and ring-substituted peroxybenzoic acid, e.g. peroxy-a- naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o- carboxybenzamidoperoxyhexanoic acid (sodium salt);

(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, e.g. peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-(3-octylsuccinoyl)aminoperoxycaproic acid (SAPA) and N,N- phthaloylaminoperoxycaproic acid (PAP);

(iii) amidoperoxyacids, e.g. monononylamide of either peroxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA).

[0096] Typical diperoxyacids useful herein include alkyl diperoxyacids and aryldiperoxyacids, such as:

(i) 1,12-diperoxydodecanedioic acid;

(ii) 1,9-diperoxyazelaic acid;

(iii) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic acid;

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

(v) 4,4'-sulfonylbisperoxybenzoic acid.

[0097] Such bleaching agents are disclosed in U.S. Patent Nos. 4,483,781 to

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

[0098] (f) Photobleaches - Suitable photobleaches for use in the treating compositions of the present invention include, but are not limited to, the photobleaches described in U.S. Patent Nos. 4,217,105 and 5,916,481.

[0099] (q) Enzyme Bleaching - Enzymatic systems may be used as bleaching agents. The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.

[00100] The present invention compositions and methods may utilize alternative bleach systems such as ozone, chlorine dioxide and the like. Bleaching with ozone may be accomplished by introducing ozone-containing gas having ozone content from about 20 to about 300 g/m ³ into the solution that is to contact the fabrics. The gasliquid ratio in the solution should be maintained from about 1:2.5 to about 1:6. U.S. Patent No. 5,346, 588 describes a process for the utilization of ozone as an alternative to conventional bleach systems and is herein incorporated by reference.

[00101] The detergent compositions of the present invention may also include any number of additional optional ingredients. These include conventional laundry detergent composition components such as non-tinting dyes, detersive builders, enzymes, enzyme stabilizers (such as propylene glycol, boric acid and/or borax), suds suppressors, soil suspending agents, soil release agents, other fabric care benefit agents, pH adjusting agents, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, dye transfer inhibiting agents, opacifying agents, optical brighteners, perfumes and coloring agents. The various optional detergent composition ingredients, if present in the compositions herein, should be utilized at concentrations conventionally employed to bring about their desired contribution to the composition or the laundering operation. Frequently, the total amount of such optional detergent composition ingredients can range from about 0.01% to about 50%, more preferably from about 0.1% to about 30%, by weight of the composition.

[00102] The liquid detergent compositions are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, polymeric colorant, and certain optional other ingredients, some of which may normally be in solid form, that have been combined with the normally liquid components of the composition, such as the liquid alcohol ethoxylate nonionic, the aqueous liquid carrier, and any other normally liquid optional ingredients. Such a solution, dispersion or suspension will be acceptably phase stable and will typically have a viscosity which ranges from about 100 to 600 cps, more preferably from about 150 to 400 cps. For purposes of this invention, viscosity is measured with a Brookfield LVDV-II+ viscometer apparatus using a #21 spindle.

[00103] The liquid detergent compositions herein can be prepared by combining the components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form a phase stable liquid detergent composition. In a preferred process for preparing such compositions, a liquid matrix is formed containing at least a major proportion, and preferably substantially all, of the liquid components, e.g., nonionic surfactant, the non-surface active liquid carriers and other optional liquid components, with the liquid components being thoroughly admixed by imparting shear agitation to this liquid combination. For example, rapid stirring with a mechanical stirrer may usefully be employed. While shear agitation is maintained, substantially all of any anionic surfactants and the solid form ingredients can be added. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a solution or a uniform dispersion of insoluble solid phase particulates within the liquid phase. After some or all of the solid-form materials have been added to this agitated mixture, particles of any enzyme material to be included, e.g., enzyme prills, are incorporated. As a variation of the composition preparation procedure hereinbefore described, one or more of the solid components may be added to the agitated mixture as a solution or slurry of particles premixed with a minor portion of one or more of the liquid components. After addition of all of the composition components, agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from about 30 to 60 minutes.

[00104] In an alternate embodiment for forming the liquid detergent compositions, the polymeric colorant is first combined with one or more liquid components to form a polymeric colorant premix, and this premix is added to a composition formulation containing a substantial portion, for example more than 50% by weight, more specifically, more than 70% by weight, and yet more specifically, more than 90% by weight, of the balance of components of the laundry detergent composition. For example, in the methodology described above, both the polymeric colorant premix and the enzyme component are added at a final stage of component additions. In a further embodiment, the polymeric colorant is encapsulated prior to addition to the detergent composition, the encapsulated polymeric colorant is suspended in a structured liquid, and the suspension is added to a composition formulation containing a substantial portion of the balance of components of the laundry detergent composition. [00105] As noted previously, the detergent compositions may be in a solid form. Suitable solid forms include tablets and particulate forms, for example, granular particles or flakes. Various techniques for forming detergent compositions in such solid forms are well known in the art and may be used herein. In one embodiment, for example when the composition is in the form of a granular particle, the polymeric colorant is provided in particulate form, optionally including additional but not all components of the laundry detergent composition. The polymeric colorant particulate is combined with one or more additional particulates containing a balance of components of the laundry detergent composition. Further, the polymeric colorant, optionally including additional but not all components of the laundry detergent composition, may be provided in an encapsulated form, and the polymeric colorant encapsulate is combined with particulates containing a substantial balance of components of the laundry detergent composition.

[00106] The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing solutions for use in the laundering of textile substrates such as fabrics. Generally, an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions. The aqueous washing solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered therewith. An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous washing solution. More preferably, from about 1,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing solution.

[00107] Fabric Treatment Compositions / Rinse Added Fabric Softening Compositions

[00108] In another specific embodiment, the polymeric colorant of the present invention may be included in a fabric treatment composition. The fabric treatment composition may be comprised of at least one polymeric colorant and a rinse added fabric softening composition (“RAFS;” also known as rinse added fabric conditioning compositions). Examples of typical rinse added softening compositions can be found in U.S. Provisional Patent Application Serial No. 60/687582 filed on October 8, 2004. The rinse added fabric softening compositions of the present invention may comprise (a) fabric softening active (“FSA”) and (b) a polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain. The rinse added fabric softening composition may comprise from about 1% to about 90% by weight of the FSA, more preferably from about 5% to about 50% by weight of the FSA. The polymeric colorant may be present in the rinse added fabric softening composition in an amount from about 0.5 ppb to about 50 ppm, more preferably from about 0.5 ppm to about 30 ppm.

[00109] In one embodiment of the invention, the fabric softening active is a quaternary ammonium compound suitable for softening fabric in a rinse step. In one embodiment, the FSA is formed from a reaction product of a fatty acid and an aminoalcohol obtaining mixtures of mono-, di-, and, in one embodiment, triester compounds. In another embodiment, the FSA comprises one or more softener quaternary ammonium compounds such, but not limited to, as a monoalkyquaternary ammonium compound, a diamido quaternary compound and a diester quaternary ammonium compound, or a combination thereof.

[00110] In one aspect of the invention, the FSA comprises a diester quaternary ammonium (hereinafter “DQA”) compound composition. In certain embodiments of the present invention, the DQA compounds compositions also encompasses a description of diamido FSAs and FSAs with mixed amido and ester linkages as well as the aforementioned diester linkages, all herein referred to as DQA.

[00111] A first type of DQA (“DQA (1)”) suitable as a FSA includes a compound comprising the formula:

{R4-m - N ⁺ - [(CH ₂ )n - Y - R ¹ ]m} X wherein each R substituent is either hydrogen, a short chain C-|-CQ, preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, poly (C ₂ -3 alkoxy), preferably polyethoxy, group, benzyl, or mixtures thereof; each m is

2 or 3; each n is from 1 to about 4, preferably 2; each Y is -0-(0)C-, -C(0)-0-, -NR-C(O)-, or -C(0)-NR- and it is acceptable for each Y to be the same or different; the sum of carbons in each R ^" ', plus one when Y is -0-(0)C- or -NR-C(O) -, is C-|2-C22’ preferably C14-C2O’ with each R ^" ' being a hydrocarbyl, or substituted hydrocarbyl group; it is acceptable for R ^" ' to be unsaturated or saturated and branched or linear and preferably it is linear; it is acceptable for each R ^" ' to be the same or different and preferably these are the same; and X can be any softener-compatible anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, and nitrate, more preferably chloride or methyl sulfate. Preferred DQA compounds are typically made by reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Some materials that typically result from such reactions include N,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride or N,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium methylsulfate wherein the acyl group is derived from animal fats, unsaturated, and polyunsaturated, fatty acids, e.g., tallow, hardened tallow, oleic acid, and/or partially hydrogenated fatty acids, derived from vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, palm oil, etc. [00112] Non-limiting examples of suitable fatty acids are listed in US Patent No. 5,759,990 at column 4, lines 45-66. In one embodiment, the FSA comprises other actives in addition to DQA (1) or DQA. In yet another embodiment, the FSA comprises only DQA (1) or DQA and is free or essentially free of any other quaternary ammonium compounds or other actives. In yet another embodiment, the FSA comprises the precursor amine that is used to produce the DQA.

[00113] In another aspect of the invention, the FSA comprises a compound, identified as DTTMAC comprising the formula: wherein each m is 2 or 3, each R1 is a CQ-C22 _> preferably C14-C2O’ but ^{no more} than one being less than about C12 and then the other is at least about 16, hydrocarbyl, or substituted hydrocarbyl substituent, preferably Ci0 ¾0 alkyl ^or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, also referred to sometimes as "alkylene"), most preferably C12-C18 alkyl or alkenyl, and branch or unbranched. In one embodiment, the Iodine Value (IV) of the FSA is from about 1 to 70; each R is H or a short chain C-|-CQ, preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R2 0)2-4H where each R2 is a C-|_Q alkylene group; and A is a softener compatible anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, or nitrate; more preferably chloride or methyl sulfate.

[00114] Examples of these FSAs include dialkydimethylammonium salts and dialkylenedimethylammonium salts such as ditallowdimethylammonium and ditallowdimethylammonium methylsulfate. Examples of commercially available dialkylenedimethylammonium salts usable in the present invention are di-hydrogenated tallow dimethyl ammonium chloride and ditallowdimethyl ammonium chloride available from Degussa under the trade names Adogen® 442 and Adogen® 470 respectively. In one embodiment, the FSA comprises other actives in addition to DTTMAC. In yet another embodiment, the FSA comprises only compounds of the DTTMAC and is free or essentially free of any other quaternary ammonium compounds or other actives.

[00115] In one embodiment, the FSA comprises an FSA described in U.S. Pat. Pub. No. 2004/0204337 A1, published Oct. 14, 2004 to Corona et al., from paragraphs 30 - 79.

In another embodiment, the FSA is one described in U.S. Pat. Pub. No. 2004/0229769 A1, published Nov. 18, 2005, to Smith et al., on paragraphs 26 - 31; or U.S. Pat. No. 6,494,920, at column 1, line 51 et seq. detailing an “esterquat” or a quaternized fatty acid triethanolamine ester salt.

[00116] In one embodiment, the FSA is chosen from at least one of the following: ditallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methyl sulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, or combinations thereof. [00117] In one embodiment, the FSA may also include amide containing compound compositions. Examples of diamide comprising compounds may include but 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.

[00118] Another specific embodiment of the invention provides for a rinse added fabric softening composition further comprising a cationic starch. Cationic starches are disclosed in US 2004/0204337 A1. In one embodiment, the rinse added fabric softening composition comprises from about 0.1% to about 7% of cationic starch by weight of the fabric softening composition. In one embodiment, the cationic starch is HCP401 from National Starch.

[00119] Suitable Laundry Care Ingredients

[00120] While not essential for the purposes of the present invention, the non-limiting list of laundry care ingredients illustrated hereinafter are suitable for use in the laundry care compositions and may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with perfumes, colorants, dyes or the like. It is understood that such ingredients are in addition to the components that were previously listed for any particular embodiment. The total amount of such adjuncts may range from about 0.1% to about 50%, or even from about 1% to about 30%, by weight of the laundry care composition.

[00121] The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used. Suitable laundry care ingredients include, but are not limited to, polymers, for example cationic polymers, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or coloring agents. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.

[00122] As stated, the laundry care ingredients are not essential to Applicants’ laundry care compositions. Thus, certain embodiments of Applicants’ compositions do not contain one or more of the following adjuncts materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or coloring agents. However, when one or more adjuncts are present, such one or more adjuncts may be present as detailed below:

[00123] Surfactants - The compositions according to the present invention can comprise a surfactant or surfactant system wherein the surfactant can be selected from nonionic and/or anionic and/or cationic surfactants and/or ampholytic and/or zwitterionic and/or semi-polar nonionic surfactants. The surfactant is typically present at a level of from about 0.1%, from about 1%, or even from about 5% by weight of the cleaning compositions to about 99.9%, to about 80%, to about 35%, or even to about 30% by weight of the cleaning compositions.

[00124] Builders - The compositions of the present invention can comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1% builder, or from about 5% or 10% to about 80%, 50%, or even 30% by weight, of said builder. Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth 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-trisulphonic acid, and carboxymethyl-oxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5- tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

[00125] Chelating Agents - The compositions herein may also optionally contain one or more copper, iron and/or manganese chelating agents. If utilized, chelating agents will generally comprise from about 0.1% by weight of the compositions herein to about 15%, or even from about 3.0% to about 15% by weight of the compositions herein. [00126] Dye Transfer Inhibiting Agents - The compositions of the present invention may also include one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. When present in the compositions herein, the dye transfer inhibiting agents are present at levels from about 0.0001%, from about 0.01%, from about 0.05% by weight of the cleaning compositions to about 10%, about 2%, or even about 1% by weight of the cleaning compositions.

[00127] Dispersants - The compositions of the present invention can 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.

[00128] Enzymes - The compositions can comprise one or more detergent enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, b-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is a cocktail of conventional applicable enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase.

[00129] Enzyme Stabilizers - Enzymes for use in compositions, for example, detergents can be stabilized by various techniques. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions that provide such ions to the enzymes.

[00130] 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 of 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 sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methyl-enephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Patent No. 4,430,243.

[00131] If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent No.

5,576,282.

[00132] Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Patent Nos. 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. Patent Nos. 5,597,936, and 5,595,967.

[00133] Compositions herein may also suitably include a transition metal complex of a macropolycyclic rigid ligand - abbreviated as “MRL”. As a practical matter, and not by way of limitation, the compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the benefit agent MRL species in the aqueous washing medium, and may provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the wash liquor.

[00134] Preferred transition-metals in the instant transition-metal bleach catalyst include manganese, iron and chromium. Preferred MRL’s herein are a special type of ultra- rigid ligand that is cross-bridged such as 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa- decane. Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in WO 00/32601, and U.S. Patent No. 6,225,464.

[00135] Exemplary Laundry Care Composition Formulations:

[00136] Liquid Detergent Formulations:

Table A provides examples of liquid detergent formulations which include at least one polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain of the present invention.

Table A - Liquid Detergent Formulations Comprising the Present Polymeric Colorant

¹ diethylenetriaminepentaacetic acid, sodium salt

² diethylenetriaminepentakismethylenephosphonic acid, sodium salt

³ ethylenediaminetetraacetic acid, sodium salt 4 a compact formula, packaged as a unitized dose in polyvinyl alcohol film

[00137] Granular Detergent Formulations:

Table B provides examples of granular detergent formulations which include at least one polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain of the present invention. Table B - Granular Detergent Formulations Comprising the Present Polymeric

Colorant [00138] Fabric Treatment Compositions:

Table C provides examples of liquid fabric treatment compositions which include at least one polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain of the present invention. Table C - Liquid Fabric Treatment Compositions Comprising the Present Polymeric Colorant ^a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride. ^b Cationic starch based on common maize starch or potato starch, containing 25% to 95% amylose and a degree of substitution of from 0.02 to 0.09, and having a viscosity measured as Water Fluidity having a value from 50 to 84. ^c Copolymer of ethylene oxide and terephthalate having the formula described in US 5,574,179 at col.15, lines 1-5, wherein each X is methyl, each n is 40, u is 4, each R ¹ is essentially 1,4-phenylene moieties, each R ² is essentially ethylene, 1,2-propylene moieties, or mixtures thereof. ^d Diethylenetriaminepentaacetic acid. ^e KATHON ^® CG available from Rohm and Haas Co. ^f Silicone antifoam agent available from Dow Corning Corp. under the trade name DC2310.

⁹ Disodium 4,4’-bis-(2-sulfostyryl) biphenyl, available from Ciba Specialty Chemicals. ^h Cocomethyl ethoxylated [15] ammonium chloride, available from Akzo Nobel.

[00139] Additionally, it is contemplated that the polymeric colorant of the current invention may be ideal for use in thermoset materials (such as, for example, polyurethane foam). Examples of specific thermoset formulations, which may be suitable for use with the polymeric colorant of the present invention, are disclosed in commonly assigned US Patent Nos. 4,284,729 to Cross et al. and 4,846,846 to Rekers et al. In general, polyurethane foam is produced through the catalyzed polymerization of the reaction products of polyols and isocyanates. Blowing agents present within the polymerization step typically provide the necessary foam-making capability. Such a reaction is well known throughout the polyurethane industry and has been practiced for many years.

[00140] Thus, further contemplated to be within the scope of the present invention is a thermoset material containing the polymeric colorant as described herein. In one aspect of the invention, the thermoset material is a polyurethane foam material. Polyurethanes are typically made by reacting isocyanate with active hydrogen-containing compounds. The polyurethane polymer is then expanded (or “blown”) to create a polyurethane foam material via the introduction of bubbles and a gas. Thus, the present invention includes a polyurethane foam material that contains at least one polyurethane foam ingredient and the polymeric colorant described herein. Polyurethane foam ingredients include, without limitation, one or more of the following: polyols, isocyanates, catalysts, silicones, antioxidants (such as phenols and hindered phenols), ultraviolent absorbing agents, blowing agents (such as carbon dioxide released from reaction of isocyanate with water), organic liquids, coloring agents (including dyes, pigments, polymeric colorants, and the like, and mixtures thereof), biocides, water, and the like.

[00141] Suitable polyols utilized within this invention include those comprising at least two alcohol moieties, preferably at least three. The free hydroxyl groups react well with the isocyanates to form the urethane components which are then polymerized to form the desired polyurethanes. Blowing agents present within the polymerization step provide the necessary foam-making capability. Preferred polyols thus comprise between three and six alcohol moieties, comprising from between one and six carbon atoms per alcohol moiety. In one aspect of the invention, a typical trifunctional polyol is utilized (such as 3022 polyol, available from Bayer).

[00142] Isocyanates, such as diisocyanates, are well known components of such polyurethane foams and include any compounds which possess at least one free cyanate reactive group, and most preferably two, although more may be utilized. Such compounds are may also be aliphatic or aromatic in nature. The most prominently utilized isocyanates are toluene diisocyanate and methylene diisocyanate. The polyol is generally reacted with a slight excess of isocyanate (ratio of from 1:1.04 to 1:1.12) to produce a soft foam product; the greater the ratio, the harder the foam thus produced). In practice, two separate streams of liquids (one of polyol, the other of isocyanate) are mixed together in the presence of a polymerization catalyst and a blowing agent in order to produce the desired polyurethane foam product. [00143] The catalyst used for foam production encompasses any type that effectuates the polymerization of the isocyanate/polyol reactants noted above to form the desired polyurethane in foam form. The term “tertiary amine-based hydroxy-containing catalyst” is intended to encompass any gelation/blowing catalyst utilized within polyurethane production which comprises at least one amine constituent. Amine-based catalysts, and more specifically, tertiary amine catalysts, are widely utilized within such specific foam-producing methods.

[00144] Other additives or solvents may also be present within the foam-making composition. Auxiliary blowing agents are required to provide the necessary foam blowing capability and reduce chances of combustion. Such compounds include methylene chloride, acetone, carbon dioxide (which may be liberated during the reaction between water and isocyanate), and the like, and are present in amounts of between about 1.0 parts per hundred parts polyol (also referred to herein as “php”) and 10 php of the entire foam-making composition. Water may thus also be added in relatively low amount (i.e., from about 3 to about 10 php; most preferably between about 3 and 7 php) to provide carbon dioxide for blowing purposes. Silicones may be added to provide desired cell structure and foam stability and are present in an amount from about 0.1 to about 2 php of the entire foammaking composition; preferably from about 0.9 to about 1.6 php.

[00145] A polymeric colorant composition of the present invention may be comprised of at least one polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain as described herein and at least one solvent. Solvents include, for example and without limitation, water, hydrocarbons (such as mineral oil), perchloroethylene, carbon tetrachloride, acetone, alcohol and the like. Further suitable solvents include C4-14 ethers and diethers, glycols, alkoxylated glycols, C ₆ -Cie glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, C _S -C _M alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof. Additional solvents suitable for use in the present invention include those listed by the American Chemical Society, Division of Organic Chemistry, “Common Organic Solvents: Table of Properties,” which is located at https://www.organicdivision.org/orig/organic_solvents.html. Any combination of the aforementioned solvents may be utilized.

EXAMPLES

[00146] The following examples further illustrate the subject matter described above but, of course, should not be construed as in any way limiting the scope thereof. [00147] Example 1

[00148] To a 250 mL 4-neck round bottom flask with an overhead stirrer and a temperature probe was charged N-ethyl m-toluidine 5EO (50 g, 0.14 mol), that is made from known procedures in the literature. The contents were heated to 70°C and finely ground KOH (11.1 g, 0.17 mol) was added, followed by the portion wise addition of sodium chloroacetate (19.7 g, 0.17 mol). The reaction was heated at 70°C for 5 hours, whereby it was judged to be complete by TLC. The pH was adjusted to 2.8 with concentrated HCI. The N-ethyl m-toluidine 5EO carboxymethyl product was collected by phase separation.

[00149] To a 250 mL 3-neck round bottom flask with temperature probe and overhead stirrer was charged N-ethyl m-toluidine 5EO carboxymethyl (0.028 mol). The contents were heated to 70°C. Urea (0.48 g, 0.008 mol) and p-dimethylamino benzaldehyde (2 g, 0.013 mol) were added. Concentrated HCI (4.1 g, 0.04 mol) was slowly added followed by 2.4 g of water. The reaction mixture was heated to 95°C for 3 hours. The pH was then adjusted to 4 with 50% aqueous sodium hydroxide. The reaction mixture was placed at 70°C in an oven and the top organic layer was collected after phase separation had occurred.

[00150] The isolated leuco dye (4.6 g 0.0048 mol) was charged to a 100 mL 3-neck round bottom flask with temperature probe, condenser and overhead stirrer. Chloranil (2.4g, 0.01 mol) and 30 mL of methyl ethyl ketone were charged to the reactor. The contents were heated to 80°C for 1 hour, then cooled to room temperature. A mixture of concentrated HCI (2.5 g) and water (30 ml_) were added to the flask. The methyl ethyl ketone was evaporated, and the solids were filtered off. The aqueous filtrate containing the blue product was washed with dichloromethane to remove the residual oxidant and the aqueous layer was concentrated to dryness to obtain the product.

[00151] 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.

[00152] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the subject matter of this application (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein.

All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the subject matter of the application and does not pose a limitation on the scope of the subject matter unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the subject matter described herein.

[00153] Preferred embodiments of the subject matter of this application are described herein, including the best mode known to the inventors for carrying out the claimed subject matter. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the subject matter described herein to be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the present disclosure unless otherwise indicated herein or otherwise clearly contradicted by context.