Hair care composition comprising a polymeric colorant

Abstract

The present invention relates to a hair care composition comprising at least one hair care ingredient and at least one polymeric colorant. The present invention also relates to a method of coloring human head or facial hair comprising the steps of: (a) providing a hair care composition comprising at least one poly(alkylene oxide)-substituted chromophore colorant; (b) applying the hair care composition to the hair; and (c) allowing the hair care composition to contact the hair for a period of time.

Description

Technical Field

[0001] This invention relates to hair care compositions comprising at least one hair care ingredient and at least one polymeric colorant. Background Technology

[0002] Because consumers want to color their hair, various hair dyes have been invented. Typically, there are two classes of hair dyes. The first class is known as oxidizing or permanent dyes, which are in the form of a dye precursor that oxidizes during application to form color. Several well-known examples of this class are phenylenediamine and p-aminophenol, which are blended with other color-forming agents such as resorcinol, m-aminophenol, etc. The other class is often referred to as non-oxidizing or direct dyes. These dyes are pre-formed dye molecules. Examples of this class include Basic Red 76, Acid Violet 43, HC Blue 15, and HC Blue 16.

[0003] However, current molecular hair dyes have drawbacks. The pre-formed dyes are conjugated, rigid organic compounds and are often difficult to dissolve in hair care compositions. Undissolved dyes can leave uneven hues or sometimes patches in treated hair. Furthermore, the toxicity of hair dyes is also a concern. Additionally, current direct dyes tend to wash off very quickly and are therefore considered semi-permanent. Therefore, continuous improvement of current hair dyes is necessary. In this regard, polymeric liquid colorants are superior to conventional hair dyes because they are easier to formulate and, due to their higher molecular weight, are less prone to skin penetration and thus have fewer toxicity issues. Polymeric liquid colorants also appear to have better washability compared to current dyes. Summary of the Invention

[0004] In one aspect, the present invention relates to a method for coloring human head or facial hair, the method comprising the steps of: (a) providing a hair care composition comprising at least one poly(alkylene oxide)-substituted chromophore colorant; (b) applying the hair care composition to hair; and (c) contacting the hair care composition with the hair for a period of time. The hair care composition may further comprise at least one hair care ingredient.

[0005] The poly(alkylene oxide)-substituted chromophore colorant can be present at a concentration of 0.001 to 20% by weight of the composition, or even 0.01 to 20% by weight of the composition. The poly(alkylene oxide) substituent in the chromophore is a polymer substituent group formed by removing hydrogen or a group from a poly(alkylene oxide) polymer containing alkylene oxide residues having 2 to 4 carbon atoms. Furthermore, the average molecular weight of the poly(alkylene oxide) substituent can be from 132 to 10,000. The chromophore colorants are selected from azo, carbazole, pyrazolone, cyanine blue, phthalocyanine, anthraquinone, aza

[18] arbutin, formazan copper complex, nitroso, nitro, diarylmethane, triarylmethane, xanthones, acridine, methine, thiazole, indamine, azazine, oxazine, thiazine, quinoline, indigoid, indophenol, lactone, amino ketone, hydroxy ketone, naphthalenedicarboximide and succinyl styrene chromophores.

[0006] In one aspect of the invention, the chromophore has the following structure:

[0007]

[0008] AR1 and AR2 are independently selected from alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl; one of the AR1 or AR2 groups may be further substituted by another azo chromophore to form a diazo.

[0009] In another aspect of the invention, the chromophore has the following structure:

[0010]

[0011] Where e and f are independent integers from 0 to 4; each R 20 and R 21 Independently selected from halogens, hydroxyl groups, nitro groups, nitrile groups, alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, aryl groups, substituted aryl groups, heteroaryl groups and substituted heteroaryl groups, ─S(O)2OH, ─S(O)2O - [M + ]、─C(O)OR5、─C(O)R5、─C(O)NR5R6、─NR5C(O)OR6、─NR5C(O)SR6、─OR5、─NR5R6、─S(O)2R5、─S(O)2NR5R6 and ─P(O)2R5; M is a cation; R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl.

[0012] In another aspect of the invention, the chromophore has a structure selected from the following:

[0013]

[0014] Where h, i, and j are independent integers from 0 to 4; the prerequisite is that, in structure IIIa, h is an integer from 0 to 2. 31 Selected from =O, =S, =NR 34 S = N + R 34 R 35 ;R 30 Selected from -O - 、─S - 、─OR 36 and NR 36 R 37 Each R 34 R 35 R 36 and R 37 Independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, -C(O)OR5, -C(O)R5, and -C(O)NR5R6. Each R 31 R 32 and R 33 The functional group is independently selected from halogen, hydroxyl, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl, ─S(O)2OH, ─S(O)2O - [M + ]、─C(O)OR5、─C(O)R5、─C(O)NR5R6、─NR5C(O)OR6、─NR5C(O)SR6、─OR5、─NR5R6、─S(O)2R5、─S(O)2NR5R6 and ─P(O)2R5; M is a cation; R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl. X 30 X 31 X 32 and X 33 Independently selected from carbon and nitrogen atoms, provided that X... 30 X 31 X 32 and X 33 No more than two of them are nitrogen atoms.

[0015] In yet another aspect of the invention, the chromophore has the following structure:

[0016]

[0017] Where X 42 Selected from oxygen atoms, sulfur atoms, and SiR 45 R 46 and NR 45 Y41 Selected from =O, =S, =NR 46 S = N + R 45 R 46 ;R 45 and R 46 Selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, ─S(O)2OH, ─S(O)2O - [M + ], ─C(O)OR5, ─C(O)R5, and ─C(O)NR5R6. l is an integer from 0 to 3 and m is an integer from 0 to 4. Each R 41 and R 42 Independently selected from halogens, hydroxyl groups, nitro groups, nitrile groups, alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, aryl groups, substituted aryl groups, heteroaryl groups and substituted heteroaryl groups, ─S(O)2OH, ─S(O)2O - [M + ], ─C(O)OR5, ─C(O)R5, ─C(O)NR5R6, ─NR5C(O)OR6, ─NR5C(O)SR6, ─OR5, ─NR5R6, ─S(O)2R5, ─SR5, ─S(O)2NR5R6 and ─P(O)2R5; M is a cation; wherein at least one R 42 The group is selected from -OR5, -SR5 and -NR5R6. R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl.

[0018] In another aspect of the invention, the chromophore has the following structure:

[0019]

[0020] AR 51 Selected from alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl; R 52 R 53 and R 54 Independently selected from hydrogen and R 51 Each R 51 Independently selected from halogens, hydroxyl groups, nitro groups, nitrile groups, alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, aryl groups, substituted aryl groups, heteroaryl groups and substituted heteroaryl groups, ─S(O)2OH, ─S(O)2O - [M +], ─C(O)OR5, ─C(O)R5, ─C(O)NR5R6, ─NR5C(O)OR6, ─NR5C(O)SR6, ─OR5, ─NR5R6, ─S(O)2R5, ─S(O)2NR5R6 and ─P(O)2R5, where M is a cation, provided that R 51 Not hydrogen; R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl, and substituted aryl; c is an integer from 1 to 10. X 50 X 51 X 52 and X 53 Independently selected from carbon and nitrogen atoms, provided that X... 50 X 51 X 52 and X 53 No more than two of them are nitrogen atoms; g is an integer from 1 to 4; and the structure V is optionally present in the form of an ionic ion accompanying its counterion to maintain electroneutrality.

[0021] In one aspect of the invention, the chromophore has the following structure:

[0022]

[0023] Among them, each R 61 R 62 R 63 and R 64 The functional group is independently selected from halogen, hydroxyl, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, -S(O)2OH, -S(O)2O - [M + ]、─C(O)OR5、─C(O)R5、─C(O)NR5R6、─NR5C(O)OR6、─NR5C(O)SR6、─OR5、─NR5R6、─S(O)2R5、─S(O)2NR5R6 and ─P(O)2R5; M is a cation; wherein n, o, p and q are independently selected from integers from 0 to 4; R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl; Q is hydrogen, metal ion or metalloid; A is an anion; x is a positive integer and y is an integer including 0 such that the divalent group ─Q x A y — Neutral.

[0024] In yet another aspect of the invention, the chromophore has the following structure:

[0025]

[0026] Among them, each R 71 R72 and R 73 The functional group is independently selected from hydrogen, halogen, hydroxyl, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, ─S(O)2OH, ─S(O)2O - [M + ], ─C(O)OR5, ─C(O)R5, ─C(O)NR5R6, ─NR5C(O)OR6, ─NR5C(O)NR6NR7R8, ─NR5C(O)SR6, ─OR5, ─NR5R6, ─S(O)2R5, ─S(O)2NR5R6 and ─P(O)2R5; M is a cation; wherein n, o, p and q are independently selected from integers from 0 to 4; R5, R6, R7 and R8 are independently selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl, provided that at least one R 72 The group is either -OR5 or -NR5R6.

[0027] In another aspect of the invention, the chromophore has a structure selected from the following:

[0028]

[0029] Where X1 and X2 are selected from carbon and nitrogen atoms; a is an integer from 0 to 5, provided that a is an integer from 0 to 4 when one of X1 and X2 is a nitrogen atom, and an integer from 0 to 3 when both X1 and X2 are nitrogen atoms; each R1 is independently selected from halogen, hydroxyl, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl, ─S(O)2OH, ─S(O)2O - [M + R1 is selected from ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, and ☐, ... + R5R6; wherein structures VIII and VIIIa may exist independently and optionally in the ionic form of their counterions to maintain electroneutrality.

[0030] In another aspect of the invention, the chromophore has the following structure:

[0031]

[0032] AR 11 Selected from alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; R 11 and R 14 Independently selected from hydrogen, halogen, hydroxyl, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, ─S(O)2OH, ─S(O)2O - [M + ]、─C(O)OR5、─C(O)R5、─C(O)NR5R6、─NR5C(O)OR6、─NR5C(O)SR6、─OR5、─NR5R6、─S(O)2R5、─S(O)2NR5R6 and ─P(O)2R5; M is a cation; R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl; b is an integer from 1 to 10.

[0033] In another aspect of the invention, at least 50 mol% of the poly(alkylene oxide)-substituted chromophore colorant has a molecular weight of less than 5000, or even less than 2000. Furthermore, the poly(alkylene oxide)-substituted chromophore colorant comprises monomer residues, and at least 75% of the monomer residues in the poly(alkylene oxide) substituent are selected from -CH2CH2O- and -CH2CH(CH3)O-. In another aspect of the invention, the poly(alkylene oxide)-substituted chromophore colorant comprises monomer residues, and at least 75% of the monomer residues in the poly(alkylene oxide) substituent are -CH2CH2O-.

[0034] In another aspect of the invention, the hair care composition is a non-oxidative hair coloring cream. The non-oxidative hair coloring cream can be a semi-permanent hair coloring cream or a temporary hair coloring cream.

[0035] In another aspect of the invention, the hair care composition is an oxidative hair coloring cream. The oxidative hair coloring cream can be a partially permanent or permanent hair coloring cream.

[0036] In another aspect of the invention, the hair care composition is a shampoo or conditioner. Detailed Implementation

[0037] The invention described herein is a hair care composition comprising at least one hair care ingredient and at least one polymer colorant. The hair care composition comprising the polymer colorant is suitable for direct application to hair (e.g., human hair, animal hair, etc.) and provides improvements in stability and shading compared to prior art hair dyes.

[0038] As used in this article, the term "hair" is intended to include keratin fibers attached to living organisms, such as human head hair, human facial hair, animal hair, etc.

[0039] As used herein, the term "alkoxy" is intended to include C1-C8 alkoxy groups and alkoxy derivatives of polyols having repeating units such as butane, glycidol oxide, ethylene oxide, or propylene oxide.

[0040] As used herein, the terms “polyalkylene oxide” and “polyoxyalkylene”, which are used interchangeably herein, generally refer to molecular structures containing the following repeating units: -CH2CH2O-, -CH2CH2CH2O-, -CH2CH2CH2CH2O-, -CH2CH(CH3)O-, -CH2CH2CH(CH3)O-, and any combination thereof. Furthermore, the polyoxyalkylene component may be selected from one or more monomers selected from the following: C 2-20 Alkylene oxides, glycidyl ether, and mixtures thereof.

[0041] As used herein, unless otherwise stated, the terms "alkyl" and "alkyl-terminated" are intended to include C2 to C3. 100 Alkyl, C2 to C 50 Alkyl, C5 to C 25 Alkyl, or even C 10 To C 20 alkyl.

[0042] As used herein, unless otherwise stated, the term "aryl" is intended to include C5 to C6. 18 Aryl groups, and in one respect, intended to include C5 to C6. 12 Aryl.

[0043] As used herein, unless otherwise stated, the term "arylalkyl" is intended to include C1 to C2. 18 Arylalkyl, and in one aspect, it is intended to include C1 to C6 arylalkyl.

[0044] As used herein, unless otherwise stated, the term "alkanoyl" refers to the formula ─C(O)R a The monovalent group, wherein R a It is an alkyl group, preferably C3 to C4. 29 alkyl.

[0045] As used herein, unless otherwise stated, the term "alkenyl" refers to a monovalent group derived from an acyclic alkene by removing a hydrogen atom from any carbon atom. In the context of this definition, the term "acyclic alkene" refers to an acyclic hydrocarbon containing one or more carbon-carbon double bonds.

[0046] As used herein, unless otherwise stated, the term "alkenoyl" refers to the formula ─C(O)R b The monovalent group, wherein R b It is alkenyl, preferably C3 to C4. 29 Alkenyl group.

[0047] As used herein, unless otherwise stated, the term "aromatic acyl" refers to the formula ─C(O)R c The monovalent group, wherein R c It is aryl, preferably C6 to C6. 10 Aryl.

[0048] The terms “ethylene oxide,” “propylene oxide,” and “butane oxide” are represented herein by their typical symbols “EO,” “PO,” and “BO,” respectively.

[0049] Unless otherwise stated, all percentages and proportions are by weight. Unless otherwise stated, all percentages and proportions are based on the total composition.

[0050] Hair care compositions can be in any physical form suitable for application to hair, including but not limited to liquids, creams, sprays, conditioners, gels, mousses, etc. Hair care compositions are intended to include, but are not limited to, oxidative hair creams, non-oxidative hair creams, bleaching compositions, shampoos, conditioners, and any other compositions that can be used as excipients for applying the ingredients described herein to hair. Further details and examples of physical forms and excipients suitable for application of the compositions of the present invention can also be found in USPN 9,820,922 by Singer et al.

[0051] In this invention, the hair care composition comprises at least one hair care ingredient. Hair care ingredients include, for example, but not limited to: emollient oils, surfactants, nonionic surfactants, anionic surfactants, cationic, amphoteric, or betaine surfactants, polar solvents, chelating agents, pH adjusters, conditioning agents, and mixtures thereof. Oxidizing agents may also be included in oxidizing formulations. Furthermore, oxidizing agents may not be included in non-oxidizing formulations.

[0052] The hair care composition of the present invention is generally water-based and contains about 0.01 to 99% by weight, preferably about 0.1 to 98% by weight, and more preferably about 45 to 95% by weight of water in the total composition.

[0053] Hair care compositions may include, for example, hair detergents based on typical anionic, amphoteric, zwitterionic, nonionic, and / or cationic surfactants. Suitable commercially available shampoos clean the hair and remove sebum residue and / or styling agent residue and other impurities from the hair surface and scalp.

[0054] Hair care compositions may also include hair conditioning agents. Hair conditioning is understood by those skilled in the art to mean treatment of hair with so-called rins-off conditioning formulations (i.e., formulations that are rinsed away) or so-called leave-on conditioning formulations (i.e., formulations that remain on the hair without being rinsed away), particularly with conditioning shampoos or conditioning agents. This treatment, in particular, makes hair easier to comb in both wet and dry conditions, both along its length and at the ends (detangling); results in improved tactile properties (e.g., smoothness, softness, and frizz); and also results in shinier hair, less static charge, and improved styling ease. Overall, a well-cared-for and healthy overall condition of the hair is thus achieved through conditioning.

[0055] Moisturizing oil

[0056] If desired, the hair cream composition may contain one or more moisturizing oils. These oils provide a conditioning effect to the hair. If present, such oils may comprise about 0.001 to 45% by weight, preferably about 0.01 to 40% by weight, and more preferably about 0.1 to 35% by weight of the total composition. Suitable oils include silicones, such as dimethicone, phenyl silicones, fatty alkyl silicones (e.g., cetyl or stearyl dimethicone), or silicone surfactants commonly referred to as dimethicone copolyol or cetyl dimethicone copolyol. Also suitable are various animal, plant, or mineral oils derived from plants or animals, or synthetic oils. Examples include oils from sunflower, castor seed, orange, lemon, jojoba, mineral oils, etc. Other common examples include cetearyl alcohol, lauryl alcohol, myristyl alcohol, lanolin alcohol, coconut alcohol, etc.

[0057] surfactants

[0058] The oxidizing dye composition may contain one or more surfactants. Suitable surfactants include anionic surfactants, nonionic surfactants, amphoteric surfactants, etc. If present, the surfactant may comprise about 0.001 to 50% by weight, preferably about 0.005 to 45% by weight, and more preferably about 0.1 to 40% by weight of the first composition.

[0059] Nonionic surfactants

[0060] Examples of nonionic surfactants include alkoxylated alcohols or ethers, alkoxylated carboxylic acids, and sorbitol derivatives. Alkoxylated alcohols or ethers are formed by reacting an alcohol with an alkylene oxide (typically ethylene oxide or propylene oxide). Preferably, the alcohol is a fatty alcohol having 6 to 30 carbon atoms and a straight or branched, saturated or unsaturated carbon chain. Examples of such components include: stearyl alcohol polyether 2-30, formed by the reaction of stearyl alcohol and ethylene oxide, wherein the number of ethylene oxide repeating units is 2 to 30; lauryl alcohol polyether 2-30, formed by the reaction of lauryl alcohol and ethylene oxide, wherein the number of ethylene oxide repeating units is 2 to 30; oleyl alcohol polyether 2-30, formed by the reaction of oleyl alcohol and ethylene oxide, wherein the number of ethylene oxide repeating units is 2 to 30; ceteareth 2-100, formed by the reaction of a mixture of cetyl alcohol and stearyl alcohol with ethylene oxide, wherein the number of ethylene oxide repeating units in the molecule is 2 to 100; ceteareth 1-45... 1-45), which are formed by the reaction of cetyl alcohol and ethylene oxide, and the number of repeating ethylene oxide units is 1 to 45, etc. Particularly preferred is that the nonionic surfactant is stearyl alcohol polyether-20 or cetearyl alcohol polyether-20. Also suitable are alkoxylated carboxylic acids, which are formed by the reaction of carboxylic acids with epoxides or with polymeric ethers.

[0061] Also suitable are various types of alkoxylated sorbitol and alkoxylated sorbitol derivatives. For example, alkoxylation of sorbitol—particularly ethoxylation—provides polyalkoxylated sorbitol derivatives. Esterification of polyalkoxylated sorbitol provides sorbitol esters, such as polysorbate esters. Examples of such components include polysorbate esters 20-85, sorbitol oleate, sorbitol palmitate, sorbitol sesquiisostearate, sorbitol stearate, etc. In a preferred embodiment, polysorbate ester 20 is preferred.

[0062] Anionic surfactants

[0063] The hair cream composition may optionally contain one or more anionic surfactants. The preferred range for anionic surfactants is about 0.01 to 25% by weight, preferably 0.5 to 20% by weight, and more preferably 1 to 15% by weight of the total oxidizing composition. Suitable anionic surfactants include those typically having the formulas ROSO3M and RO(C2H4O). xSO3M is an alkyl sulfate and an alkyl ether sulfate, wherein R is an alkyl or alkenyl group with about 10 to 20 carbon atoms, x is 1 to about 10, and M is a water-soluble cation, such as ammonium, sodium, potassium, or triethanolamine cation.

[0064] Another type of anionic surfactant that can be used in the compositions of the present invention is a water-soluble salt of an organic sulfuric acid reaction product of the general formula R1—SO3-M, wherein R1 is selected from a saturated aliphatic hydrocarbon group having about 8 to about 24 carbon atoms, preferably 12 to about 18 carbon atoms, either straight-chain or branched; and M is a cationic surfactant. Examples of such anionic surfactants are salts of organic sulfuric acid reaction products of hydrocarbons (e.g., ortho-chain hydrocarbons having 8 to 24 carbon atoms) and sulfonating agents (e.g., sulfur trioxide).

[0065] Other suitable anionic surfactants include fatty acids esterified with hydroxyethyl sulfonic acid and neutralized with sodium hydroxide, or reaction products of fatty acids reacting with alkanolamines or ammonium hydroxide. Fatty acids can be derived from, for example, coconut oil. Examples of fatty acids also include lauric acid, stearic acid, oleic acid, and palmitic acid.

[0066] In addition, succinates and succinimates are suitable anionic surfactants. These substances include compounds such as disodium N-octadecyl sulfosuccinate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinate; and esters of sodium sulfosuccinate, such as dihexyl sulfosuccinate and dioctyl sulfosuccinate.

[0067] Other suitable anionic surfactants include olefin sulfonates having about 12 to 24 carbon atoms. The term "olefin sulfonate" refers to a compound prepared by sulfonation of an α-olefin via uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture under conditions that cause hydrolysis of any sulcolones formed in the reaction to yield the corresponding hydroxyalkyl sulfonate. The α-olefin from which the olefin sulfonate is derived is a monoolefin having about 12 to 24 carbon atoms, preferably about 14 to 16 carbon atoms.

[0068] Other suitable anionic organic surfactants are β-alkoxyalkyl sulfonates or their water-soluble soaps, such as C 10-20 Salts of fatty acids, such as those used in coconut and butter-based soaps. Preferred salts are ammonium, potassium, and sodium salts.

[0069] Another class of anionic surfactants includes N-acyl amino acid surfactants and their salts (alkali metal salts, alkaline earth metal salts, and ammonium salts) having the following formula: where R1 is C 8-24 Alkyl or alkenyl, preferably C 10-18R2 represents H and C. 1-4 Alkyl, phenyl, or -CH2COOM; R3 is CX2- or C 1-2 Alkyl groups, wherein each X is independently H or C. 1-6 Alkyl or alkyl ester, n is 1 to 4, and M is H or a cation forming a salt as described above. Examples of such surfactants include N-acylsarcosine salts, including lauroylsarcosine, myristylsarcosine, cocoylsarcosine, and oleylsarcosine, preferably in sodium or potassium form.

[0070] Cationic, amphoteric, or betaine surfactants

[0071] Certain types of amphoteric, zwitterionic, or cationic surfactants can also be used as amphiphilic surfactants. A description of such surfactants can be found in US Patent No. 5,843,193, the entire contents of which are incorporated herein by reference.

[0072] Amphoteric surfactants that can be used in the compositions of the present invention are generally described as derivatives of aliphatic secondary or tertiary amines, wherein one aliphatic group is a straight-chain or branched alkyl group of 8 to 18 carbon atoms, and the other aliphatic group contains an anionic group, such as a carboxyl group, sulfonate group, sulfate group, phosphate group, or phosphonate group.

[0073] Other suitable amphoteric surfactants are monocarboxylate or dicarboxylate, such as cocamphocarboxypropionate, cocoamphocarboxypropionic acid, cocamphocarboxyglycinate, and cocoamphoacetate.

[0074] Other types of amphoteric surfactants include those with the formula R—NH(CH2). n COOM's aminoalkyl salt or formula R—[(CH2)] m [COOM]2 iminodialkylates and mixtures thereof, wherein n and m are 1 to 4, and R is C 8-22Alkyl or alkenyl groups, where M is hydrogen, an alkali metal, an alkaline earth metal, ammonium, or an alkanol ammonium. Examples of such amphoteric surfactants include n-alkylaminopropionates and n-alkyliminopropionates. Amphoteric surfactants are also suitable for use in the compositions of the invention, comprising betaines, such as higher alkyl betaines, such as cocoyl dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl α-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl γ-carboxyethyl betaine, and mixtures thereof. Also suitable are sulfonyl betaines and amide betaines, such as cocoyl dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, etc. Cocamidopropyl betaine is particularly preferred.

[0075] polar solvents

[0076] The hair cream composition may also contain various non-aqueous polar solvents other than water, including monohydric alcohols, dihydric alcohols, or polyhydric alcohols and similar water-soluble components. If present, such polar solvents may be from about 0.02 to 25% by weight, preferably from about 0.05 to 15% by weight, and more preferably from about 0.1 to 10% by weight in the first composition. Examples of suitable monohydric alcohols include ethanol, isopropanol, benzyl alcohol, butanol, pentanol, ethoxyethanol, etc. Examples of dihydric or polyhydric alcohols that can be used, as well as sugars and other types of humectants, include glycerin, glucose, fructose, mannose, mannitol, maltitol, lactitol, inositol, etc. Suitable diols include propylene glycol, butylene glycol, ethylene glycol, polyethylene glycol having 4 to 250 repeating ethylene glycol units, ethoxydiethylene glycol, etc.

[0077] Chelating agents

[0078] The oxidizing dye composition may optionally contain 0.0001 to 5%, preferably 0.0005 to 3%, more preferably 0.001 to 2%, of one or more chelating agents capable of complexing with and deactivating metal ions to prevent adverse effects on the stability or effectiveness of the composition. In particular, the chelating agent chelates metal ions present in water and prevents these ions from interfering with dye deposition and the reaction of the dye with the surface of hair fibers. Suitable chelating agents include EDTA and its calcium, sodium, or potassium derivatives, HEDTA, sodium citrate, TEA-EDTA, etc.

[0079] pH adjuster

[0080] Alternatively, a small amount of acid or base may be added to adjust the pH of the oxidizing dye composition to the desired pH range. Suitable acids include hydrochloric acid, phosphoric acid, hydroxyethyl phosphate, etc. Suitable bases include sodium hydroxide, ammonium hydroxide, potassium hydroxide, etc. Also suitable are primary, secondary, or tertiary amines, or their derivatives such as aminomethylpropanol, monoethanolamine, etc. Phosphates, such as potassium phosphate, disodium hydrogen phosphate, etc., may also be used. The recommended range for the pH adjuster is about 0.00001 to 8% by weight of the total composition, preferably about 0.00005 to 6% by weight, more preferably about 0.0001 to 5% by weight.

[0081] Conditioner

[0082] Hair cream compositions may also contain hair conditioning agents. Suitable conditioning agents for use herein include, but are not limited to, cationic surfactants, insoluble silicones, non-volatile hydrocarbons, non-volatile hydrocarbon esters, and mixtures thereof.

[0083] Preferred conditioning agents used herein include cationic surfactants, cationic polymers, insoluble silicone conditioning agents, amino-functionalized silicones, and saturated C14-C22 linear fatty alcohols and mixtures thereof.

[0084] When present, the insoluble silicone conditioner is present in the composition at a level of about 0.1 to 10% by weight, preferably about 0.1% to about 5% by weight, more preferably about 1% to about 3% by weight. Suitable insoluble silicones include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyethersiloxane copolymers, and mixtures thereof.

[0085] Other components

[0086] The compositions of the present invention typically also contain many other components commonly used in hair care compositions (e.g., shampoos, conditioners, styling aids, and colorants) known to those skilled in the art, such as thickeners and diluents. Additionally, many optional materials may be added to the compositions described herein at levels of about 0.001% to about 5% by weight, preferably about 0.01% to about 3% by weight, and more preferably about 0.05% to about 2% by weight. This material includes: proteins and peptides and their derivatives; water-soluble or soluble preservatives, such as DMDM ​​hydantoin, Germall 115, methyl, ethyl, propyl, and butyl esters of hydroxybenzoic acid, EDTA, Euxyl(RTM) K400, natural preservatives (such as benzyl alcohol, potassium sorbate, and bisabolol), benzoic acid, sodium benzoate, and 2-phenoxyethanol; antioxidants, such as sodium sulfite, hydroquinone, sodium bisulfite, sodium metabisulfite, and thioglycolic acid, sodium dithionite, and erythrobic acid. acid) and other thiols; H2O2 stabilizers, such as tin compounds (e.g., sodium stannate, tin hydroxide and stannous octoate), acetanilide, phenacetin, colloidal silica (e.g., magnesium silicate), hydroxyquinoline sulfate, sodium phosphate and tetrasodium pyrophosphate; and >hydroxybenzoates; wetting agents, such as hyaluronic acid, chitin and starch-grafted sodium polyacrylate, as well as methylcellulose, starch, higher fatty alcohols, paraffin oil, fatty acids, etc.; solvents; antibacterial agents; low-temperature phase modifiers, such as ammonium ion sources (e.g. NH4Cl); viscosity control agents, such as magnesium sulfate and other electrolytes; quaternary ammonium compounds, such as distearate-, dilauryl-, dihydrotallow-, dimethylammonium chloride, dicetyldiethylammonium ethyl sulfate, ditallowdimethylammonium methylsulphate, diisoya dimethylammonium chloride and dicoco dimethylammonium chloride. Ammonium chloride); enzyme stabilizers, such as water-soluble sources of calcium or borate substances; TiO2 and TiO2-coated mica; fragrances and fragrance stabilizers; zeolites and their derivatives; and metal ion chelating agents (e.g., polycarboxylates, amino polycarboxylates, polyphosphonates, amino polyphosphonates, etc.) and water softeners (e.g., sodium citrate, inorganic peroxide oxidants, and enzymes).

[0087] Oxidizing agent composition

[0088] In addition, the aqueous hair cream composition may also contain an oxidizing agent. Most commonly, hydrogen peroxide is used as the aqueous oxidizing agent, but other peroxides or oxidizing agents, such as calcium peroxide, may be used. Preferably, the concentration of hydrogen peroxide in the aqueous oxidizing agent composition ranges from about 10 to 40 volumes, i.e., the volume-based amount of hydrogen peroxide present in the composition.

[0089] Other suitable oxidants (also referred to herein as “bleaching agents”) include, for example, sources of hydrogen peroxide, such as those described in detail in Kirk Othmer’s Encyclopedia of Chemical Technology (4th edition, 1992, John Wiley & Sons), Volume 4, pp. 271–300, “Bleaching Agents (Survey)”. These sources of hydrogen peroxide include various forms of sodium perborate and sodium percarbonate, including various coated and modified forms of these compounds.

[0090] Preferred sources of hydrogen peroxide used herein may be any convenient source, including hydrogen peroxide itself. For example, perborates such as sodium perborate (any hydrate, but preferably monohydrate or tetrahydrate), sodium carbonate peroxyhydrate or equivalent percarbonates, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide may be used herein. Also available are readily available oxygen sources, such as persulfate bleaching agents (e.g., potassium persulfate preparations (OXONE) manufactured by DuPont). Sodium perborate monohydrate, sodium percarbonate, sodium persulfate, and potassium persulfate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources may also be used.

[0091] The compositions of the present invention may also contain chlorine-based bleaching materials as bleaching agents. Such agents are well known in the art and include, for example, sodium dichloroisocyanurate (“NaDCC”).

[0092] In one aspect of the invention, the peroxide bleaching component in the composition is formulated together with an activator (a peroxyacid precursor). The activator is present in the composition at a level of from about 0.01% by weight (preferably from about 0.5% by weight, more preferably from about 1% by weight) to about 15% by weight (preferably from about 10% by weight, more preferably from about 8% by weight). The bleaching activator used herein is any compound whose source, when used with hydrogen peroxide, results in the in-situ generation of a peroxyacid corresponding to the bleaching activator. Various non-limiting examples of activators are disclosed in US Patent Nos. 5,576,282, 4,915,854, and 4,412,934. See also US Patent No. 4,634,551 for other typical bleaching agents and activators that may be used herein.

[0093] Preferred activators are selected from tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenyl benzoate (PhBz), and decanoyloxybenzenesulfonate (C). 10 -OBS), benzoylcaprolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS), perhydrolyzable esters and mixtures thereof, with benzoylcaprolactam and benzoylcaprolactam being the most preferred. Particularly preferred bleaching activators in the pH range of about 8 to about 11 are those having the OBS or VL leaving group.

[0094] Preferred hydrophobic bleaching activators include, but are not limited to: nonanoyloxybenzenesulfonate (NOBS); sodium 4-[N-(nonanoyl)aminohexanoyloxy]-benzenesulfonate (NACA-OBS), examples of which are described in US Patent No. 5,523,434; lauroyloxybenzenesulfonate (LOBS or C 12 -OBS); 10-Undecenoyloxybenzenesulfonate (UDOBS or C with an unsaturated C at the 10 position) 11 -OBS); and decanoyloxybenzoic acid (DOBA).

[0095] Preferred bleaching activators are those described in US Patent No. 5,998,350 by Burns et al., US Patent No. 5,698,504 by Christie et al., US Patent No. 5,695,679 by Christie et al., US Patent No. 5,686,401 by Willey et al., US Patent No. 5,686,014 by Hartshorn et al., US Patent No. 5,405,412 by Willey et al., US Patent No. 5,405,413 by Willey et al., US Patent No. 5,130,045 by Mitchel et al., and US Patent No. 4,412,934 by Chung et al., as well as co-pending patent application serial number 08 / 064,564, all of which are incorporated herein by reference.

[0096] It may also contain a quaternary substituted bleaching activator. The compositions of the present invention preferably contain a quaternary substituted bleaching activator (QSBA) or a quaternary substituted peracid (QSP) (preferably a quaternary substituted percarboxylic acid or a quaternary substituted peroxyimino acid); more preferably the former. Preferred QSBA structures are also described in US Patent No. 5,686,015 of Willey et al., US Patent No. 5,654,421 of Taylor et al., US Patent No. 5,460,747 of Gosselink et al., US Patent No. 5,584,888 of Miracle et al., and US Patent No. 5,578,136 of Taylor et al., all of which are incorporated herein by reference.

[0097] Other bleaching activators that may be used herein are amide-substituted, as described in US Patent Nos. 5,698,504, 5,695,679 and 5,686,014, each of which is incorporated herein by reference. Preferred examples of such bleaching activators include (6-octanoylaminohexanoyl)oxybenzenesulfonate, (6-nonanoylaminohexanoyl)oxybenzenesulfonate, (6-decanoylaminohexanoyl)oxybenzenesulfonate, and mixtures thereof.

[0098] Other available activators are disclosed in US Patent Nos. 5,698,504, 5,695,679, and 5,686,014, each of which is cited above; and in US Patent No. 4,966,723 by Hodge et al. These activators include benzoxazine-type activators, for example, fused at the 1,2-position to a portion of --C(O)OC(R). 1 )=N-C6H4 ring.

[0099] Nitriles (such as acetonitrile and / or ammonium nitrile and other quaternary nitrogen-containing nitriles) are another class of activators that can be used herein. Non-limiting examples of such nitrile bleaching activators are described in US 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 EP Nos. 790 244, 775 127, 1,017 773, 1,017 776 and WO99 / 14302, WO 99 / 14296, WO96 / 40661, all of which are incorporated herein by reference.

[0100] Depending on the activator and precise application, good bleaching results can be obtained from bleaching systems with a pH of about 6 to about 13, preferably about 9.0 to about 11.5, at the time of use. Typically, activators with electron-withdrawing moieties are used, for example, in a pH range close to neutral or sub-neutral. Bases and buffers can be used to ensure such a pH.

[0101] Acyllactam activators (such as those described in US Patent Nos. 5,698,504, 5,695,679 and 5,686,014, each of which is cited above) may also be used herein, especially acylcaprolactam (see, for example, WO 94-28102A) and acylvalerolactam (see US Patent No. 5,503,639 of Willey et al., which is incorporated herein by reference).

[0102] Organic peroxides—especially diacyl peroxides—are also suitable for use. Extensive examples of these substances can be found in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982, pp. 27–90, and especially pp. 63–72, all of which are incorporated herein by reference. If diacyl peroxides are used, they are preferably those that have the least adverse effects on fabric care, including color care.

[0103] The compositions and methods of the present invention may optionally include a metal-containing bleaching catalyst, preferably a bleaching catalyst containing manganese and cobalt.

[0104] One type of metal-containing bleaching catalyst comprises a catalyst system consisting of: a transition metal cation (e.g., copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cation) with defined bleaching catalytic activity; an auxiliary metal cation (e.g., zinc or aluminum cation) with little or no bleaching catalytic activity; and a sequestrate having defined stability constants for the catalytic metal cation and the auxiliary metal cation, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid), and their water-soluble salts. Such a catalyst is disclosed in Bragg's US Patent No. 4,430,243.

[0105] If desired, the compositions described herein can be catalyzed by manganese compounds. Such compounds and their levels of use are well known in the art, and include, for example, manganese-based catalysts disclosed in US Patent Nos. 5,576,282, 5,246,621, 5,244,594, 5,194,416 and 5,114,606, and European Patent Application Publication Nos. 549,271A1, 549,272A1, 544,440A2 and 544,490A1. Preferred examples of these catalysts include Mn IV 2(uO)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2、Mn III 2(uO)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(ClO4)2、Mn IV 4(uO)6(1,4,7-triazacyclononane)4(ClO4)4、Mn III Mn IV 4(uO)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2(ClO4)3、Mn IV (1,4,7-Trimethyl-1,4,7-triazacyclononane)-(OCH3)3(PF6) and mixtures thereof. Other metal-based bleaching catalysts include those disclosed in US Patent Nos. 4,430,243 and 5,114,611. The use of manganese with various complex ligands to enhance bleaching has also been reported in the following patents: US 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.

[0106] Cobalt bleaching catalysts that can be used in this document are known and described, for example, in US Patent Nos. 5,597,936, 5,595,967 and 5,703,030 and MLTobe, “Base Hydrolysis of Transition-Metal Complexes”. Adv.Inorg.Bioinorg.Mech. (1983), 2, pp. 1-94. The most preferred cobalt catalyst used in this paper is one having the formula [Co(NH3)5OAc]T y (where “OAc” represents the acetate portion and “T” represents the acetate portion.) y Cobalt pentamine acetate (with anions), especially cobalt pentamine acetate chloride [Co(NH3)5OAc]Cl2, and [Co(NH3)5OAc](OAc)2, [Co(NH3)5OAc](PF6)2, [Co(NH3)5OAc](SO4), [Co(NH3)5OAc](BF4)2 and [Co(NH3)5OAc](NO3)2 ("PAC" in this document).

[0107] These cobalt catalysts can be readily prepared by known processes, such as those taught in the following documents: for example, US patents 6,302,921, 6,287,580, 6,140,294, 5,597,936, 5,595,967 and 5,703,030; Tobe articles and references cited therein; and US patent 4,810,410; J. Chem. Ed. (1989), 66(12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg.Chem. , 18 , 1497-1502 (1979); Inorg.Chem., 21 , 2881-2885(1982); Inorg.Chem. , 18 , 2023-2025(1979); Inorg.Synthesis, 173-176(1960); and Journal of Physical Chemistry , 56 , 22-25 (1952).

[0108] The compositions described herein may also suitably comprise transition metal complexes with large polycyclic rigid ligands as bleaching catalysts. The amounts used are catalytically effective amounts, suitably about 1 ppb or more, for example not more than about 99.9%, more typically about 0.001 ppm or more, preferably about 0.05 ppm or about 500 ppm (where “ppb” means parts by weight per billion parts by weight and “ppm” means parts by weight per million parts by weight).

[0109] Transition metal bleaching catalysts suitable for use with macrocyclic rigid ligands in the compositions of the present invention typically include known compounds, non-limiting examples of any of the following:

[0110] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0111] Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0112] Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)Hexafluorophosphate

[0113] Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)Hexafluorophosphate

[0114] Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III)Hexafluorophosphate

[0115] Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)tetrafluoroborate

[0116] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(III) hexafluorophosphate

[0117] Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(III) hexafluorophosphate

[0118] Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0119] Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0120] Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0121] Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0122] Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II).

[0123] As a practical problem, and not as a limitation, the compositions and methods described herein can be modified to provide a bleaching catalyst active material of about at least one part per hundred million in the composition comprising the lipophilic fluid and the bleaching system, and preferably about 0.01 ppm to about 25 ppm, more preferably about 0.05 ppm to about 10 ppm and most preferably about 0.1 ppm to about 5 ppm in the composition comprising the lipophilic fluid and the bleaching system.

[0124] The compositions described herein may contain one or more bleach boosting compounds. These compounds provide enhanced bleaching efficacy in lower temperature applications. The bleach boosters work in conjunction with conventional peroxy bleaching sources to provide enhanced bleaching efficacy. This is typically achieved through in-situ formation of reactive oxygen species (ROS) such as ethylene oxide, oxaziridine, or oxaziridinium. Alternatively, pre-formed ethylene oxide, oxaziridine, and oxaziridinium may be used.

[0125] Suitable bleaching enhancing compounds used according to the invention contain cationic imines, zwitterionic imines, anionic imines, and / or polyionic imines, as well as mixtures thereof, with a net charge of about +3 to about -3. These imine bleaching enhancing compounds of the invention include those with the following general formulas:

[0126]

[0127] Where R 1 To R 4 It can be hydrogen, or an unsubstituted or substituted group selected from phenyl, aryl, heterocyclic, alkyl and cycloalkyl groups.

[0128] Preferred bleaching enhancers include zwitterionic bleaching enhancers, described in US Patent Nos. 5,576,282 and 5,718,614. Other bleaching enhancers include cationic bleaching enhancers described in US 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.

[0129] The peroxide source is well known in the art, and any peroxide source that can be used in this invention may include any of these known sources (including peroxide compounds and compounds that provide an effective amount of peroxide in situ under consumer use conditions). The peroxide source may include: a hydrogen peroxide source, in-situ formation of peracid anions through a reaction of a hydrogen peroxide source and a bleaching activator, a pre-formed peracid compound, or a mixture of suitable peroxide sources. Of course, those skilled in the art will recognize that other peroxide sources can be used without departing from the scope of this invention. Bleaching enhancement compounds, when present, are preferably used in conjunction with the peroxide source in the bleaching system of this invention.

[0130] Pre-formed peracids are also suitable as bleaching agents. The pre-formed peracid compounds used herein are any convenient compounds that are stable and provide an effective amount of peracid or peracid anion under consumer use conditions. Pre-formed peracid compounds may be selected from percarboxylic acids and their salts, percarbonic acids and their salts, perimino acids and their salts, peroxymonosulfate and their salts, and mixtures thereof. Examples of these compounds are described in US Patent No. 5,576,282 by Miracle et al.

[0131] A suitable class of organic peroxycarboxylic acids has the general formula:

[0132]

[0133] Wherein R is an alkylene or substituted alkylene containing 1 to 22 carbon atoms, or a phenylene or substituted phenylene; and Y is hydrogen, halogen, alkyl, aryl, -C(O)OH or -C(O)OOH.

[0134] The organic peroxyacids suitable for use in this invention may contain one or two peroxy groups and may be aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula:

[0135]

[0136] Where Y can be, for example, H, CH3, CH2Cl, C(O)OH, or C(O)OOH; and n is an integer from 0 to 20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

[0137]

[0138] Y can be, for example, hydrogen, alkyl, alkyl halogen, halogen, C(O)OH or C(O)OOH.

[0139] Typical monoperoxy acids that can be used in this article include alkyl and aryl peroxy acids, for example:

[0140] (i) Peroxybenzoic acid and cyclically substituted peroxybenzoic acid, such as peroxy-α-naphthoic acid, monoperoxybenzoic acid (magnesium salt hexahydrate) and o-carboxybenzoamide peroxyhexanoic acid (sodium salt).

[0141] (ii) Aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, such as peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxyhexanoic acid (NAPCA), N,N-(3-octylsuccinoyl)aminoperoxyhexanoic acid (SAPA) and N,N-phthaloylaminoperoxyhexanoic acid (PAP).

[0142] (iii) Acylaminoperoxyacids, such as monononylamide of peroxysuccinic acid (NAPSA) or monononylamide of peroxyadipic acid (NAPAA).

[0143] Typical diperox acids that can be used in this article include alkyl diperox acids and aryl diperox acids, for example:

[0144] (i) 1,12-disperoxydodecanoic acid;

[0145] (ii) 1,9-Disperoxyazelaic acid;

[0146] (iii) Disperoxytridecanoic acid, disperoxysedicarboxylic acid and disperoxyisophthalic acid;

[0147] (iv) 2-decyl diperperoxybut-1,4-diacid;

[0148] (v)4,4'-sulfonyl diperoxybenzoic acid.

[0149] Such bleaching agents are disclosed in Hartman's US Patent No. 4,483,781 and Burns et al.'s US Patent No. 4,634,551, Banks et al.'s European Patent Application No. 0,133,354, and Chung et al.'s US Patent No. 4,412,934. Sources also include 6-nonylamino-6-oxoperoxyhexanoic acid as described in Burns et al.'s US Patent No. 4,634,551. Persulfate compounds (e.g., potassium persulfate preparations (OXONE) commercially manufactured by EIDuPont de Nemours of Wilmington, DE) can also be used as suitable sources of peroxymonosulfate. PAP is disclosed, for example, in US Patent Nos. 5,487,818, 5,310,934, 5,246,620, 5,279,757, and 5,132,431.

[0150] Photobleaching agents are also suitable for use in the compositions of the present invention, and include, but are not limited to, the photobleaching agents described in US Patent Nos. 4,217,105 and 5,916,481.

[0151] Enzymatic systems can be used as bleaching agents. Hydrogen peroxide can also be produced by adding an enzyme system capable of generating hydrogen peroxide (i.e., an enzyme and a substrate for it). Such an enzyme system is disclosed in EP patent application 91202655.6, filed on October 9, 1991.

[0152] The compositions and methods of this invention can utilize alternative bleaching systems, such as ozone, chlorine dioxide, etc. Bleaching with ozone can be achieved by using an ozone concentration of about 20 to about 300 g / m³. 3The process involves introducing an ozone-containing gas into the solution to be in contact with the hair. The gas-to-liquid ratio in the solution should be maintained at approximately 1:2.5 to approximately 1:6. US Patent No. 5,346,588 describes a method using ozone as an alternative to conventional bleaching systems, and that patent is incorporated herein by reference.

[0153] Colorant

[0154] The coloring compositions disclosed herein may optionally comprise one or more non-polymeric colorants. These coloring compounds may be selected from oxidizing dye precursors, direct dyes, pigments, and mixtures thereof. Oxidizing dyes are generally selected from one or more oxidizing chromogenic bases optionally combined with one or more color-forming agents. For example, oxidizing chromogenic bases are selected from p-phenylenediamines, bis(phenyl)alkylene diamines, p-aminophenols, o-aminophenols, and heterocyclic bases, as well as their addition salts.

[0155] Among the p-phenylenediamine class, examples that may be mentioned include p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-di(β-hydroxyethyl)-p-phenylenediamine, 4-N,N-di(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-di(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, and 2-fluoro-p-phenylenediamine. Phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(β-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-3-methyl-p-phenylenediamine, N-ethyl-N-(β-hydroxyethyl)-p-phenylenediamine, N-(β,γ-dihydroxypropyl)-p-phenylenediamine, N-(4'-aminophenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-β-hydroxyethyloxy-p-phenylenediamine, 2-β-acetaminoethyloxy-p-phenylenediamine, N-(β-methoxyethyl)-p-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-p-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene, and 3-hydroxy-1-(4'-aminophenyl)pyrrolidine, and their addition salts with acids.

[0156] Among the p-phenylenediamines mentioned above, p-phenylenediamine, p-toluenediamine, 2-isopropyl-p-phenylenediamine, 2-β-hydroxyethyl-p-phenylenediamine, 2-β-hydroxyethyloxy-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, N,N-di(β-hydroxyethyl)-p-phenylenediamine, 2-chloro-p-phenylenediamine and 2-β-acetaminoethyloxy-p-phenylenediamine, as well as their addition salts with acids are particularly preferred.

[0157] Among bis(phenyl)alkylene diamines, examples that may be mentioned are N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(4-methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine, and 1,8-bis(2,5-diaminophenoxy)-3,6-dioxane and their addition salts.

[0158] Among the p-aminophenols, examples include p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol, and 4-amino-2-fluorophenol, as well as their acid addition salts. Among the o-aminophenols, examples include 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, and 5-acetamido-2-aminophenol, as well as their addition salts. Among heterocyclic bases, examples include pyridine derivatives, pyrimidine derivatives, and pyrazole derivatives.

[0159] Among pyridine derivatives, compounds such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, and 3,4-diaminopyridine, as well as their addition salts, may be mentioned. Other pyridine oxidation chromogenic bases that can be used in this disclosure are 3-aminopyrazolo[1,5-a]pyridine oxidation chromogenic bases or their addition salts, as described, for example, in patent application FR 2 801308. Examples that may be mentioned include pyrazolo[1,5-a]pyridin-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyridin-3-ylamine, 2-morpholin-4-ylpyrazolo[1,5-a]pyridin-3-ylamine, 3-aminopyrazolo[1,5-a]pyridin-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyridin-3-ylamine, (3-aminopyrazolo[1,5-a]pyridin-7-yl)methanol, 2-(3-aminopyrazolo[1,5-a]pyridin-5-yl)ethanol, 2-(3- Aminopyrazolo[1,5-a]pyridin-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyridin-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridin-3,7-diamine, 7-morpholin-4-ylpyrazolo[1,5-a]pyridin-3-ylamine, pyrazolo[1,5-a]pyridin-3,5-diamine, 5-morpholin-4-ylpyrazolo[1,5-a]pyridin-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyridin-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[1,5-a]pyridin-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol, 3-aminopyrazolo[1,5-a]pyridin-6-ol, 3-aminopyrazolo[1,5-a]pyridin-7-ol, 2-tetra-hydroxyethoxy-3-amino-pyrazolo[ [1,5-a]pyridine (2-.quadrature.-hydroxyethoxy-3-amino-pyrazolo[1,5-a]pyridine), 2-(4-dimethylpyperazinium-1-yl)-3-amino-pyrazolo[1,5-a]pyridine, and their addition salts.

[0160] The more particular oxidative chromogenic bases used in this disclosure are selected from 3-aminopyrazolo[1,5-a]pyridines, and are preferably substituted at the carbon atom at position 2 as follows:

[0161] (a) A (di) (C1 to C6) (alkyl)amino group, wherein the alkyl group may be substituted with at least one hydroxyl, amino, or imidazolium group;

[0162] (b) A heterocyclic alkyl group comprising a 5- to 7-membered chain and 1 to 3 heteroatoms, which may be cationic and may be substituted with one or more (C1 to C6 alkyl) groups, such as di(C1 to C4)alkylpiperazineonium; or

[0163] (c) An (C1 to C6) alkoxy group, which may be substituted by one or more hydroxyl groups, such as tetra-hydroxyalkoxy;

[0164] And their addition salts.

[0165] Among pyrimidine derivatives, those that may be mentioned include compounds such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts, as well as their tautomer forms when tautomerism equilibrium is present.

[0166] Among pyrazole derivatives, those mentioned include 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diamino-pyrazole, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazylpyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4, Compounds of 5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and their addition salts. 4,5-diamino-1-(β-methoxyethyl)pyrazole may also be used.

[0167] Also mentioned are diamino-N,N-dihydropyrazolopyrazolinones, such as the following compounds and their addition salts: 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-isopropylamino-6,7 -dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-(pyrrolid-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1 2-Di(2-hydroxyethyl)-1,2-dihydropyrazole-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazole[1,2-a]pyrazole-1-one, 2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazole[1,2-a]pyrazole-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridyl Zizo[1,2-a]pyrazol-1-one, 4-amino-1,2-diethyl-5-(pyrrolidone-1-yl)-1,2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidone-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one. Preferably, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and / or their salts are used. Preferably, 4,5-diamino-1-(β-hydroxyethyl)pyrazole and / or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazole-1-one and / or their salts are used as heterocyclic bases.

[0168] The compositions according to this disclosure may optionally contain one or more coloring agents, advantageously selected from those conventionally used for dyeing or coloring keratin fibers. Among these coloring agents, m-phenylenediamine, m-aminophenol, resorcinol, naphthalene-based coloring agents and heterocyclic coloring agents, as well as their addition salts, are particularly mentioned. Examples of possible names include 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 5-amino-6-chloro-o-cresol (3-amino-2-chloro-6-methylphenol), 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diamino-phenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylamino-benzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6- Hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzimorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(J-hydroxyethylamino)toluene, 6-hydroxy-dihydroindole, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole and 6-methylpyrazolo[1,5-a]benzimidazole, their addition salts with acids, and mixtures thereof.

[0169] Typically, the addition salts of the oxidizing chromogenic bases and color-forming agents used in the context of this disclosure are particularly selected from addition salts of acids, such as hydrochlorides, hydrobroms, sulfates, citrates, succinates, tartrates, lactates, toluenesulfonates, benzenesulfonates, phosphates, and acetates. One or more oxidizing chromogenic bases are each advantageously present in an amount from 0.001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the compositions disclosed herein. If one or more color-forming agents are present, they are each advantageously present in an amount from 0.001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the compositions disclosed herein.

[0170] Compositions according to this disclosure may comprise b) one or more synthetic or natural direct dyes or pigments. Suitable dyes or pigments include, but are not limited to, those listed in Annex IV of Regulation (EC) 1223 / 2009 of the European Parliament and the Council. Examples of suitable direct dyes that may be mentioned include: azo direct dyes, (poly)methylene dyes (e.g., cyanine blue, semi-cyanine blue, and styryl), carbonyl dyes, azazine dyes, nitro(hetero)aryl dyes, tri(hetero)arylmethane dyes, porphyrin dyes, phthalocyanine dyes, and natural direct dyes, which exist alone or in mixtures. Many direct dyes are cationic direct dyes. Hydrazine cationic dyes, azo cationic dyes, and diazo cationic dyes may be mentioned. Specific examples include Basic Red 51, Basic Yellow 87, and Basic Orange 31 or derivatives thereof. Among the natural direct dyes that can be used according to this disclosure, references may be made to henna quinone, juglone, alizarin, cinnamon, carmine, cinnamic acid, rubigin, protocatechaldehyde, indigo, indigo, curcumin, spinulosin, apigenidin, and physorein. Extracts or decoctions containing these natural dyes, as well as pastes or extracts based particularly on henna, may also be used. When one or more direct dyes are present, they more particularly constitute 0.001% to 10% by weight, and preferably 0.005% to 5% by weight, of the total weight of the compositions disclosed herein.

[0171] Alkalizing agent

[0172] Hair care compositions may have an alkaline pH. Exemplary pH values ​​include 7, 8, 9, 10, 11, 12, 13, or 14. In some embodiments, the pH of the hair coloring composition may be from about 7, 8, or 9 to about 9, 10, 11, or 12. The alkalinity of the hair coloring composition may be obtained by one or more alkalizing agents. In some embodiments, the alkalizing agent may be ammonia or a compound that generates ammonia gas, and / or an amine- or ammonium-based compound, in an amount sufficient to make the composition alkaline. In other embodiments, the alkalizing agent may be selected from alkanolamines, such as monoethanolamine (MEA) and isopropanolamine. Alkalinity may also be obtained by ammonium compounds (e.g., NH4OH). One or more alkalizing agents may be present in an amount greater than about 0 or from 1, 2, 3, 4, 5, 10 to about 5, 10, 13, 15, 18, 20, 25, or 30% by weight of the total composition.

[0173] Hair care compositions may be in the form of creams, aqueous solutions, homogeneous dispersions, suspensions of surfactants, or even liquids. Such compositions are acceptablely phase-stable and typically have a viscosity of about 1 to 1,000,000 cps, more preferably about 10 to 100,000, and most preferably 100 to 20,000 cps. For the purposes of this invention, viscosity is measured at 1 rpm at room temperature using a Brookfield LVDV-II+ viscometer with a corresponding cup and rotor.

[0174] The hair care composition of the present invention comprises at least one poly(alkylene oxide)-substituted chromophore colorant. The term "poly(alkylene oxide)-substituted chromophore colorant" generally refers to a colorant having at least one chromophore moiety attached to at least one oligomeric or polymeric poly(alkylene oxide) chain, wherein said chain has at least two repeating units, and preferably at least three repeating units. The oligomeric or polymeric substituent can be attached to the chromophore moiety by any suitable means, such as covalent bonding, ionic bonding, or suitable electrostatic interaction. Typically, polymeric colorants can be characterized by having absorbance in the range of about 300 nm to about 900 nm as measured by UV-vis spectroscopy. In one aspect of the invention, the polymeric colorant has a maximum absorbance in the range of 400 nm to 700 nm.

[0175] Depending on their manufacturing method, the molecular weight of polymer colorants is typically expressed as a molecular weight distribution. Therefore, the molecular weight of polymer colorants is usually reported as an average molecular weight, which is determined by their molecular weight distribution.

[0176] The chromophore moiety of polymer colorants can vary widely and can include compounds characterized in the art as dyes or pigments. The actual group used depends largely on, for example, the desired color, colorfastness, and stability characteristics. The chromophore moiety can be linked to at least one polyalkylene oxide substituent via suitable linking sites such as nitrogen, oxygen, sulfur, etc.

[0177] In one aspect, the polymer colorant can be a neutral or uncharged molecule. In another aspect, the polymer colorant can be nonionic, anionic, or cationic. The polymer colorant can contain chromophore groups that simultaneously possess both positive and negative charges. Furthermore, the polymer colorant can be zwitterionic or amphoteric.

[0178] Examples of chromophores include nitroso, nitro, azo (including monoazo, diazo, triazo, tetraazo and polyazo), formazan, azomethyl bases and their metal complexes, bis-bis-bis-phenylene, biphenyl, oligostyrene, fluorene, coumarin, napthalamide, diarylmethane, triarylmethane, xanthones, acridine, quinoline, methine (including polymethyl), thiazole, indoleamine, indophenol, acridine, thiazide, oxazine, amino ketone, hydroxy ketone, anthraquinone (including anthraquinone, anthrone, anthraquinone, anthrimidine, flavanone, pinantrone, benzoantrone, pyrene, perinone, naphthalenediimide and other structures formally related to anthraquinone), indigo (including thioindigo), phthalocyanine chromophore groups, and mixtures thereof. In one aspect of the invention, the polymer colorant is an azo polymer colorant.

[0179] A suitable example of a polymer chain is a polyalkylene oxide chain. The term "polyalkylene oxide" as used herein generally refers to a molecular structure containing the following repeating units: -CH2CH2O-, CH2CH2CH2O-, -CH2CH2CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(CH2CH3)O-, CH2CH2CH(CH3)O-, CH2CH(O-)(CH2O-), and any combination thereof.

[0180] Typical groups that can be attached to chromophore groups are polymeric epoxide groups, such as polyalkylene oxide groups and their copolymer groups. Typical polyalkylene oxides and their copolymers that can be used to provide colorants include those prepared from alkylene oxide monomers containing two to twenty carbon atoms, or more preferably two to six carbon atoms. Examples include: polyethylene oxide; polypropylene oxide; polybutane oxide; oxetane; tetrahydrofuran; copolymers of polyethylene oxide, polypropylene oxide, and polybutane oxide; and other copolymers, including block copolymers, wherein most of the polymer substituents are polyethylene oxide, polypropylene oxide, and / or polybutane oxide. Furthermore, such polyalkylene oxide groups can have an average molecular weight in the range of about 132 to about 10,000, preferably about 176 to about 5,000.

[0181] It should be understood that because colorants may or may not chemically bind to the components constituting the hair care composition, the precise chemical identity of the end groups on the polyalkylene groups may not be critical, as long as the colorant in the composition functions appropriately. With this in mind, certain preferred colorants are defined as those that will define certain end groups. This enumeration of end groups should not be construed as limiting the invention in any way to its broader embodiments. According to such preferred embodiments, the colorant can be characterized as follows:

[0182] R{A[(alkylene oxide component)] n R1] m} x

[0183] Wherein R is an organic chromophore group, A is a chemical linking bond (including single, double, and triple bonds) or a portion of the organic chromophore group independently selected from -N=, -O-, -SO2-, -SO2N=, or -CO2-, the alkylene portion of the alkylene oxygen component comprises 2 to about 4 carbon atoms, n is an integer independently selected from 0 to about 230, and at least one n is not less than 2. When A is -O-, -SO2-, or -CO2-, m is 1, and when A is -N= and -SO2N=, m is 1 or 2; x is an integer from 1 to 5, and the sum of all n values ​​is 2 to about 230, and R1 is independently selected from hydrogen, alkyl, and the following:

[0184]

[0185] Wherein R2 is H, an alkyl group containing no more than about 20 carbon atoms, or a carboxyl-terminated alkyl group containing no more than about 20 carbon atoms, j and k are OH, OM, or OR3, wherein M is a cationic moiety of an alkali metal, alkaline earth metal, transition metal (e.g., nickel), or ammonium, and R3 is an alkyl group containing no more than about 20 carbon atoms, and R4 is selected from -CH2-, -CH2CH2-, CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2CH3)-, CH2CH2CH(CH3)-, CH2CH(OR1)(CH2)-.

[0186] The oligomer can be any suitable component, including but not limited to oligomers selected from: (i) oligomers comprising at least two monomers or repeating units selected from C2 to C3. 20 (ii) alkylene oxide groups, glycidyl groups and glycidyl groups, and aromatic or aliphatic low polyesters conforming to structure (I):

[0187] (I)

[0188] And combinations of (iii), (i), and (ii). In structure (I), R2 and R3 are independently selected from hydrogen and C1 to C2. 10Alkyl, f is an integer between 1 and 10, including 1 and 10, and g is any positive integer or fraction between 1 and 20, including 1 and 20. As those skilled in the art will understand, suitable g values ​​include both integers and fractions because the length of the oligomer components on each polymer colorant molecule can vary. Therefore, the g value represents the average ester chain length of a given sample or collection of polymer colorant molecules. In some embodiments, the polymer colorant may contain one or more oligomer components consisting of two or more ethylene oxide monomer groups.

[0189] The polymer colorant may be alkoxylated. Alkoxylation is carried out by a process known to those skilled in the art (see, for example, US Patent Nos. 4,137,243, 5,082,938, 5,135,972, 5,591,833, 6,593,483, 7,587,857, 9,056,963 and 9,068,081).

[0190] Exemplary polymer colorants include Polymer colorants, Polymer liquid concentrate colorant Polymer colorants and Polymer colorants, all of which are available from Milliken Chemical (a division of Milliken & Company in Spartanburg, SC). Polymer colorants are characterized by being water-soluble and non-staining. They are widely used in laundry detergents, fabric softeners, and other consumer and industrial cleaning products. Polymer colorants are typically bright liquid colorants, with varying degrees of solubility in water depending on the specific colorant. These colorants are also characterized by their compatibility with other chemicals present in their final formulations and their generally ease of handling. Polymer colorants can be used to provide color in both aqueous and solid systems. The unique polymer properties of polymer colorants provide reduced contamination of skin, textiles, hard surfaces, equipment, and more.

[0191] Polymer colorants are liquid polymer colorants used for coloring polyurethane and other thermosetting resins. These colorants are reactive polymer colorants composed of chromophores chemically bonded to polyols. This arrangement allows the polymer colorant to react and enter the polyurethane polymer matrix. Unlike pigment pastes (which are dispersions of solid particles in a liquid), The polymer colorant is a 100% homogeneous liquid, soluble in polyols and does not settle over time. Due to its pure liquid nature and easy dispersibility, it can be blended online and on-the-fly in the preparation of polyurethane foams and resins. Coloring agent.

[0192] Polymer colorants are liquid colorants specifically developed for washable applications, such as markings, paints, and other art products. They are free of heavy metals, non-toxic, and exhibit excellent non-staining properties on skin, fabrics, and other surfaces. Polymer colorants have excellent compatibility with water-based ink formulations and provide bright colors.

[0193] In one aspect of the invention, the chromophore has the following structure:

[0194]

[0195] AR1 and AR2 are independently selected from alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; one of the AR1 or AR2 groups may be further substituted by another azo chromophore to form a diazo. In one aspect, the substituted heteroaryl is a substituted thiazolonium group.

[0196] In another aspect of the invention, the chromophore has the following structure:

[0197]

[0198] Where e and f are independent integers from 0 to 4; each R 20 and R 21 Independently selected from halogens, hydroxyl groups, nitro groups, nitrile groups, alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, aryl groups, substituted aryl groups, heteroaryl groups and substituted heteroaryl groups, ─S(O)2OH, ─S(O)2O - [M + ]、─C(O)OR5、─C(O)R5、─C(O)NR5R6、─NR5C(O)OR6、─NR5C(O)SR6、─OR5、─NR5R6、─S(O)2R5、─S(O)2NR5R6 and ─P(O)2R5; M is a cation; R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl.

[0199] In another aspect of the invention, the chromophore has a structure selected from the following:

[0200]

[0201] Where h, i, and j are independent integers from 0 to 4; the prerequisite is that, in structure IIIa, h is an integer from 0 to 2. 31 Selected from =O, =S, =NR 34 S = N + R 34 R 35 ;R 30 Selected from -O - 、─S - 、─OR 36 and NR 36 R 37 Each R 34 R 35 R 36 and R 37 Independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, -C(O)OR5, -C(O)R5, and -C(O)NR5R6. Each R 31 R 32 and R 33 The functional group is independently selected from halogen, hydroxyl, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl, ─S(O)2OH, ─S(O)2O - [M + ]、─C(O)OR5、─C(O)R5、─C(O)NR5R6、─NR5C(O)OR6、─NR5C(O)SR6、─OR5、─NR5R6、─S(O)2R5、─S(O)2NR5R6 and ─P(O)2R5; M is a cation; R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl. X 30 X 31 X 32 and X 33 Independently selected from carbon and nitrogen atoms, provided that X... 30 X 31 X 32 and X 33 No more than two of them are nitrogen atoms.

[0202] In another aspect of the invention, the chromophore has the following structure:

[0203]

[0204] Where X 42 Selected from oxygen atoms, sulfur atoms, and SiR 45 R 46 and NR 45 Y 41 Selected from =O, =S, =NR46 S = N + R 45 R 46 ;R 45 and R 46 Selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, ─S(O)2OH, ─S(O)2O - [M + ], ─C(O)OR5, ─C(O)R5, and ─C(O)NR5R6. l is an integer from 0 to 3 and m is an integer from 0 to 4. Each R 41 and R 42 Independently selected from halogens, hydroxyl groups, nitro groups, nitrile groups, alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, aryl groups, substituted aryl groups, heteroaryl groups and substituted heteroaryl groups, ─S(O)2OH, ─S(O)2O - [M + ], ─C(O)OR5, ─C(O)R5, ─C(O)NR5R6, ─NR5C(O)OR6, ─NR5C(O)SR6, ─OR5, ─NR5R6, ─S(O)2R5, ─SR5, ─S(O)2NR5R6 and ─P(O)2R5; M is a cation; wherein at least one R 42 The group is selected from -OR5, -SR5 and -NR5R6. R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl.

[0205] In another aspect of the invention, the chromophore has the following structure:

[0206]

[0207] AR 51 Selected from alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; R 52 R 53 and R 54 Independently selected from hydrogen and R 51 Each R 51 Independently selected from halogens, hydroxyl groups, nitro groups, nitrile groups, alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, aryl groups, substituted aryl groups, heteroaryl groups and substituted heteroaryl groups, ─S(O)2OH, ─S(O)2O - [M + ], ─C(O)OR5, ─C(O)R5, ─C(O)NR5R6, ─NR5C(O)OR6, ─NR5C(O)SR6, ─OR5, ─NR5R6, ─S(O)2R5, ─S(O)2NR5R6 and ─P(O)2R5, where M is a cation, provided that R 51Not hydrogen; R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl, and substituted aryl; c is an integer from 1 to 10. X 50 X 51 X 52 and X 53 Independently selected from carbon and nitrogen atoms, provided that X... 50 X 51 X 52 and X 53 No more than 2 of them are nitrogen atoms; g is an integer from 1 to 4; wherein structure V can exist in the form of an ion accompanying its counterion to maintain electroneutrality.

[0208] In another aspect of the invention, the chromophore has the following structure:

[0209]

[0210] Among them, each R 61 R 62 R 63 and R 64 The functional group is independently selected from halogen, hydroxyl, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, -S(O)2OH, -S(O)2O - [M + ], ─C(O)OR5, ─C(O)R5, ─C(O)NR5R6, ─NR5C(O)OR6, ─NR5C(O)SR6, ─OR5, ─NR5R6, ─S(O)2R5, ─S(O)2NR5R6 and ─P(O)2R5; M is a cation; where n, o, p and q are independently selected from integers from 0 to 4. R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl. Q is hydrogen, a metal ion or metalloid; A is an anion. x is a positive integer and y is an integer including 0 such that the divalent group ─Q x A y — Neutral.

[0211] In another aspect of the invention, the chromophore has the following structure:

[0212]

[0213] Among them, each R 71 R 72 and R 73 The functional group is independently selected from hydrogen, halogen, hydroxyl, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, ─S(O)2OH, ─S(O)2O - [M+ R5, R6, R7, and R8 are independently selected from hydrogen, alkyl, substituted alkyl, aryl, and substituted aryl, provided that at least one R is present. 72 The group is either -OR5 or -NR5R6.

[0214] In another aspect of the invention, the chromophore has a structure selected from the following:

[0215]

[0216] Where X1 and X2 are selected from carbon and nitrogen atoms; a is an integer from 0 to 5, provided that a is an integer from 0 to 4 when one of X1 and X2 is a nitrogen atom, and an integer from 0 to 3 when both X1 and X2 are nitrogen atoms; each R1 is independently selected from halogen, hydroxyl, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl, ─S(O)2OH, ─S(O)2O - [M + R1 is selected from ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, ☐, and ☐, ... + R5R6; where structures VIII and VIIIa can exist in ionic form accompanying their counterions to maintain electroneutrality.

[0217] In another aspect of the invention, the chromophore has the following structure:

[0218]

[0219] AR 11 Selected from alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; R 11 and R 14Independently selected from hydrogen, halogen, hydroxyl, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, ─S(O)2OH, ─S(O)2O - [M + ]、─C(O)OR5、─C(O)R5、─C(O)NR5R6、─NR5C(O)OR6、─NR5C(O)SR6、─OR5、─NR5R6、─S(O)2R5、─S(O)2NR5R6 and ─P(O)2R5; M is a cation; R5 and R6 are independently selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl; b is an integer from 1 to 10.

[0220] In one aspect of the invention, the colorant has the following structure:

[0221]

[0222] Among them, each R a11 To R a110 The groups are independently selected from hydrogen, deuterium, and R. v Each R v Independently selected from halogens, nitro groups, nitriles, alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, aryl groups, substituted aryl groups, alkynyl groups, substituted alkynyl groups, and -(CH2). n ─O─R x 、─(CH2) n ─NR x R y 、─C(O)R x 、─C(O)OR x 、─C(O)O - 、─C(O)NR x R y 、─OC(O)R x 、─OC(O)OR x 、─OC(O)NR x R y 、─S(O)2R x 、─S(O)2OR x 、─S(O)2O - 、─S(O)2NR x R y 、─NR x C(O)R y 、─NR x C(O)OR y 、─NR x C(O)SR y 、─NR x C(O)NR y Rz 、─OR x 、─NR x R y 、─P(O)2R x 、─P(O)(OR x )2、─P(O)(OR x )O - and─P(O)(O - )2; where the label n is an integer from 0 to 4; and where R x R y and R z Independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl and R u ;R u An organic group comprising one or more organic monomers, wherein the molecular weight of said monomers is 28 to 500. In another aspect of the invention, R a11 R a12 and R a13 At least one of them is an electron-withdrawing group selected from the following: halogen, nitro, nitrile, nitroso, -C(O)R x 、─C(O)OR y 、─C(O)NR x R y 、─OC(O)R x 、─OC(O)OR x 、─OC(O)NR x R y 、─S(O)2R x 、─S(O)2OR x 、─P(O)2R x and ─P(O)(OR x )2 group. In another aspect, R a11 and R a13 The group is a -CN group, and R a12 It is methyl. In another aspect of the invention, R a16 R a17 R a18 R a19 R a110 Independently selected from hydrogen, halogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, tert-butyl, and -(CH2). n ─O─R x 、─(CH2) n ─NR x R y 、─OR x and NR x R y And Ra16 R a17 R a18 R a19 R a110 At least one of them is -OR x Or -NR x R y In another aspect, R a16 R a17 R a18 R a19 R a110 Two or more of the rings in formula IA are covalently linked to each other to form a ring structure fused with the benzene ring in formula IA. In another aspect, the ring structure fused with the benzene ring in formula IA is one of naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, dihydroindole, and isoindoleline. In yet another aspect, the ring structure is formed by one or more R... a16 Group substitution. In another aspect, R... x R y Or R z Two of the rings are attached to the same carbon or nitrogen group and form a ring structure. In another aspect, the ring structure is one of piperazine, piperidine, and pyrrolidine. In yet another aspect, the ring structure is formed by one or more R groups. a16 The groups are further substituted.

[0223] In one aspect of the invention, the colorant is a thiophene azo colorant according to the following structure:

[0224]

[0225] Each x and y is an independent integer from 0 to 20.

[0226] Also within the scope of this invention is the possibility that other colorants may be combined with polymeric colorants to form the colorant portion of a hair care composition. For example, colorants selected from one or more of the following categories may be suitable: acid dyes, basic dyes, direct dyes, solvent dyes, vat dyes, mordant dyes, indigo dyes, reactive dyes, disperse dyes, sulfur dyes, fluorescent dyes; pigments, organic and inorganic; natural colorants, etc. Therefore, the colorant of a hair care composition may comprise blends or mixtures of polymeric and non-polymeric colorants. Polymeric and non-polymeric colorants may have the same chromophore group, or they may have different chromophore groups.

[0227] The hair care composition of the present invention is prepared by combining at least one hair care ingredient with at least one polymer colorant. The hair care composition thus formed can be a substantially homogeneous mixture.

[0228] The method for preparing a hair care composition according to the present invention includes the following steps:

[0229] (a) Provides at least one hair care ingredient;

[0230] (b) providing at least one polymer colorant; and

[0231] (c) Combining the at least one hair care ingredient and the at least one polymer colorant to form a hair care composition comprising the polymer colorant.

[0232] The method for applying color to hair according to the present invention includes the following steps:

[0233] (a) Providing a hair care composition comprising a polymer colorant;

[0234] (b) Applying the hair care composition containing the polymer colorant to hair;

[0235] (c) Contacting the hair care composition containing the polymer colorant with the hair for a period of time; and

[0236] (d) Optionally, the hair care composition containing the polymer colorant is removed from the hair.

[0237] The method for bleaching and coloring hair according to the present invention includes the following steps:

[0238] (a) A hair care composition comprising a polymer colorant, wherein the composition further comprises an oxidant;

[0239] (b) Apply the composition to hair;

[0240] (c) subjecting the composition to contact with the hair for a period of time; and

[0241] (d) Optionally, remove the composition from the hair.

[0242] The hair care composition can be applied to hair for a period of time ranging from 10 seconds to 1 hour, or from 30 seconds to 45 minutes, or from 1 minute to 30 minutes, or from 3 minutes to 15 minutes. The hair can be moistened with water before applying the hair care composition; or the hair can be dry when applied.

[0243] Hair care compositions can be permanent (e.g., 80% of the original color intensity is still visible after 20 wash cycles), semi-permanent (e.g., 80% of the original color intensity is visible up to 20 wash cycles but not visible after 20 wash cycles), or temporary (e.g., 80% of the original color intensity is visible up to 5 wash cycles but not visible after 5 wash cycles). The persistence of hair color on hair can depend on the specific polymeric colorant contained in the composition and / or the amount of polymeric colorant contained in the composition. For example, increasing the amount of polymeric colorant in the hair care composition results in longer-lasting color on the hair. Conversely, containing less polymeric colorant in the composition results in shorter-lasting color on the hair. Furthermore, the length of time the hair care composition remains in contact with the hair during the coloring process affects the amount of color, color depth and / or hue on the hair, and the persistence of the hair color. For example, leaving the composition on the hair for a longer period during the hair coloring process results in a deeper hue and / or color depth on the hair and longer-lasting color.

[0244] In one aspect of the invention, the amount of polymer colorant in the hair cream is in the range of 0.0001 to 10%, or in the range of 0.1% to 5%.

[0245] In one aspect of the invention, the molecular weight of the polymer colorant in the hair cream is in the range of 100 to 10,000 Daltons, or in the range of 200 to 5,000 Daltons, or in the range of 300 to 2,000 Daltons.

[0246] At least one polymeric colorant described herein can be added to hair care compositions for hair coloring. Therefore, the invention also covers hair (or keratin-containing materials) comprising at least one polymeric colorant. The invention also covers methods for bleaching and / or coloring hair (or keratin-containing materials), the method comprising the steps of: providing hair, applying the hair care composition described herein to the hair and / or depositing the hair care composition onto the hair, allowing the composition to contact the hair for a period of time, and further agitating, rinsing, and / or drying the so-called treated hair.

[0247] For application in non-oxidizing systems, a single-component formula is typically used, often a cream (but not limited to) containing the hair care ingredients listed above and a colorant mixed together. The single-component cream is applied to the hair, and the colorant is deposited directly onto the hair. The colored cream is then washed off, leaving the colorant on the hair.

[0248] For application in oxidizing systems, there are typically two components. One component contains an oxidizing agent (e.g., hydrogen peroxide). The second component contains other substances (which are usually designed to raise the pH), but may also contain other oxidizing agents such as persulfates. In one aspect of the invention, the two components are mixed together before application to the hair. The initial application includes a polymeric colorant in the hydrogen peroxide paste, rather than in the second component. However, it is conceivable to alternatively place the polymeric colorant in the second component.

[0249] Therefore, in one embodiment, at least one polymeric colorant is mixed into the oxidant-containing paste. Just before use, the paste containing the polymeric colorant / hydrogen peroxide is mixed with at least one other component to raise the pH to an amount sufficient to activate the hydrogen peroxide. In an alternative embodiment, the polymeric colorant can be added to a second component. In this case, the second component is added to the uncolored hydrogen peroxide paste immediately before use.

[0250] While the invention described herein is primarily directed to hair care compositions containing polymeric colorants, it is not limited to only those compositions. Compositions may contain combinations of polymeric colorants with other colorants. Other colorants include, for example, dyes, pigments, and combinations thereof.

[0251] Suitable dyes include small molecule dyes. Suitable small molecule dyes include those selected from the following: dyes that fall into the color index (CI) classification of Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue, Basic Violet, and Basic Red, or mixtures thereof. Examples of small molecule dyes include those selected from the following: color index (CI). (Colourists), Bradford, UK) Direct Violet 9, Direct Violet 35, Direct Violet 48, Direct Violet 51, Direct Violet 66, Direct Violet 99, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid Violet 43, Acid Red 52, Acid Violet 49, Acid Violet 50, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80, Acid Blue 8 3. Acid Blue 90 and Acid Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47, Basic Blue 66, Basic Blue 75, Basic Blue 159, selected from color indices (British Institute of Dyers, Bradford, UK) Acid Violet 17, Acid Violet 43, Acid Red 52, Acid Red 73, Acid Red 88, Acid Red 150, Acid Blue 25, Acid Blue 29, Acid Blue 45, Acid Blue 113, Acid Black 1, Direct Blue 1, Direct Blue 71, small molecule dyes.

[0252] Suitable pigments include those selected from: flavanones, indigoanthraquinones, indigoanthraquinone chloride containing 1 to 4 chlorine atoms, pinanthraquinones, dichloropinanthraquinones, monobromodichloropinanthraquinones, dibromodichloropinanthraquinones, tetrabromopinanthraquinones, pyrene-3,4,9,10-tetracarboxylic acid diimide (wherein the imide group may be unsubstituted or substituted with a C1-C3 alkyl or phenyl or heterocyclic group, and wherein the phenyl and heterocyclic groups may additionally have substituents that do not impart solubility in water), anthraquinone carboxylic acid amides, violetanthraquinones, isovioletanthraquinones, dioxazine pigments, copper phthalocyanines containing no more than 2 chlorine atoms per molecule, polychlorinated copper phthalocyanines, or polybrominated copper phthalocyanines containing no more than 14 bromine atoms per molecule, and mixtures thereof.

[0253] In one aspect of the invention, the components of a hair care composition can be prepared by combining the components in any convenient order and by mixing (e.g., stirring) the resulting combination of components to form a phase-stable semi-liquid (i.e., paste) composition. In another method of preparing the composition, a liquid matrix comprising at least most—preferably substantially all—of the liquid components is formed, wherein the liquid components are thoroughly incorporated by applying shear stirring to such a liquid combination. For example, rapid stirring with a mechanical stirrer can be usefully used. While maintaining shear stirring, substantially all of any solid form of the components can be added. The mixture is stirred continuously, and if necessary, stirring can be increased at this point to form a homogeneous dispersion of a solution or insoluble solid particles in the liquid phase. As a variation of the composition preparation process described above, one or more of the solid components can be added to a stirred mixture as a solution or a premixed slurry with a small portion of the liquid components. After all the composition components have been added, the mixture is stirred for a period sufficient to form a composition with the required viscosity and phase stability characteristics. This typically includes a stirring period of about 30 to 60 minutes.

[0254] The hair care composition of the present invention can be combined with other molecules, compounds, and / or reagents that can be used to apply the composition to hair and / or to enhance color performance. Other molecules, compounds, and / or reagents include, for example, surfactants, solvents, preservatives, antimicrobial agents, antibacterial agents, fragrances, and combinations thereof.

[0255] The hair care compositions of the present invention may also contain any number of additional optional ingredients. These ingredients include conventional hair coloring composition components, such as moisturizing oils, surfactants (which may include nonionic, anionic, cationic, amphoteric, and betaine surfactants), polar solvents, chelating agents, pH adjusters, conditioning agents, and other ingredients. Various optional hair cream composition ingredients, if present in the compositions described herein, should be used at concentrations conventionally used to bring their desired contribution to the composition and / or coloring method. Typically, the total amount of the optional hair cream composition ingredients may be from about 0.01% by weight to about 50% by weight, more preferably from about 0.1% by weight to about 30% by weight, in the composition.

[0256] Example

[0257] The following polymer colorants were prepared and evaluated in various hair care compositions:

[0258] Table 1: Polymer colorants prepared and evaluated

[0259]

[0260]

[0261]

[0262]

[0263]

[0264] All of the above-described colorants are capable of imparting color to hair, as demonstrated in the various application examples below. Because these materials are polymeric, there is a distribution around an average number of repeating units; for the materials listed in the table above, the average number of repeating units is listed.

[0265] To prepare a hair care composition containing a polymer colorant, the polymer colorant can be mixed with a hair colorant, or the colorant can be added to a previously prepared hair care composition. For example, the following hair care compositions according to the present invention can be prepared:

[0266] Hair cream ingredients 1 to 3

[0267] Table 2: Examples of hair cream formulations

[0268]

[0269] The hair care composition can be prepared as follows: Water is placed in a beaker equipped with a homogenizer mill and heated to 70-75°C. The homogenizer mill is then turned on, and modified magnesium aluminum silicate (Veegum) is sprinkled into the beaker. The mixture is milled for 15 minutes. While maintaining the temperature, ethoxydiethylene glycol, disodium EDTA, ascorbic acid, and methylparaben are added to the mixture, and it is further milled for about 15 minutes. In a separate beaker, aminomethylpropanol, monoethanolamine, and water are combined, and this mixture is then added to the mixture of other components. The batch is then transferred to a turbine / sweep kettle.

[0270] Individually, the oil components—oleic acid, cetearyl alcohol, emulsified wax, oleyl alcohol polyether-20, oleyl alcohol, and stearyl alcohol polyether-21—are combined and heated to 70 to 75°C. The oil phase is then combined with the other components and thoroughly mixed while maintaining the temperature at 70 to 75°C. The compound is cooled to 35 to 40°C. The essential oils and colorants are added, and the composition is mixed again for 15 minutes. The compound is then cooled to 25°C.

[0271] Alternatively, the hair care compositions according to the invention can be prepared by mixing the above-described examples of polymeric colorants with commercially available hair care compositions. These hair care compositions may include semi-permanent hair coloring creams. Such examples may include Igora ColorWorx Dilutor (Schwarzkopf), Colorista Clear Mixer (L'Oreal), Color Charm Paints Clear (Wella), and Color Fresh Create Tomorrow Clear (Wella). These hair care compositions may also include shampoos. Examples of such products may include After Color Treatment Shampoo (Fanola), Tresemme Pro Pure Micellar Moisture Shampoo (Unilever), Pantene Nutrient Blends Illuminating Color Care Shampoo (P&G), BCBonacure pH 4.5 Color Freeze Micellar Rich Shampoo (Schwarzkopf), Free&Clear Shampoo for Sensitive Skin (Pharmaceutical Specialties, Inc.), EverPure Blonde Shampoo (L'Oreal), and Schuma 7Herbs Shampoo (Schwarzkopf). These hair care compositions may also include conditioning agents, deep conditioners, and conditioning masks. Examples of such products may include Everpure Blonde Conditioner (L'Oreal), Pantene Nutrient Blends Illuminating Color Care Conditioner (P&G), Pantene Pro-V Classic Clean Conditioner (P&G), Nutri Care Restructuring Conditioner (Fanola), and Schuma 7Herbs Conditioner (Schwarzkopf). These hair care compositions may also include various leave-in products, such as leave-in conditioners, hair sprays, mousses, gels, and waxes.

[0272] The polymer colorant was also evaluated through the following steps: The polymer colorant was added to the hair care composition. Each sample was mixed with a SpeedMixer at 1500 rpm until a visually homogeneous mixture was obtained (SpeedMixer Inc., Landrum, SC). The colored hair care composition was transferred to a large boat-shaped weighing pan containing the hair sample. A specific amount of the mixture was applied to the entire hair and rubbed into the hair with fingertips until the mixture was evenly distributed and fully incorporated into the hair. The amount varied depending on the type of hair care composition and was specifically specified in each example. The colored hair care composition was left on the hair for a specific duration, and then the hair sample was thoroughly rinsed with warm water, combed, and dried in an oven at 60°C for 45 minutes. The duration varied depending on the type of hair care composition and was specifically specified in each example. The hair color was measured using an X-Rite Color i7 with a 6 mm orifice. The results of each measurement are based on L*, a*, b* values ​​for a D-65, 10° observer. When performing measurements, twist the hair tightly and press it onto the hole. Use the average of 6 to 8 measurements. The primary means of comparing samples or evaluating the amount of color deposited on the hair are ΔE calculated as described below and the Yellowness Index (YI) calculated according to ASTM Method E313.

[0273] The method used to calculate ΔE:

[0274] ΔE is used to represent the effectiveness of the polymer colorant in dyeing hair. The L*, a*, b* values ​​are taken from hair before and after dyeing. The changes in L*, a*, b* (ΔL*, Δa*, Δb*) are calculated and converted to ΔE values ​​using the following equation:

[0275]

[0276] A higher ΔE value means a greater change in hair color before and after dyeing, thus making the hair coloring agent more effective.

[0277] Application Example 1

[0278] The polymer colorant of this invention was evaluated as a semi-permanent hair colorant by coloring a sample of golden hair (a bleached gold from deep black). Golden human hair samples are typically used for color evaluation by hairstylists, and these samples are available from many different retailers. The hair care composition in this example is an uncolored semi-permanent hair coloring cream, Igora ColorWorx Dilutor (Schwarzkopf). For each colorant, the amount of color in the cream was adjusted so that each sample exhibited the same color intensity, meaning that the amount of chromophores or absorbance was the same in each cream, despite differences in polymer chain length. The maximum absorbance of the colored cream was 0.1 when measured at a concentration of 1 g / L in methanol over a 1 cm path length. The amount of cream used was 1 g cream / g hair. The cream was left in contact with the hair for 20 minutes before rinsing off. To evaluate the amount of color deposited on yak hair, the ΔE value of the colored hair relative to the uncolored hair was used. The results are shown in Table 3. The example compounds in Table 1 that were not evaluated in Table 3 were evaluated in other tests.

[0279] Table 3: Colorant deposition from semi-permanent hair coloring cream on bleached hair

[0280]

[0281]

[0282] Application Example 2

[0283] As shown in Table 3, the polymer chain length appears to affect deposition on bleached hair (e.g., comparisons of Examples 6 vs. 7, 12 vs. 13, 18 vs. 20, and 28 vs. 29). Shorter polymer lengths tend to provide higher deposition. To further investigate this effect on substrates different from bleached hair, three different colorants with the same chromophores but different polymer lengths were measured on yak belly hair. The hair care composition in this example is an uncolored semi-permanent hair coloring cream, Igora ColorWorx Dilutor (Schwarzkopf). The amount of color in the cream was adjusted so that each sample exhibited the same color intensity, meaning that the amount of chromophores or absorbance was the same in each cream, despite the different polymer chain lengths. Similar to Application Example 1, the maximum absorbance of the colored cream was 0.1 when measured at a concentration of 1 g / L in methanol over a 1 cm optical path length. For this study, yak belly hair was used as the hair substrate, and the hair was colored using the above-described process. The amount of paste used was 2 g paste / g hair. The paste was left in contact with the hair for 20 minutes before rinsing off. To evaluate the amount of color deposited on the yak hair, the ΔE value of the colored hair relative to the uncolored hair was used. The results are shown in Table 4. The amount of color deposited decreased with increasing polymer chain length. The amount of deposition tended to decrease with increasing number of EO units. The results indicate that 5 to 6 EO units are optimal.

[0284] Table 4: Colorant deposition from semi-permanent hair coloring paste on yak hair

[0285] Colorant The average # of EO units ΔE deposition Example 30 5 48.8 Example 28 10 32.4 Example 27 20 13.5

[0286] Application Example 3

[0287] The polymer colorants of the present invention were compared with currently commercially available hair dyes by coloring golden hair (a bleached gold from deep black). A red colorant (Example 16) was added at 1.5 wt% to Igora ColorWorx diluter and compared with a currently commercially available Igora ColorWorx Red diluter containing the dyes 4-hydroxypropylamino-3-nitrophenol and 3-nitro-p-hydroxyethylaminophenol. Similarly, a yellow colorant (Example 35) was added at 1.5 wt% to Igora ColorWorx diluter and compared with a currently commercially available Igora ColorWorx Yellow diluter containing the dyes HC Yellow No. 13 and HC Yellow No. 2.

[0288] Apply each coloring paste to the hair as described above. The amount of paste used is 2g paste / g hair. Allow the paste to remain in contact with the hair for 20 minutes before rinsing. Then, measure the L*a*b* color of the hair as described above. Next, wash the hair with Schauma7Herbs Shampoo (Schwarzkopf) and dry it with a hairdryer using the following steps: Completely wet the hair with 40°C tap water. Then add shampoo (0.2g shampoo / 1g hair) to the hair and massage with your fingers for 30 seconds. Let the hair and shampoo remain in the dish for another 30 seconds, then rinse with 40°C tap water for 30 seconds. Then, dry the hair sample with a hairdryer. Wash and dry the hair twice, then measure its L*a*b* color. Then wash and dry the hair twice more, and measure again. To evaluate the amount of color deposited on the hair and the amount of color retained on the hair after each wash, the ΔE value relative to uncolored hair at any given wash state is used. The retained hair color after two and four washes is evaluated by dividing the ΔE value of the washed hair by the ΔE value of the initial deposited hair color before washing. Higher values ​​indicate better color retention during washing, with a 100% value signifying no color loss.

[0289] Compared to the comparison dyes (Igora Red and Igora Yellow), the polymer colorant exhibited superior washing performance. The red polymer colorant showed significantly more color retention than Igora Red after four washes. The absolute ΔE value of the polymer colorant was almost twice that of the dye product, and the color retention was close to 85%, compared to only 48% for the dye. The yellow polymer colorant showed an even greater improvement compared to the yellow dye product. The yellow polymer colorant retained 78% of the color, compared to only 37% for the yellow dye.

[0290] Table 5: Evaluation of color removal performance on bleached hair

[0291]

[0292] The behavior illustrated in Table 5 is unexpected, as test results indicate that reducing polymer size increases deposition; therefore, one might expect dyes with effectively zero polymer length to be superior to polymer colorants. Then, though not bound by theory, polymer colorants are thought to exhibit better washing performance than dyes because the polymer prevents any aggregation of the colorant, the most common occurrence in dyes (especially in general lipophilic pastes typically used for hair coloring). Because polymer colorants do not aggregate and are completely dispersed in the paste, they are thought to coat the hair fibers more evenly than dyes, which have a greater likelihood of aggregation. This more evenly coated hair fibers exhibit less color loss during washing compared to dyes, which have less evenly coated hair fibers due to aggregated dye.

[0293] Application Example 4

[0294] Polymer colorants, like conventional hair dyes, can be widely used in a variety of different hair coloring formulations. This is demonstrated by the following: a single polymer colorant (Example 10) was mixed at 0.16% by mass into several different commercially available uncolored semi-permanent hair coloring pastes and applied to bleached blonde hair. The amount of paste used was 1 g paste / g hair. The paste was allowed to remain in contact with the hair for 20 minutes before rinsing off. The amount of color deposited on the hair was evaluated by measuring ΔE of the colored hair relative to the uncolored hair, and is shown in Table 6.

[0295] Four different ointments were evaluated, each with different ingredients. Igora ColorWorx Dilutor (Schwarzkopf) contains water, cetearyl alcohol, PEG-8-cocoyl alcohol, cetearyl alcohol polyether-20, disodium cocoamphodipropionate, methylparaben, xanthan gum, sulfuric acid, sodium silicate, propylparaben-hydroxyethyl phosphate, and ethanolamine. Colorista Clear Mixer (L'Oreal) contains water, cetearyl alcohol, behentrimonium chloride, amino-terminated polydimethylsiloxane, cetyl alcohol, C12-15 alkyl benzoate, isopropanol, hydroxyethyl cellulose, trideceth-6, guar hydroxypropyltrimonium chloride, chlorhexidine digluconate, stearyl alcohol, myristyl alcohol, citric acid, hexadecyltrimethylammonium chloride, 2-oleoylamino-1,3-octadecanediol, fumaric acid, and sodium hydroxide. Color Charm Paints Clear (Wella) contains water, cetearyl alcohol, propylene glycol, stearyl alcohol polyether-20, phenoxyethanol, fragrance (Parfum / Fragrance), potassium phosphate, hexyl cinnamaldehyde, sodium hydroxide, and citric acid. Color Fresh Create Tomorrow Clear (Wella) contains water, cetearyl alcohol, propylene glycol, stearyl alcohol polyether-20, phenoxyethanol, mica, potassium phosphate, titanium dioxide / C177891, sodium hydroxide, and citric acid. The polymeric colorants were highly effective in all evaluated pastes, indicating that these materials work in a wide range of different formulations, each with a diverse range of ingredients.

[0296] Table 6: Deposition properties of polymer colorants (Example 10) in different semi-permanent hair coloring formulations

[0297]

[0298]

[0299] Application Example 5

[0300] While specially designed hair coloring creams are commonly used for hair coloring, it is also desirable to use other hair care compositions for coloring or tinting hair. Shampoos are commonly used hair care compositions that can also be used to deposit color onto hair. A range of polymeric colorants can be used in shampoo formulations to color hair. The hair care composition in this example is a shampoo, BC Bonacure pH 4.5 Color Freeze Micellar Rich Shampoo (Schwarzkopf). For each colorant, the amount of colorant in the shampoo was adjusted so that each sample exhibited the same color intensity, meaning that the amount or absorbance of chromophores was the same in each shampoo, despite differences in polymer chain length and chromophore type. The maximum absorbance of the colored shampoo was 0.25 when measured at a concentration of 1 g / L in methanol over a 1 cm optical path length. For this study, bleached blonde hair was used as the hair substrate and the hair was colored using the process described above. The amount of shampoo used was 0.2g shampoo / g hair. The shampoo was left in contact with the hair for 3 minutes before rinsing. To evaluate the amount of color deposited on the hair, the ΔE value of the hair after shampooing was used relative to the hair before shampooing.

[0301] In addition, the yellowness index (YI) of hair samples before and after shampooing was calculated, and the change in YI (ΔYI) from the shampooing treatment was also calculated. When hair is deeply bleached, certain melanins are preferentially destroyed, resulting in bleached hair with an unwanted warm orange / yellow or "brass" hue. A major application of dyes in shampoos is to neutralize this warm hue to a cooler or lighter tone. By evaluating the ΔYI of the hair, the desired effect of color correction or neutralization of unwanted warm tones can be observed. The greater the decrease in YI, the less yellow or brass the hair appears; in other words, the larger the absolute negative value of the ΔYI from the shampooing treatment, the better the colorant masks the unwanted yellow hue.

[0302] In addition to the polymer colorants evaluated for shampoo, commercially available dyes commonly used in shampoos were included as comparative samples. External D&C Violet 2 (also known as Acid Violet 43) was formulated in the same manner as the polymer colorants in terms of absorbance / g shampoo. Additional mixing and time were required to fully disperse the powdered dye into the shampoo. The results are shown in Table 7. The polymer colorants exhibit a range of deposition properties as judged by ΔE. Unexpectedly, some of the polymer colorants showed more deposition on the hair in the shampoo compared to the commonly used dye (Ext. D&C Violet 2). When the shade of the polymer colorant was suitable for neutralizing the yellow hue of the hair (e.g., Examples 10 and 11), ΔYI had a larger negative absolute value compared to the comparative dyes, meaning they were more effective at neutralizing yellow hues. Some colorants were not the desired shade for neutralizing yellow hues in bleached hair, such as Example 30, but could be used for other colors, such as yellow, red, pink, etc.

[0303] Table 7: Deposition properties of different colorants in shampoos

[0304] Colorant ΔE ΔYI Comparison example: Ext.D&C Purple 2 7.0 -12.0 Example 10 17.7 -29.5 Example 11 11.6 -21.1 Example 30 7.5 2.3 Example 2 7.0 -11.0 Example 4 5.4 -7.6 Example 12 4.7 -8.3 Example 22 3.6 -1.4 Example 26 2.7 -5.5 Example 5 2.4 -3.3 Example 1 1.3 -1.2

[0305] Application Example 6

[0306] It is known that shampoos containing dyes for coloring bleached hair cannot be used daily because the dye tends to continue depositing or accumulating throughout each wash cycle. Therefore, as the colorant continues to accumulate, the hair will go from yellow to the desired color and then to an undesirable purple or blue. Because polymer colorants have different physical properties compared to dyes, they can exhibit better leveling behavior, where they accumulate to a certain level and then stop depending on the load. This allows people to safely use the shampoo daily and achieve the desired level of color without undesirably over-coloring the hair or obtaining a purple / blue hue. A polymer colorant (Example 10) was formulated into a shampoo, and hair was repeatedly washed and dried in multiple cycles. A comparative example shampoo was prepared using Ext.D&C Violet 2, and the same experiment was performed with it.

[0307] For this example, the shampoo was BC Bonacure pH 4.5 Color Freeze Micellar Rich Shampoo (Schwarzkopf). For each colorant / dye, the amount of colorant in the shampoo was adjusted so that each sample exhibited the same color intensity; the maximum absorbance of the colored shampoo was 0.043 when measured at a concentration of 1 g / L in methanol over a 1 cm optical path length. This is a colorant loading level similar to many commercially available tinted shampoos. Bleached blonde hair was used as the hair substrate. The amount of shampoo used was 0.2 g shampoo / g hair. The shampoo was left in contact with the hair for 3 minutes before rinsing. To evaluate the amount of color deposited on the hair during each wash, the ΔE value of the hair after each shampoo wash relative to before each shampoo wash was used. The results are shown in Table 8. As previously mentioned, the polymer colorant deposited more than the dye in the first wash. Compared to the first wash, both the dye and polymer colorant showed lower deposition in the second and third washes. Surprisingly, after the third wash, the polymer colorant showed a progressively decreasing deposition with each subsequent wash, indicating even coloring; while the dye showed a stable amount of deposition after the third wash, indicating continued accumulation of dye on the hair. In this case, the polymer colorant exhibited the desired behavior: strong initial deposition followed by rapid even coloring. This allows consumers to observe clear results after only one or two washes, but safely continue using the shampoo with reduced concerns about over-toning or unwanted purple or blue hues.

[0308] Table 8: Deposition behavior after repeated shampoo washing

[0309]

[0310] Application Example 7

[0311] Many different shampoo formulations can be used to deliver polymer colorants to hair. This was demonstrated by taking a single polymer colorant (Example 2), mixing it at 0.65% by mass into several different commercially available shampoos, and applying it to bleached blonde hair. The amount of shampoo used was 0.2 g shampoo / g hair. The shampoo was allowed to remain in contact with the hair for 3 minutes before rinsing. The amount of color deposited on the hair was evaluated by measuring ΔE of the washed hair relative to the unwashed, uncolored hair, and is shown in Table 9.

[0312] Seven different shampoos were evaluated, each with different ingredients. Free&Clear Shampoo for Sensitive Skin (Pharmaceutical Specialties, Inc.) contains purified water, lauryl glucoside, cocoyl glucoside, acrylate copolymer, disodium cocoyl glutamate, sodium cocoyl glycinate, glycerin, sucrose cocoate, panthenol, 1,2-pentylene glycol, 1,2-hexanediol, sodium cocoyl glutamate, disodium EDTA, 1,2-caprylyl glycol, sodium hydroxide, and sodium chloride. After Color Treatment Shampoo (Fanola) contains water (Aqua), ammonium lauryl sulfate, sodium myreth sulfate, sodium cocoamphoacetate, sodium chloride, ethylene glycol distearate, sodium lauryl sulfate, fragrance, cocamide MEA, citric acid, guar hydroxypropyltrimethylammonium chloride, lauryl ether-10, hydrolyzed wheat protein, triethylene glycol, benzyl alcohol, propylene glycol, tocopheryl acetate, sodium benzoate, phenoxyethanol, methylchloroisothiazolinone, methylisothiazolinone, linnum (Linum Usitatissimum) seed oil, magnesium nitrate, and magnesium chloride. Tresemme Pro Pure Micellar Moisture Shampoo (Unilever) contains water, cocamidopropyl betaine, sodium cocoyl methyl taurate, sodium chloride, fragrance, sodium benzoate, citric acid, coconut acid, polyquaternium-10, stearamide-10, disodium EDTA, PPG-9, benzyl salicylate, hexyl cinnamaldehyde, limonene, and linalool.Schauma 7Herbs Shampoo (Schwarzkopf) contains water, sodium lauryl ether sulfate, sodium chloride, cocamidopropyl betaine, hydrolyzed soy protein, nicotinamide, magnesium chloride, chamomile flower extract, sage leaf extract, melissa leaf extract, nettle extract, euphorbia tirucalli extract, hornwort extract, rosemary leaf extract, hop extract, and jojoba seed oil. Oil), disodium cocoamphodiacetate, PEG-7 glyceryl cocoate, sodium benzoate, cocoamide MEA, citric acid, ethylene glycol distearate, fragrance, lauryl ether-4, hydrogenated castor oil, PEG-40 hydrogenated castor oil, polyquaternium-10, linalool, benzyl alcohol, propylene glycol, hexyl cinnamaldehyde, CI 47005, CI 42090. Pantene Nutrient Blends Illuminating Color Care Shampoo (P&G) contains water, lauramidopropyl betaine, sodium cocoyl hydroxyethyl sulfonate, sodium lauroyl sarcosinate, sodium citrate, citric acid, fragrance, sodium benzoate, sodium salicylate, polyquaternium-10, dimethiconol, tetrasodium EDTA, panthenol, panthenyl ethyl ether, histidine, and biotin.BC Bonacure pH 4.5 Color Freeze Micellar Rich Shampoo (Schwarzkopf) contains water, sodium lauryl ether sulfate, lactic acid, cocamidopropyl betaine, cocamidopropylamine (MEA), hydrolyzed keratin, stearyl dimethylammonium hydroxypropyl hydrolyzed keratin, apricot kernel oil (Prunus armeniaca, Apricot), panthenol, PEG-12 dimethicone, disodium cocoamphodiacetate, PEG-7 glyceryl cocoate, polyquaternium-10, calcium hydroxide, sodium benzoate, sodium chloride, fragrance, ethylene glycol distearate, PEG-40 hydrogenated castor oil, lauryl ether-4, hydrogenated castor oil, PEG-120 methyl gluconate dioleate, PEG-12 allyl ether, benzophenone-4, PEG-12, mica, benzoyl salicylate, and butylphenyl methylpropionaldehyde. Methylpropional), linalool, limonene, propylene glycol, calcium carbonate, CI 77891 (titanium dioxide), CI 17200 (red 33). EverPure Blonde Shampoo (L'Oreal) contains water, cocobetaine, disodium lauryl sulfosuccinate, sodium cocoyl hydroxyethyl sulfonate, sodium lauryl sulfoacetate, sodium lauroyl sarcosinate, ethylene glycol distearate, sodium chloride, decyl glucoside, fragrance, polyquaternium-10, amino-terminated polydimethylsiloxane, PPG-5-cetyl ether-20, propylene glycol, PEG-55 propylene glycol oleate, hydrogenated coconut oil acid, carbomer, sodium hydroxide, acrylate / beheneth-25 methacrylate copolymer. Copolymer), benzophenone-4, sodium hydroxyethyl sulfonate, butanediol, benzoic acid, trideceth-6, linalool, hydroxycitronellol, sodium acetate, cetyltrimethylammonium chloride, sodium benzoate, isopropanol, Iris Florentina Root Extract, Celendula Officinalis Flower Extract, methylchloroisothiazolinone, CI60730 / EXT. Violet 2, magnesium chloride, methylisothiazolinone, CI 17200 / Red 33, citric acid.

[0313] Polymer colorants showed deposition in all evaluated shampoos, demonstrating the effectiveness of these materials in a variety of different formulations, each with its own diverse ingredients. Shampoos contain a wide variety of surfactants, including those without sulfates or betaines and some with various other additives (e.g., cationic additives, silicones, etc.). Although some variations exist in the properties of different formulations, the relative differences are generally small.

[0314] Table 9: Single-application deposition performance of polymer colorants (Example 2) in different shampoo formulations

[0315] Shampoo ΔE ΔYI Free&Clear Shampoo for Sensitive Skin 8.7 -13 After Color Treatment Shampoo 8.6 -13 Tresemme Pro Pure Micellar Moisture Shampoo 8.5 -12 Schauma 7Herbs Shampoo 7.7 -11 Illuminating Color Care with Biotin Shampoo 7.5 -10 BC Bonacure pH 4.5Color Freeze Shampoo 6.3 -8 EverPure Blonde Shampoo 6.1 -8

[0316] Application Example 8

[0317] Other hair care compositions were also desired for coloring or tinting hair. Conditioners are common hair care compositions that can also be used to deposit color on hair. A range of polymeric colorants can be used in conditioner formulations to color hair. The hair care composition in this example is the conditioner EverPure Blonde Conditioner (L'Oreal). For each colorant, the amount of colorant in the conditioner was adjusted so that each sample exhibited the same color intensity, meaning that the amount or absorbance of chromophores in each conditioner was the same, despite differences in polymer chain length and chromophore type. The maximum absorbance of the colored conditioner was 0.25 when measured at a concentration of 1 g / L in methanol over a 1 cm optical path length. For this study, bleached blonde hair was used as the hair substrate, and the hair was colored using the above-described process. The amount of conditioner used was 0.2 g conditioner / g hair. The conditioner was left in contact with the hair for 3 minutes before rinsing. To evaluate the amount of color deposited on the hair, the ΔE value of the hair after treatment with the conditioner is used relative to the hair before treatment with the conditioner.

[0318] In addition, as described above, the yellowness index (YI) was calculated before and after conditioner treatment. In addition to the polymer colorants evaluated for the conditioners, commercially available dyes commonly used in conditioners were included as comparative samples. External D&C Violet 2 (also known as Acid Violet 43) was formulated in the same manner as the polymer colorants in terms of absorbance / g conditioner. The results are shown in Table 10. Unexpectedly, all evaluated polymer colorants showed more deposition on hair in the conditioner than the commonly used dye (Ext. D&C Violet 2). ΔYI had larger negative absolute values ​​compared to the comparative dyes, meaning they were more effective at neutralizing yellow hues. Also unexpectedly, several polymer colorants showed significantly higher deposition in the conditioner than in the shampoo. Example 1 showed a ΔE 13 times greater in the conditioner than in the shampoo (see Table 7); similarly, Example 2 showed a ΔE more than twice as much in the conditioner as in the shampoo. Polymer colorants exhibit excellent blendability into conditioning agents due to their liquid properties.

[0319] Table 10: Deposition performance of different polymer colorants in conditioners after a single application

[0320] paste ΔE ΔYI Comparison of dye examples: Ext. D&C Violet 2 3.4 -4.0 Example 33 18.7 -21.8 Example 1 16.9 -24.1 Example 2 14.8 -22.4

[0321] Application Example 9

[0322] Many different conditioning formulations can be used to deliver polymeric colorants to hair. This was demonstrated by taking a single polymeric colorant (Example 1), mixing it at 1% by mass into several different commercially available conditioning formulations, and applying it to bleached blonde hair. The amount of conditioning agent used was 0.2 g conditioner / g hair. The conditioner was allowed to remain in contact with the hair for 3 minutes before rinsing. The amount of color deposited on the hair was evaluated by measuring ΔE in the conditioned hair relative to the untreated, uncolored hair, and is shown in Table 11.

[0323] Four different conditioners were evaluated, each with different ingredients. Pantene Pro-V ClassicClean Conditioner (P&G) contains water, stearyl alcohol, stearamide-propyl dimethylamine, cetyl alcohol, glutamic acid, fragrance, diaminopropyl dimethicone, benzyl alcohol, citric acid, disodium EDTA, histidine, panthenol, panthenol ethyl ether, methylchloroisothiazolinone, and methylisothiazolinone. Pantene Nutrient Blends Illuminating Color CareConditioner (P&G) contains water, stearyl alcohol, silicone quaternium-26, behenyltrimethylammonium chloride, cetyl alcohol, fragrance, benzyl alcohol, disodium EDTA, panthenol, panthenol ethyl ether, histidine, citric acid, sodium hydroxide, biotin, methylchloroisothiazolinone, and methylisothiazolinone. Nutri Care Restructuring Conditioner (Fanola) contains water, stearyl alcohol, polysiloxane quaternary ammonium salt-26, behenyltrimethylammonium chloride, cetyl alcohol, fragrance, benzyl alcohol, disodium EDTA, panthenol, panthenol ethyl ether, histidine, citric acid, sodium hydroxide, biotin, methylchloroisothiazolinone, and methylisothiazolinone. EverPure Blonde Conditioner (L'Oreal) contains water, cetearyl alcohol, glycerin, behenyltrimethylammonium chloride, cetyl ester, isopropyl myristate, propylene glycol quaternium-80, fragrance, polysorbate 20, isopropanol, phenoxyethanol, polyquaternium-37, liquid mineral oil (Huile Minerale), tocopheryl acetate, butylene glycol, linalool, chlorhexidine dihydrochloride, citric acid, PPG-1 tridecyl ether-6, hexyl cinnamaldehyde, hydroxycitronellol, acrylate copolymer, sorbitan oleate, Iris Florentina Root Extract, Calendula Officinalis Flower Extract, CI60730 / EXT. Purple 2, CI17200 / Red 33, BHT.

[0324] In this context, some differences exist in the performance of certain conditioners, but the polymer colorant exhibited strong deposition across all evaluated conditioners. This demonstrates that these materials function effectively in a wide variety of formulations, each with its own diverse components.

[0325] Table 11: Single-application deposition performance of polymer colorants (Example 1) in different conditioning agent formulations

[0326] paste ΔE ΔYI Pantene Pro-V Classic Clean Cond.(P&G) 22.8 -33 Pantene Illuminating Color Care Cond.(P&G) 21.7 -31 Nutri Care Restructuring Conditioner(Fanola) 16.9 -26 EverPure Blonde Conditioner(L'Oreal) 16.5 -24

[0327] Application Example 10

[0328] The examples above demonstrate that polymeric colorants offer unexpected advantages and differences compared to conventional hair dyes. Assuming the colorants are completely dissolved in the paste, one might expect them to have poor stability in certain hair care products—especially oxidative hair creams containing hydrogen peroxide. Surprisingly, several examples of this type of polymeric colorant have been found to be stable in oxidative creams containing 12% hydrogen peroxide, as described below.

[0329] The stability and coloring properties of several polymeric colorants in commercially available oxidative hair creams were tested. Each sample was added to Fanola 40Vol Perfumed Cream Developer (available from Fanola Italy) containing approximately 12% hydrogen peroxide. Each sample was mixed with a SpeedMixer at 1500 rpm until a visually homogeneous mixture was obtained (minimum 90 seconds; SpeedMixer from Inc., Landrum, SC). The amount of colorant in each sample was adjusted to ensure that each sample exhibited the same color intensity. The maximum absorbance of the colored cream was 0.67 when measured at a concentration of 1 g / L in methanol over a 1 cm path length. After mixing, the samples were first stored at room temperature for 7 days and then transferred to a 40°C oven. Color stability was evaluated by the number of room temperature equivalent days required to achieve 50% color loss in the cream, where the color loss was based on the original colorimeter measurement at zero time and measured by UV-VIS. Color loss is due to discoloration resulting from chemical changes in the colorants in the oxidizing paste components, including peroxides. Many of these evaluated colorants are stable in oxidizing emulsions, as shown in Table 13 below.

[0330] The equivalent number of days at room temperature is calculated using the following equation:

[0331] Equivalent days at room temperature = Number of days stored at room temperature + Number of days stored at 40℃ * 3.48

[0332] The ratings were generated according to the table below using the equivalent number of days at room temperature during which the color degraded to 50%. A value of "1" indicates that the composition is the most stable, while a value of "5" indicates that it is the least stable.

[0333] Table 12: Stability rating scale for oxidative hair creams containing polymer colorants

[0334] grade Achieving 50% of the equivalent number of days at room temperature 1 Longer than 300 days 2 From 150 days to 300 days 3 From 50 days to 150 days 4 From 20 days to 50 days 5 Less than 20 days

[0335] Table 13: Stability of the polymer colorant of the present invention in oxidative hair cream

[0336] polymer colorants grade Example 1 1 Example 37 1 Example 18 2 Example 10 1

[0337] Application Example 11

[0338] In addition to strongly coloring hair to bright shades such as blue, red, and yellow, it is desirable to controllably deposit less noticeable amounts of certain colors to neutralize the undertones exposed during hair bleaching or lightening. For example, light brown hair will expose a yellow undertone when bleached. Therefore, according to color laws, a purple-based toner will neutralize the light yellow hue to produce a platinum or silver-gold hue. The concentration of the toner can be adjusted so that the enhancement is not masked by the color deposition. According to the invention, there is a single-step method using a composition of hair bleaching agents that can simultaneously bleach hair and efficiently deposit various color hues. This is achieved by including dyes in the bleaching composition. As demonstrated above, several of the blue and purple polymer colorants exhibit good stability in oxidizing creams, so purple colorants can be premixed into oxidizing hair creams and then deposited simultaneously with hair bleaching to neutralize unwanted yellow hues. This is confirmed below.

[0339] Material:

[0340] Golden fur (lightly bleached dark brown fur), trimmed to 3cm wide and 20cm long.

[0341] Fanola Violet Bleach Powder

[0342] Fanola 40 Vol. (12% Peroxide) Oxidizing Paste

[0343] Process:

[0344] First, weigh the hair to calculate the required amount of paste (4g paste / g hair). Mix the colorant and oxidizing paste developer as described above. Check the mixture and remix if necessary to ensure the colorant is completely homogeneous. Weigh Fanola Violet Bleach Powder (available from Fanola Italy) into a small boat-shaped weighing pan (two parts paste: one part bleaching powder). Add the appropriate amount of oxidizing paste to the bleaching powder. Using the wooden end of a cotton swab applicator, stir the bleach / paste until fully mixed. Transfer the bleach / paste mixture to a large boat-shaped weighing pan containing the hair sample. Apply the mixture to the entire hair and rub it into the hair with your fingertips until the mixture is evenly distributed and fully incorporated. Leave the bleach on the hair for 15 minutes, then rinse the hair sample thoroughly with warm water, comb it, and dry it in an oven at 60°C for 45 minutes. Hair color was measured using an X-Rite Color–eye with a 6mm aperture and a D-65 light source. The hair was twisted and pressed against the aperture during measurement. The average of 6 to 8 measurements was used.

[0345] As mentioned earlier, the yellowness index (YI) was calculated for each sample. YI is a good indicator of the quality of hair bleaching. The initial hair had a yellowness index (YI) of 48.9 due to its yellow color. After treatment, the YI value decreased, indicating that the hair had been bleached. The difference in YI between the treated hair and the initial hair was recorded as ΔYI. The larger the absolute value of the negative ΔYI, the better the bleaching of the hair.

[0346] The YI and ΔYI values ​​for initial hair, bleach control (no dye), and bleach compositions containing Example 1 and Comparative Example External D&C Violet 2 are shown in Table 14. The bleach composition of Example 1 provides better bleaching than the bleach control and the bleach composition containing Comparative Example External D&C Violet 2.

[0347] Table 14: Color Evaluation for Simultaneous Bleaching and Tinting of Hair

[0348]

[0349] All references cited in this paper (including publications, patent applications and patents) are incorporated herein by reference to the same extent that each reference is individually and specifically indicated to be incorporated herein by reference, and all of their contents are described herein.

[0350] In the context of describing the subject matter of this application (especially in the context of the appended claims), the terms “a” and “an”, “the”, and similar designations shall be construed as encompassing both singular and plural forms, unless otherwise stated herein or clearly conflicting with the context. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” shall be construed as open-ended terms (i.e., meaning “including, but not limited to”). Unless otherwise stated herein, the enumeration of numerical ranges herein is intended only as a shorthand method of individually referring to each individual numerical value falling within that range, and each individual numerical value is incorporated into the specification as if it were individually enumerated herein. Unless otherwise stated herein or clearly conflicting with the context, all methods described herein may be implemented in any suitable order. The use of any and all instances or exemplary language provided herein (e.g., “for example”) is merely intended to better elucidate the subject matter of this application and not to limit the scope of the subject matter, unless otherwise claimed. No word in the specification shall be construed as indicating any unclaimed element as necessary for practicing the subject matter described herein.

[0351] This document describes preferred embodiments of the subject matter of this application, including the best modes known to the inventors for implementing the claimed subject matter. Variations of those preferred embodiments may become apparent to those skilled in the art after reading the foregoing description. The inventors anticipate that those skilled in the art will appropriately employ these variations, and that the inventors intend to practice the subject matter described herein in ways different from those specifically described herein. Therefore, this disclosure includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. Furthermore, unless otherwise stated herein or clearly contradicted by the context, this disclosure covers any combination of the foregoing elements in all possible variations.

Claims

1. A non-therapeutic method of coloring human head or facial hair, the method comprising the steps of: (a) providing a hair care composition comprising at least one poly(alkylene oxide)-substituted chromophore colorant, wherein the average molecular weight of the poly(alkylene oxide) substituent is from 132 to 10,000, and at least 50 mole % of the poly(alkylene oxide)-substituted chromophore colorant has a molecular weight of less than 5,000, wherein the poly(alkylene oxide) substituent in the chromophore colorant is a polymeric group comprising alkylene oxide residues having from 2 to 4 carbon atoms, and the colorant is selected from the group consisting of: a thiophene azo colorant according to the structure: wherein each x and y is independently an integer from 0 to 20, a colorant having the structure: , and combinations thereof; (b) applying the hair care composition to the hair; and (c) allowing the hair care composition to contact the hair for a period of time.

2. The method of claim 1, wherein the hair care composition additionally comprises at least one hair care ingredient.

3. The method of claim 1, wherein the method further comprises removing the hair care composition from the hair.

4. The method of claim 1, wherein the poly(alkylene oxide)-substituted chromophore colorant is present at a concentration of from 0.001 to 20% by weight of the composition.

5. The method of claim 1, wherein the poly(alkylene oxide)-substituted chromophore colorant is present at a concentration of from 0.01 to 20% by weight of the composition.

6. The method of claim 1, wherein the thiophene azo colorant has the structure: 。 7. The method of claim 1, wherein the poly(alkylene oxide)-substituted chromophore colorant comprises monomeric residues, and wherein at least 75% of the monomeric residues in the poly(alkylene oxide) substituent are selected from the group consisting of -CH2CH2O- and -CH2CH(CH3)O-.

8. The method of claim 1, wherein at least 50 mole % of the poly(alkylene oxide)-substituted chromophore colorant has a molecular weight of less than 2,000.

9. The method of claim 8, wherein the poly(alkylene oxide)-substituted chromophore colorant comprises monomeric residues, and wherein at least 75% of the monomeric residues in the poly(alkylene oxide) substituent are -CH2CH2O-.

10. The method of claim 1, wherein the hair care composition is a non-oxidative hair coloring paste.

11. The method of claim 10, wherein the non-oxidative hair coloring paste is a semi-permanent hair coloring paste.

12. The method of claim 10, wherein the non-oxidative hair coloring paste is a temporary hair coloring paste.

13. The method of claim 1, wherein the hair care composition is an oxidative hair coloring paste.

14. The method of claim 13, wherein the oxidative hair coloring paste is a partial permanent hair coloring paste.

15. The method of claim 14, wherein the oxidative hair coloring paste is a permanent hair coloring paste.

16. The method of claim 1, wherein the hair care composition is a shampoo.

17. The method of claim 1, wherein the hair care composition is a conditioner.

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