Hair care composition containing polymeric colorant

Abstract

To provide a method for coloring human hair or facial hair.SOLUTION: Provided is a method comprising the following steps: (a) providing a hair care composition that contains at least one poly(alkyleneoxy) substituted chromophore colorant; (b) applying the hair care composition to hair; and (c) allowing the hair care composition to contact the hair for a period of time.SELECTED DRAWING: None

Description

Technical Field

[0001]

[0001] The present invention relates to a hair care composition containing at least one hair care raw material component and at least one polymeric colorant. Background

[0002]

[0002] With the consumer's desire to color their own hair, various hair dyes have been invented. Typically, there are two categories of hair dyes. The first category is known as oxidative or permanent dyes in the form of professional dyes, which oxidize during application to form color. Some well-known examples of this class are phenylenediamine and para-aminophenol, which are blended with additional couplers (e.g., resorcinol, m-aminophenol, etc.). The other category is often called non-oxidative or direct dyes. These dyes are pre-formed dye molecules. Examples within this category include Basic Red 76, Acid Violet 43, HC Blue 15, and HC Blue 16.

[0003]

[0003] However, current molecular hair dyes have weaknesses. Pre-formed dyes are conjugated, rigid organic compounds that are often difficult to dissolve in hair care compositions. Undissolved dyes can leave an uneven hue or sometimes color spots on the treated hair. In addition, the toxicity of hair dyes is also a concern. Furthermore, current direct dyes tend to be washed out very rapidly and are thus considered semi-permanent. Therefore, there is a continuing need to further improve current hair dyes. In this regard, polymeric liquid colorants are superior to conventional hair dyes because they are easy to formulate and their high molecular weight makes it difficult for them to penetrate the skin, resulting in less concern about toxicity. Polymeric liquid colorants also appear to have superior washing performance compared to current dyes. Brief Summary

[0004]

[0004] On one side, the present invention is a method for coloring human hair or facial hair, comprising the following steps: (a) preparing a hair care composition containing at least one poly(alkyleneoxy) substituted chromophore colorant; (b) applying the hair care composition to the hair; and (c) contacting the hair care composition with the hair for a certain period. The hair care composition may further contain at least one hair care raw material component.

[0005]

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

[18] annulene, formazan copper complex, nitroso, nitro, diarylmethane, triarylmethane, xanthene, acridine, methine, thiazole, indamine, azine, oxazine, thiazine, quinoline, indigoid, indophenol, lactone, aminoketone, hydroxyketone, naphthalimide, and stilbene chromophores.

[0006]

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

[0007]

Chemical formula

[0008] [wherein, AR1 and AR2 are independently selected from the group consisting of alkenyl groups, substituted alkenyl groups, aryl groups, substituted aryl groups, heteroaryl groups, and substituted heteroaryl groups; and one of the AR1 or AR2 groups can be further substituted with another azo chromophore to form a bisazo].

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

[0010] [ka]

[0011] [In the formula, e and f are independently an integer of 0 to 4; 20 and R 21 is a halogen, a hydroxy group, a nitro group, a nitrile group, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group, -S(O)2OH, -S(O)2O - [M + ], —C(O)OR, —C(O)R, —C(O)NRR, —NRC(O)OR, —NRC(O)SR, —OR, —NRR, —S(O)R, —S(O)NRR, and —P(O)R; M is a cation; and R and R are independently selected from the group consisting of hydrogen, alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups.

[0012] In a further aspect of the invention, the chromophore is

[0013] [ka]

[0014] wherein h, i, and j are independently integers from 0 to 4, provided that in Structure IIIa, h is an integer from 0 to 2. 31 are =O, =S, and =NR 34 , and =N + R 34 R 35 selected from the group consisting of: R 30 -O - , -S - , -OR 36and -NR 36 R 37 is selected from the group consisting of. Each R 34 R 35、 R 36 and R 37 is independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaryl group, a substituted heteroaryl group, an acyl group, -C(O)OR5, -C(O)R5, and -C(O)NR5R6. Each R 31、 R 32 and R 33 group is independently selected from the group consisting of halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, and substituted heteroaryl group, -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 the group consisting of hydrogen, alkyl group, substituted alkyl group, aryl group, and substituted aryl group. X 30 X 31 X 32 and X 33 is independently selected from the group consisting of carbon atoms and nitrogen atoms, provided that no more than two of X 30 X 31 X 32 and X 33 are nitrogen atoms] is selected.

[0015]

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

[0016]

Chemical formula

[0017] [wherein X 42is selected from the group consisting of an oxygen atom, a sulfur atom, SiR 45 R 46 , and NR 45 ; Y 41 is selected from the group consisting of =O, =S, =NR 46 , and =N + R 45 R 46 ; R 45 and R 46 are each independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaryl group, a substituted heteroaryl group, -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 is independently selected from the group consisting of a halogen, a hydroxy group, a nitro group, a nitrile group, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group, -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)2R 5、 -SR5, -S(O)2NR5R6, and -P(O)2R5; M is a cation, and at least one R 42 group is selected from the group consisting of -OR5, -SR5, and -NR5R6. R5 and R6 are each independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group].

[0018]

[0010] In another aspect of the present invention, the chromophore has the structure:

[0019]

Chemical formula

[0020] [wherein, AR51 is selected from the group consisting of an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group; R 52 , R 53 and R 54 are independently selected from the group consisting of hydrogen and R 51 ; each R 51 is independently selected from halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, and substituted heteroaryl group, -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 is not hydrogen; R5 and R6 are independently selected from the group consisting of hydrogen, alkyl group, substituted alkyl group, aryl group, and substituted aryl group; c is an integer from 1 to 10. X 50 , X 51 , X 52 , and X 53 are independently selected from the group consisting of a carbon atom and a nitrogen atom, provided that no more than two of X 50 , X 51 , X 52 , and X 53 are nitrogen atoms, and g is an integer from 1 to 4]; Structure V optionally exists in an ionic form that maintains electrical neutrality by being accompanied by its counterion.

[0021]

[0011] In one aspect of the present invention, the chromophore has the structure:

[0022]

Chemical formula

[0023] [wherein each R 61 , R 62 , R63 and R 64 groups are independently selected from halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, -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, n, o, p and q are integers independently selected from 0 to 4; R5 and R6 are independently selected from the group consisting of hydrogen, alkyl group, substituted alkyl group, aryl group, and substituted aryl group; Q is hydrogen, a metal ion, or a metalloid; A is an anion; x is a positive integer, y is an integer including zero, and the divalent group -Q x A y - is neutral].

[0024]

[0012] In yet a further aspect of the present invention, the chromophore has the structure:

[0025]

Chemical formula

[0026] [wherein each R 71 , R 72 and R 73 groups are independently selected from hydrogen, halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, -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; n, o, p, and q are integers independently selected from 0 to 4; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, provided that at least one R 72 group is an -OR5 or -NR5R6 group].

[0027]

[0013] In another aspect of the present invention, the chromophore is

[0028]

Chemical formula

[0029] [wherein X1 and X2 are selected from the group consisting of a carbon atom and a nitrogen atom; a is an integer from 0 to 5, provided that when one of X1 and X2 is a nitrogen atom, a is an integer from 0 to 4, and when both X1 and X2 are nitrogen atoms, a is an integer from 0 to 3; each R1 is a halogen, a hydroxy group, a nitro group, a nitrile group, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group, -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, independently selected from the group consisting of; M is a cation; R5 and R6 are independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group; R2 and R3 are selected from the group consisting of an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group; Y1 is =O, =S, =NR5, and =N + selected from the group consisting of R5R6]; Structures VIII and VIIIa may independently and optionally exist in ionic forms that maintain electrical neutrality by being accompanied by their counterions.

[0030]

[0014] In a further aspect of the present invention, the chromophore has the structure:

[0031]

Chemical formula

[0032] [wherein, AR 11 is selected from the group consisting of an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group; R 11 and R 14 are hydrogen, halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, -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, independently selected from the group consisting of; M is a cation; R5 and R6 are independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group; b is an integer from 1 to 10].

[0033]

[0015] In another aspect of the present invention, at least 50 mol% of the poly(alkyleneoxy) substituted chromophore colorant has a molecular weight of less than 5000, or even less than 2000. In addition, the poly(alkyleneoxy) substituted chromophore colorant contains monomer residues, and at least 75% of the monomer residues in the poly(alkyleneoxy) substituent are selected from -CH2CH2O- and -CH2CH(CH3)O-. In a further aspect of the present invention, the poly(alkyleneoxy) substituted chromophore colorant contains monomer residues, and at least 75% of the monomer residues in the poly(alkyleneoxy) substituent are -CH2CH2O-.

[0034]

[0016] In a further aspect of the present invention, the hair care composition is a non-oxidative hair coloring cream agent. The non-oxidative hair coloring cream agent may be a semi-permanent hair coloring cream agent or a temporary hair coloring cream agent.

[0035]

[0017] In yet another aspect of the present invention, the hair care composition is an oxidative hair coloring cream agent. The oxidative hair coloring cream agent may be a semi-permanent hair coloring cream agent or a permanent hair coloring cream agent.

[0036]

[0018] In a further aspect of the present invention, the hair care composition is a shampoo or a conditioner. Detailed Description

[0037]

[0019] The present invention described herein is a hair care composition containing at least one hair care raw material component and at least one polymeric colorant. The hair care composition containing a polymeric colorant is suitable for direct application to hair (e.g., human hair, animal hair, etc.), and has improved stability and shading compared to conventional hair dyes.

[0038]

[0020] As used herein, the term "hair" is intended to include keratin fibers attached to a living body, such as human head hair, human facial hair, animal hair, and the like.

[0039]

[0021] As used herein, the term "alkoxy" is intended to include C1-C8 alkoxy and alkoxy derivatives of polyols having repeating units such as butylene oxide, glycidol oxide, ethylene oxide, or propylene oxide.

[0040]

[0022] As used herein, the terms "polyalkyleneoxy" and "polyoxyalkylene" are used interchangeably herein and generally refer to a molecular structure containing the following repeating units: -CH2CH2O-, -CH2CH2CH2O-, -CH2CH2CH2CH2O-, -CH2CH(CH3)O-, -CH2CH2CH(CH3)O-, and any combination thereof. Further, the polyoxyalkylene constituent material may be selected from the group consisting of one or more monomers selected from alkylene oxides, glycidol, and mixtures thereof. 2~20 One or more monomers selected from the group consisting of alkylene oxides, glycidol, and mixtures thereof.

[0041]

[0023] As used herein, unless otherwise specified, the terms "alkyl" and "alkyl-capped" are intended to include C2-C 100 alkyl group, C2-C 50 alkyl group, C5-C 25 alkyl group, or even C 10 ~C 20 alkyl group.

[0042]

[0024] As used herein, unless otherwise specified, the term "aryl" means a C5-C 18 aryl group and, in one aspect, is intended to include a C5-C 12 aryl group.

[0043]

[0025] As used herein, unless otherwise specified, the term "arylalkyl" means a C1-C 18 arylalkyl group and, in one aspect, is intended to include a C1-C6 arylalkyl group.

[0044]

[0026] As used herein, unless otherwise specified, the term "alkanoyl" means a group of the formula -C(O)R a (wherein R a is an alkyl group, preferably a C3-C 29 alkyl group).

[0045]

[0027] As used herein, unless otherwise specified, the term "alkenyl" means a monovalent group obtained by removing a hydrogen atom from any carbon atom of an acyclic olefinic hydrocarbon. In the context of this definition, the term "acyclic olefinic hydrocarbon" means an acyclic hydrocarbon containing one or more carbon-carbon double bonds.

[0046]

[0028] As used herein, unless otherwise specified, the term "alkenoyl" means a group of the formula -C(O)R b (wherein R b is an alkenyl group, preferably a C3-C 29 alkenyl group).

[0047]

[0029] As used herein, unless otherwise specified, the term "aroyl" means a group of the formula -C(O)R c (wherein R c is an aryl group, preferably a C6-C 10 aryl group).

[0048]

[0030] The terms "ethylene oxide", "propylene oxide", and "butylene oxide" may each be referred to herein by their typical names "EO", "PO", and "BO".

[0049]

[0031] Unless otherwise indicated, all percentages and ratios are calculated by weight. Unless otherwise indicated, all percentages and ratios are calculated based on the total composition.

[0050]

[0032] The hair care composition may be in any physical form suitable for application to the hair, including but not limited to liquids, creams, sprays, conditioners, gels, mousses, etc. The hair care composition is intended to include, but is not limited to, oxidative hair creams, non-oxidative hair creams, depigmenting compositions, shampoos, conditioners, and any other composition useful as a vehicle for applying the raw material components described herein to the hair. Further details and examples of suitable physical forms and vehicles for the application of the compositions of the present invention can also be found in Singer et al.'s USPN 9,820,922.

[0051]

[0033] In the present invention, the hair care composition contains at least one hair care raw material component. Examples of hair care raw material components include, but are not limited to, skin softening oils, surfactants, non-ionic surfactants, anionic surfactants, cationic, zwitterionic or betaine surfactants, polar solvents, chelating agents, pH adjusters, conditioning agents, and mixtures thereof. Oxidizing agents may also be included in oxidative formulations. Further, oxidizing agents may be excluded from non-oxidative formulations.

[0052]

[0034] The hair care composition of the present invention is generally water-based, containing from about 0.01 to 99% by weight, preferably from about 0.1 to 98% by weight, more preferably from about 45 to 95% by weight of water of the total composition.

[0053]

[0035] The hair care composition may include, for example, a hair shampoo based on conventional anionic, amphoteric, zwitterionic, non-ionic, and / or cationic surfactants. Suitable commercially available shampoos clean the hair and remove residues of sebum and / or styling agents and other impurities from the hair surface and the scalp.

[0054]

[0036] The hair care composition may also include a hair conditioner. Hair conditioning is understood by those skilled in the art to mean treating the hair with a so-called rinse-off formulation for care (i.e., a formulation that is rinsed off) or a so-called leave-on formulation (i.e., a formulation that remains on the hair without being rinsed off), in particular using a shampoo or conditioner for care. This treatment, in both wet and dry states, improves the ease of combing (resistance to tangling) along the entire length and at the tips of the hair, improves tactile properties such as smoothness, softness, and flexibility, further improves the luster of the hair, reduces static electricity, and improves styling ease. Thus, overall, a cared-for and overall healthy hair condition is achieved through conditioning.

[0055]

[0037] Skin softening oil If desired, the hair cream composition may contain one or more skin softening oils. Such oils provide a conditioning effect on the hair. When present, such oils may be in the range of about 0.001 to 45% by weight, preferably about 0.01 to 40% by weight, more preferably about 0.1 to 35% by weight of the total composition. Suitable oils include silicones such as dimethicone, phenyl silicone, fatty alkyl silicones such as 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 or synthetic oils derived from plants or animals. Examples include oils derived from sunflower, castor seeds, orange, lemon, jojoba, mineral oil, etc. Other common examples include cetearyl alcohol, lauryl alcohol, myristyl alcohol, lanolin alcohol, coconut alcohol, etc.

[0056]

[0039] Surfactant

[0040] The oxidative dye composition may contain one or more surfactants. Suitable surfactants include anionic surfactants, nonionic surfactants, amphoteric surfactants, etc. When present, the surfactant may be in the range of about 0.001 to 50% by weight, preferably about 0.005 to 45% by weight, more preferably about 0.1 to 40% by weight of the first composition.

[0057]

[0041] Nonionic surfactant Examples of nonionic surfactants include alkoxylated alcohols or ethers, alkoxylated carboxylic acids, sorbitan derivatives, etc. Alkoxylated alcohols, or ethers, are formed by the reaction of an alcohol with an alkylene oxide, usually ethylene oxide or propylene oxide. Preferably, the alcohol is an aliphatic alcohol having 6 to 30 carbon atoms and a straight-chain or branched, saturated or unsaturated carbon chain. Examples of such raw material components include Steareth 2 - 30 (formed by the reaction of stearyl alcohol and ethylene oxide, and the number of repeating units of ethylene oxide is 2 - 30); Laureth 2 - 30 (formed by the reaction of lauryl alcohol and ethylene oxide, and the number of repeating units of ethylene oxide is 2 - 30); Oleth 2 - 30 (formed by the reaction of oleyl alcohol and ethylene oxide, and the number of repeating units of ethylene oxide is 2 - 30); Ceteareth 2 - 100 (formed by the reaction of a mixture of cetyl and stearyl alcohols and ethylene oxide, and the number of repeating units of ethylene oxide in the molecule is 2 - 100); Cete 1 - 45 (formed by the reaction of cetyl alcohol and ethylene oxide, and the number of repeating units of ethylene oxide is 1 - 45), etc. Particularly preferred is the case where the nonionic surfactant is Steareth 20 or Ceteareth 20 (cetearth - 20). Similarly suitable is alkoxylated carboxylic acid, which is formed by the reaction of a carboxylic acid with an alkylene oxide or a polymeric ether.

[0058]

[0042] Also suitable are various types of alkoxylated sorbitans and alkoxylated sorbitan derivatives. For example, the alkoxylation of sorbitan, especially ethoxylation, results in polyalkoxylated sorbitan derivatives. The esterification of polyalkoxylated sorbitan results in sorbitan esters, such as polysorbates. Examples of such raw material components include polysorbate 20 - 85, sorbitan oleate, sorbitan palmitate, sorbitan sesquioleate, sorbitan stearate, etc. In a preferred embodiment, polysorbate 20 is preferred.

[0059]

[0043] Anionic surfactant

[0044] The hair cream composition may optionally contain one or more anionic surfactants. The preferred range of the anionic surfactant is about 0.01 to 25% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight of the total oxidative composition. Suitable anionic surfactants include the formulas ROSO3M and RO(C2H4O) x SO3M (wherein R is an alkyl or alkenyl of about 10 to 20 carbon atoms, x is from 1 to about 10, and M is a water-soluble cation such as ammonium, sodium, potassium, or triethanolamine cation), and alkyl sulfates and alkyl ether sulfates generally having the formula.

[0060]

[0045] Another type of anionic surfactant that can be used in the composition 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 the group consisting of linear or branched, saturated aliphatic hydrocarbon radicals having from about 8 to about 24 carbon atoms, preferably from 12 to about 18 carbon atoms, and M is a cation). Examples of such anionic surfactants are salts of organic sulfuric acid reaction products of hydrocarbons, such as n-paraffins having from 8 to 24 carbon atoms, and sulfonating agents such as sulfur trioxide.

[0061]

[0046] Also suitable as an anionic surfactant is the reaction product of a fatty acid esterified with isethionic acid and neutralized with sodium hydroxide, or the reaction product of a fatty acid with an alkanolamine or ammonium hydroxide. The fatty acid may be derived from, for example, coconut oil. Examples of fatty acids also include lauric acid, stearic acid, oleic acid, palmitic acid, and the like.

[0062] In addition, succinates and succinamates are suitable anionic surfactants. This class includes compounds such as sodium dioctyl sulfosuccinate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinate; and esters of sodium sulfosuccinate, such as dihexyl ester of sodium sulfosuccinate, dioctyl ester of sodium sulfosuccinate, and the like.

[0063]

[0048] Other suitable anionic surfactants include olefin sulfonates having about 12 to 24 carbon atoms. The term "olefin sulfonate" means a compound that can be produced by sulfonating an alpha olefin by means of sulfur trioxide that has not formed a complex, and subsequently neutralizing the acidic reaction mixture under conditions such that any sultone formed during the reaction is hydrolyzed to give the corresponding hydroxy-alkane sulfonate. The alpha olefin from which the olefin sulfonate is obtained is a monoolefin having about 12 to 24 carbon atoms, preferably about 14 to 16 carbon atoms.

[0064]

[0049] Another class of suitable anionic organic surfactants is β-alkoxyalkane sulfonates or their water-soluble soaps, such as C 10~20 Salts of fatty acids, such as coconut and tallow-based soaps. Preferred salts are ammonium, potassium, and sodium salts.

[0065]

[0050] As yet another class of anionic surfactants, the formula: (R1 is C 8~24 alkyl or alkenyl radical, preferably C 10~18 ; R2 is H, C 1~4 alkyl, phenyl, or -CH2COOM; R3 is CX2- or C 1~2 alkoxy, and each X is independently H or C 1~6which is an alkyl or alkyl ester, n is from 1 to 4, and M is H or a salt-forming cation as described above), and salts thereof (alkali, alkaline earth, and ammonium salts). Examples of such surfactants are N-acyl sarcosinates, including lauroyl sarcosinate, myristoyl sarcosinate, cocoyl sarcosinate, and oleoyl sarcosinate, preferably in the form of sodium or potassium.

[0066]

[0051] Cationic, zwitterionic or betaine surfactants

[0052] Certain types of amphoteric, zwitterionic, or cationic surfactants can also be used as amphiphilic surfactant materials. Descriptions of such surfactants are provided in U.S. Patent No. 5,843,193, which is hereby incorporated by reference in its entirety.

[0067]

[0053] The amphoteric surfactants that can be used in the compositions of the present invention are generally described as derivatives of aliphatic secondary or tertiary amines, in which one aliphatic radical is a straight-chain or branched-chain alkyl of 8 to 18 carbon atoms and the other aliphatic radical contains an anionic group such as carboxy, sulfonate, sulfate, phosphate, or phosphonate.

[0068]

[0054] Also suitable amphoteric surfactants are monocarboxylates or dicarboxylates such as cocoamphocarboxypropionate, cocoamphocarboxylic acid, cocoamphocarboxyglycinate, and cocoamphoacetate.

[0069]

[0055] As other types of amphoteric surfactants, aminoalkanoates of R-NH(CH2) n COOM or iminodiacanoates of the formula: R-[(CH2) m COOM]2 and mixtures thereof (wherein n and m are from 1 to 4 and R is C 8~22(which is alkyl or alkenyl, and M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or alkanolammonium). Examples of such amphoteric surfactants include n-alkylaminopropionate and n-alkyliminodipropionate. Zwitterionic surfactants are also suitable for use in the compositions of the present invention and include betaines such as higher alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxylethyl betaine, and mixtures thereof. Also suitable are sulfo- and amido-betaines such as coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine and the like. Particularly preferred is cocamidopropyl betaine.

[0070]

[0056] Polar solvent

[0057] The hair cream composition may also contain various non-aqueous polar solvents other than water, including monohydric, dihydric, or polyhydric alcohols, and similar water-soluble raw material components. When present, such polar solvents may be in the range of about 0.01 to 25% by weight, preferably about 0.05 to 15% by weight, more preferably about 0.1 to 10% by weight of the first composition of the polar solvent. Examples of suitable monohydric alcohols include ethanol, isopropanol, benzyl alcohol, butanol, pentanol, ethoxyethanol, and the like. Examples of dihydric or polyhydric alcohols, as well as sugars and other types of humectants that can be used, include glycerin, glucose, fructose, mannose, mannitol, maltitol, lactitol, inositol, and the like. Suitable glycols include propylene glycol, butylene glycol, ethylene glycol, polyethylene glycol, ethoxydiglycol, and the like having 4 to 250 repeating ethylene glycol units.

[0071]

[0058] Chelating agent

[0059] The oxidation dye composition can optionally contain 0.0001 to 5%, preferably 0.0005 to 3%, more preferably 0.001 to 2% of one or more chelating agents that can complex with metal ions and inactivate them to prevent these harmful effects on the stability or action of the composition. In particular, the chelating agent chelates metal ions found in water and prevents these ions from interfering with the deposition and reaction of the dye on the hair fiber surface. Suitable chelating agents include EDTA and its calcium, sodium, or potassium derivatives, HEDTA, sodium citrate, TEA-EDTA, and the like.

[0072]

[0060] pH adjuster

[0061] It may also be desirable to add a small amount of acid or base to adjust the pH of the oxidation dye composition to the desired pH range. Suitable acids include hydrochloric acid, phosphoric acid, ethylenediphosphonic acid, and the like. Suitable bases include sodium hydroxide, ammonium hydroxide, potassium hydroxide, and the like. Also suitable are primary, secondary, or tertiary amines or their derivatives, such as aminomethylpropanol, monoethanolamine, and the like. Phosphates, such as potassium phosphate, disodium phosphate, and the like, can also be used. The suggested range of the pH adjuster is about 0.00001 to 8% by weight, preferably about 0.00005 to 6% by weight, more preferably about 0.0001 to 5% by weight of the total composition.

[0073]

[0062] Conditioning agent

[0063] The hair cream composition may also contain a hair conditioning agent. 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.

[0074] Preferred conditioning agents for use herein include cationic surfactants, cationic polymers, insoluble silicone conditioning agents, amino-functionalized silicones, and saturated C14-C22 straight-chain fatty alcohols and mixtures thereof.

[0075] When present, the insoluble silicone conditioning agent is present at a level of about 0.1 to 10% by weight of the composition, 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, polyether siloxane copolymers, and mixtures thereof.

[0076]

[0066] Other additional components

[0067] The composition of the present invention typically further comprises several other components commonly used in hair care compositions, such as shampoos, conditioners, styling aids, and colorants, which are well known to those skilled in the art, such as thickeners and diluents. Additionally, several optional materials can be added to the compositions described herein at levels of from about 0.001% to about 5% by weight, preferably from about 0.01% to about 3% by weight, more preferably from about 0.05% to about 2% by weight of the composition.Such materials include proteins and polypeptides and their derivatives; water-soluble or solubilizing 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, disodium bisulfite, and thioglycolic acid, sodium dithionite, erythorbic acid, and other mercaptans; H2O2 stabilizers such as tin compounds such as sodium stannate, stannic hydroxide, and tin octoate, acetanilide, phenacetin, colloidal silica such as magnesium silicate, oxyquinoline sulfate, sodium phosphate, and tetrasodium pyrophosphate; and hydroxybenzoate; humectants such as hyaluronic acid, chitin, and starch-grafted sodium polyacrylate, as well as methylcellulose, starch, higher aliphatic alcohols, paraffin oil, fatty acids, etc.; solvents; antibacterial agents; low-temperature phase modifiers such as ammonium ion sources (e.g., NH4Cl); viscosity regulators such as magnesium sulfate and other electrolytes; quaternary amine compounds such as distearyl-, dilauryl-, dihydrogenated tallow-, dimethylammonium chloride, cetyl diethylmethylammonium sulfate, ditallow dimethylmethyl sulfate ammonium, soy dimethylammonium chloride, and coco dimethylammonium chloride; enzyme stabilizers such as water-soluble sources of calcium or borate species; TiO2 and TiO2-coated mica; perfumes and perfume solubilizers; and zeolites and their derivatives and metal ion scavengers such as polycarboxylates, aminopolycarboxylates, polyphosphonates, aminopolyphosphonates, etc., as well as water softeners such as sodium citrate, inorganic peroxide oxidants, and enzymes are included.

[0077]

[0068] Oxidizing agent composition In addition, the aqueous hair cream composition may also contain an oxidizing agent. The most commonly used aqueous oxidizing agent is hydrogen peroxide, but other peroxides or oxidizing agents, such as calcium peroxide, can also be used. Preferably, the hydrogen peroxide concentration in the aqueous oxidizing agent composition ranges from about 10 to 40 volumes, which is the volume-based amount of hydrogen peroxide present in the composition.

[0078]

[0070] Additional suitable oxidizing agents (herein also referred to 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, pages 271 - 300, "Bleaching Agents (Survey)", which is incorporated herein by reference. These sources of hydrogen peroxide include various forms of sodium perborate and sodium percarbonate, including coated and modified forms of these compounds.

[0079]

[0071] The preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example, perborates, such as sodium perborate (any hydrate but preferably the mono - or tetrahydrate), sodium carbonate hydroperoxide or an equivalent percarbonate, sodium pyrophosphate hydroperoxide, urea hydroperoxide, or sodium peroxide can be used here. Sources of available oxygen, such as persulfate bleaching agents (e.g., OXONE made by DuPont), are also useful. Sodium perborate monohydrate, sodium percarbonate, sodium persulfate, and potassium persulfate are particularly preferred. Mixtures of any convenient source of hydrogen peroxide can also be used.

[0080]

[0072] The composition of the present invention may also contain a chlorine - based bleaching substance as a bleaching agent. Such agents are well - known in the art and include, for example, sodium dichloroisocyanurate ("NaDCC").

[0081]

[0073] In one aspect of the present invention, the peroxygen bleaching agent component in the composition is formulated with an activator (peracid precursor). The activator is present at a level from about 0.01% by weight of the composition, preferably from about 0.5% by weight, more preferably from about 1% to about 15% by weight, preferably up to about 10% by weight, more preferably up to about 8% by weight. The bleaching activator, when used herein, is any compound which, when used with hydrogen peroxide, results in the in situ formation of a peracid whose source corresponds to the bleaching activator. Various non-limiting examples of activators are disclosed in U.S. Patent Nos. 5,576,282; 4,915,854, and 4,412,934. See also U.S. Patent No. 4,634,551 for other typical bleaching agents and activators useful herein.

[0082]

[0074] Preferred activators are tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulfonate (C 10 -OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS), perhydrolyzable esters, and mixtures thereof, most preferably selected from the group consisting of benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleaching activators in the pH range of about 8 to about 11 are selected from those having an OBS or VL leaving group.

[0083]

[0075] Preferred hydrophobic bleaching activators include nonanoyloxybenzenesulfonate (NOBS); sodium 4-[N-(nonanoyl)aminohexanoyloxy]-benzenesulfonate (NACA-OBS) this example is described in U.S. Patent No. 5,523,434; dodecanoyloxybenzenesulfonate (LOBS or C 12-OBS); 10-undecenoyl oxybenzenesulfonate (UDOBS or C11-OBS having unsaturation at the 10-position); and decanoyl oxybenzoic acid (DOBA), among others, but not limited thereto.

[0084]

[0076] Preferred decolorizing activators are those described in U.S. Patent No. 5,998,350 to Burns et al.; U.S. Patent No. 5,698,504 to Christie et al.; U.S. Patent No. 5,695,679 to Christie et al.; U.S. Patent No. 5,686,401 to Willey et al.; U.S. Patent No. 5,686,014 to Hartshorn et al.; U.S. Patent No. 5,405,412 to Willey et al.; U.S. Patent No. 5,405,413 to Willey et al.; U.S. Patent No. 5,130,045 to Mitchel et al.; and U.S. Patent No. 4,412,934 to Chung et al., as well as co-pending patent application serial number 08 / 064,564, all of which are hereby incorporated by reference.

[0085]

[0077] Also, a quaternary-substituted decolorizing activator may be included. The composition of the present invention preferably includes a quaternary-substituted decolorizing activator (QSBA) or a quaternary-substituted peracid (QSP, preferably a quaternary-substituted percarboxylic acid or a quaternary-substituted peroxyimidic acid); more preferably, the former is included. Preferred QSBA structures are further described in U.S. Patent No. 5,686,015 to Willey et al.; U.S. Patent No. 5,654,421 to Taylor et al.; U.S. Patent No. 5,460,747 to Gosselink et al.; U.S. Patent No. 5,584,888 to Miracle et al.; and U.S. Patent No. 5,578,136 to Taylor et al.; all of which are hereby incorporated by reference.

[0086]

[0078] Additional decolorizing agent activators useful herein are amide-substituted as described in U.S. Patent Nos. 5,698,504; 5,695,679; and 5,686,014, each of which is hereby incorporated by reference herein. Preferred examples of such decolorizing activators include (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.

[0087]

[0079] Other useful activators are disclosed in U.S. Patent Nos. 5,698,504; 5,695,679; and 5,686,014, each of which is hereby incorporated by reference herein, as well as in U.S. Patent No. 4,966,723 to Hodge et al. Such activators include benzoxazine-type activators, for example, a C6H4 ring condensed at the 1,2-position with a --C(O)OC(R 1 )=N- moiety.

[0088]

[0080] Nitriles, such as acetonitrile and / or ammonium nitrile and other quaternary nitrogen-containing nitriles, are another class of activators useful herein. Non-limiting examples of such nitrile decolorizing activators are described in U.S. Patent Nos. 6,133,216; 3,986,972; 6,063,750; 6,017,464; 5,958,289; 5,877,315; 5,741,437; 5,739,327; and 5,004,558; as well as European Patent Nos. 790 244, 775 127, 1 017 773, and 1 017 776; and WO99 / 14302, WO99 / 14296, and WO96 / 40661, all of which are hereby incorporated by reference herein.

[0089]

[0081] Depending on the activator and the specific application, good decolorization results can be obtained from a decolorizing system with a pH during use of about 6 to about 13, preferably about 9.0 to about 11.5. For example, for pH ranges near or below neutral, activators typically having an electron-withdrawing moiety are used. Such pH can be ensured using alkalis and buffers.

[0090]

[0082] The acyl lactam activators described in U.S. Patent Nos. 5,698,504; 5,695,679 and 5,686,014, each of which is hereby incorporated by reference above, especially acyl caprolactam (see, for example, WO94-28102A) and acyl valerolactam (see U.S. Patent No. 5,503,639 to Willey et al., which is hereby incorporated by reference) may also be useful here.

[0091]

[0083] Organic peroxides, especially diacyl peroxides, may also be suitable for use. These are described in detail in Kirk Othmer, Encyclopedia of Chemical Technology, Volume 17, John Wiley and Sons, 1982, pages 27 - 90, especially pages 63 - 72, all of which are hereby incorporated by reference. When diacyl peroxide is used, it preferably has a minimal adverse effect on fabric care including color care.

[0092]

[0084] The compositions and methods of the present invention can also optionally include a metal-containing decolorization catalyst, preferably a manganese and cobalt-containing decolorization catalyst.

[0093]

[0085] One type of metal-containing decolorizing catalyst is a catalyst system comprising a transition metal cation having a determined decolorizing catalytic activity (for example, copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cation), an auxiliary metal cation having little or no decolorizing catalytic activity (for example, zinc or aluminum cation), and a sequestering agent having a determined stability constant with respect to the catalyst and the auxiliary metal cation, in particular ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid), and water-soluble salts thereof. Such catalysts are disclosed in U.S. Patent No. 4,430,243 to Bragg.

[0094]

[0086] If desired, the composition herein can be catalyzed by a manganese compound. Such compounds and the degree of use are well known in the art, and examples include the manganese-based catalysts disclosed in U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Patent Application Publication Nos. 549,271A1; 549,272A1; 544,440A2; and 544,490A1. Preferred examples of these catalysts include Mn IV 2(μ-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mn III 2(μ-O)1(μ-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(ClO4)2, Mn IV 4(μ-O)6(1,4,7-triazacyclononane)4(ClO4)4, Mn III Mn IV 4(μ-O)1(μ-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 decolorizing catalysts include those disclosed in U.S. Patent Nos. 4,430,243 and 5,114,611. The use of manganese with various complex ligands to enhance decolorization has also been reported below: U.S. Patent Nos. 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

[0095]

[0087] Cobalt decolorizing catalysts useful herein are known, for example, from U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; and as described in M.L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pp. 1-94. The most preferred cobalt catalysts useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc]Ty, where "OAc" represents the acetate moiety and "Ty" represents an anion, in particular, cobalt pentaamine acetate chloride [Co(NH3)5OAc]Cl2; and [Co(NH3)5OAc](OAc)2; [Co(NH3)5OAc](PF6)2; [Co(NH3)5OAc](SO4); [Co(NH3)5OAc](BF4)2; and [Co(NH3)5OAc](NO3)2 (herein "PAC").

[0096]

[0088] These cobalt catalysts can be readily prepared by known procedures, for example, as taught in U.S. Patent Nos. 6,302,921; 6,287,580; 6,140,294; 5,597,936; 5,595,967; and 5,703,030; the papers of Tobe and the references cited therein; as well as U.S. Patent No. 4,810,410; J. Chem. Ed. (1989), 66(12), 1043 - 45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice - Hall; 1970), pp. 461 - 3; Inorg. Chem., 18, 1497 - 1502 (1979); Inorg. Chem., 21, 2881 - 2885 (1982); Inorg. Chem., 18, 2023 - 2025 (1979); Inorg. Synthesis, pp. 173 - 176 (1960); and Journal of Physical Chemistry, 56, 22 - 25 (1952).

[0097]

[0089] The compositions herein may also preferably contain a transition metal complex of a macrocyclic rigid ligand as a decolorizing catalyst. The amount used is a catalytically effective amount, preferably about 1 ppb or more, for example, about 99.9% or less, more typically about 0.001 ppm or more, preferably about 0.05 ppm to about 500 ppm (where "ppb" represents parts by weight per billion and "ppm" represents parts by weight per million).

[0098]

[0090] Examples of transition metal decolorizing catalysts of macrocyclic rigid ligands suitable for use in the compositions of the present invention include generally known compounds, but are non - limitatively exemplified by any of the following: Dichloro - 5,12 - dimethyl - 1,5,8,12 - tetraazabicyclo[6.6.2]hexadecane manganese(II) Dichloro - 5,12 - diethyl - 1,5,8,12 - tetraazabicyclo[6.6.2]hexadecane manganese(II) Diaco-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) hexafluorophosphate Diaco-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) hexafluorophosphate Aco-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(III) hexafluorophosphate Diaco-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) tetrafluoroborate Dichloro-5,12-dimethyl-1,5,8,12 tetraazabicyclo[6.6.2]hexadecane manganese(III) hexafluorophosphate Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(III) hexafluorophosphate Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane manganese(II) Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane manganese(II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane manganese(II) As a practical matter, and not by way of limitation, the compositions and methods herein can be adjusted such that the active decolorizing catalyst species are on the order of at least one part per hundred million in a composition comprising a lipophilic fluid and a decolorizing system, and preferably result in from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm of active decolorizing catalyst species in a composition comprising a lipophilic fluid and a decolorizing system.

[0099] The compositions herein may include one or more decolorization enhancing compounds. The decolorization enhancing compounds increase the effectiveness of decolorization in low temperature applications. The decolorization enhancer acts in conjunction with a conventional oxygen bleaching source to increase the effectiveness of decolorization. Typically, this is accomplished by in situ generation of an active oxygen transfer agent, such as dioxolane, oxaziridine, or oxaziridinium. Alternatively, preformed dioxolane, oxaziridine, and oxaziridinium may be used.

[0100] Cationic imines, zwitterionic imines, anionic imines, and / or polyionic imines having a net charge of from about +3 to about -3, and mixtures thereof, are included in decolorization enhancing compounds suitable for use in accordance with the present invention. These imine decolorization enhancing compounds of the present invention have the general structural formula:

[0101] [wherein,

[0102] R ~R 1 ~ may be unsubstituted or substituted radicals selected from the group consisting of hydrogen, or phenyl, aryl, heterocyclic ring, alkyl, and cycloalkyl radicals] 4 and those of which are exemplified.

[0103] ​

[0094] Zwitterionic decolorization enhancers are preferred decolorization enhancing compounds and are described in U.S. Pat. Nos. 5,576,282 and 5,718,614. Other decolorization enhancing compounds include those described in U.S. Pat. Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 5,482,515; and 5,550,256; and cationic decolorization enhancers described in WO95 / 13351, WO95 / 13352, and WO95 / 13353.

[0104]

[0095] Oxygen sources are well known in the art and the oxygen sources that may be utilized in the present invention may include any of these well-known oxygen sources, which include, in addition to oxygen source compounds, compounds that produce an effective amount of oxygen in situ under consumer use conditions. The oxygen source may include a source of hydrogen peroxide, in situ formation of peracid anions by reaction of a hydrogen peroxide source and a decolorization activator, a preformed peracid compound, or a mixture of suitable oxygen sources. Of course, those skilled in the art will recognize that other sources of oxygen may be utilized without departing from the scope of the present invention. The decolorization enhancing compound, if present, is preferably utilized with the oxygen source in the decolorizing system of the present invention.

[0105]

[0096] Preformed peracids are also suitable as decolorizing agents. The preformed peracid compound, as used herein, is any convenient compound that is stable and produces an effective amount of peracid or peracid anion under consumer use conditions. The preformed peracid compound may be selected from the group consisting of percarboxylic acids and their salts, percarbonic acids and their salts, perimidic acids and their salts, peroxymonosulfuric acid and its salts, and mixtures thereof. Examples of these compounds are described in U.S. Pat. No. 5,576,282 to Miracle et al.

[0106]

[0097] One class of suitable organic percarboxylic acids has the general formula:

[0107]

Chemical formula

[0108] [wherein, R is an alkylene or substituted alkylene group containing 1 to about 22 carbon atoms, or a phenylene or substituted phenylene group, Y is hydrogen, halogen, alkyl, aryl, -C(O)OH, or -C(O)OOH] has.

[0109] The organic peroxyacids suitable for use in the present invention can contain one or two peroxy groups and can be aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula:

[0110]

Chemical formula

[0111] [wherein, Y can be, for example, H, CH3, CH2Cl, C(O)OH, or C(O)OOH; n is an integer from 0 to 20] has. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

[0112]

Chemical formula

[0113] [wherein, Y can be, for example, hydrogen, alkyl, alkyl halogen, halogen, C(O)OH, or C(O)OOH] has.

[0114]

[0098] Typical monoperoxyacids useful here include alkyl and aryl peroxyacids, for example, (i) Peroxybenzoic acid and ring-substituted peroxybenzoic acids, such as peroxy-α-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o-carboxybenzamide peroxyhexanoic acid (sodium salt); (ii) Aliphatic, substituted aliphatic, and arylalkyl monoperoxy acids, such as peroxy lauric acid, peroxy stearic acid, N-nonanoyl aminoperoxycaproic acid (NAPCA), N,N-(3-octylsuccinoyl) aminoperoxycaproic acid (SAPA), and N,N-phthaloyl aminoperoxycaproic acid (PAP); (iii) Amide peroxy acids, such as the monononylamide of peroxysuccinic acid (NAPSA) or peroxyadipic acid (NAPAA) may be mentioned.

[0115]

[0099] Typical diperoxy acids useful here include alkyl diperoxy acids and aryl diperoxy acids, such as (i) 1,12-diperoxydodecanedioic acid; (ii) 1,9-diperoxyazelaic acid; (iii) Diperoxybrucic acid; diperoxysebacic acid, and diperoxyisophthalic acid; (iv) 2-decyldiperoxybutane-1,4-dioic acid; (v) 4,4’-sulfonylbisperoxybenzoic acid may be mentioned.

[0116]

[0100] Such bleaching agents are disclosed in Hartman U.S. Patent No. 4,483,781 and Burns et al. No. 4,634,551; Banks et al. European Patent Application No. 0,133,354; and Chung et al. U.S. Patent No. 4,412,934. The source also includes 6-nonylamino-6-oxoperoxycaproic acid as described in Burns et al. U.S. Patent No. 4,634,551. Persulfate compounds, such as OXONE manufactured and commercially available by E.I. DuPont de Nemours of Wilmington, DE, can also be utilized as a suitable source of peroxymonosulfuric acid. PAP is disclosed, for example, in U.S. Patent Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757, and 5,132,431.

[0117]

[0101] Photobleaches may also be suitable for use in the compositions of the present invention and include, but are not limited to, those described in U.S. Patent Nos. 4,217,105 and 5,916,481.

[0118]

[0102] An enzyme system may be used as a bleaching agent. Also, hydrogen peroxide may be present by adding an enzyme system capable of generating hydrogen peroxide (i.e., an enzyme and its substrate). Such an enzyme system is disclosed in European Patent Application No. 91202655.6 filed on October 9, 1991.

[0119]

[0103] The compositions and methods of the present invention may utilize another bleaching system, such as ozone and chlorine dioxide, etc. Bleaching with ozone may be achieved by introducing an ozone-containing gas having an ozone content of about 20 to about 300 g / m 3 into the solution in contact with the hair. The gas:liquid ratio in the solution should be maintained at 1:2.5 to about 1:6. U.S. Patent No. 5,346,588 describes a method for utilizing ozone as an alternative to conventional bleaching systems and is hereby incorporated by reference.

[0120]

[0104] Colorant

[0105] The colorant composition of the present disclosure may optionally contain one or more colorants other than polymer colorants. These color compounds can be selected from oxidative dye precursors, direct dyes, pigments, and mixtures thereof. Oxidative dyes are generally selected from one or more oxidative bases optionally combined with one or more couplers. By way of example, the oxidative base is selected from para-phenylenediamine, bis(phenyl)alkylenediamine, para-aminophenol, ortho-aminophenol and heterocyclic bases, and addition salts thereof.

[0121] Among the paraphenylenediamines that can be mentioned are, for example, paraphenylenediamine, paratoluenediamine, 2-chloro-paraphenylenediamine, 2,3-dimethyl-paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 2,6-diethyl-paraphenylenediamine, 2,5-dimethyl-paraphenylenediamine, N,N-dimethyl-paraphenylenediamine, N,N-diethyl-paraphenylenediamine, N,N-dipropyl-paraphenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(beta-hydroxyethyl)-paraphenylenediamine, 4-N,N-bis(beta-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(beta-hydroxyethyl)amino-2-chloroaniline, 2-beta-hydroxyethyl-paraphenylenediamine, 2-methoxymethyl-paraphenylenediamine, 2-fluoro-paraphenylenediamine, 2-isopropyl-paraphenylenediamine, N-(beta-hydroxypropyl)-paraphenylenediamine, 2-hydroxymethyl-paraphenylenediamine, N,N-dimethyl-3-methyl-paraphenylenediamine, N-ethyl-N-(beta-hydroxyethyl)-paraphenylenediamine, N-(beta,gamma-dihydroxypropyl)-paraphenylenediamine, N-(4'-aminophenyl)-paraphenylenediamine, N-phenyl-paraphenylenediamine, 2-beta-hydroxyethyloxy-paraphenylenediamine, 2-beta-acetylaminoethyloxy-paraphenylenediamine, N-(beta-methoxyethyl)-paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-paraphenylenediamine, 2-beta-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4'-aminophenyl)pyrrolidine, and addition salts thereof with acids.

[0122] Among the para-phenylenediamines described above, para-phenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2-beta-hydroxyethyl-para-phenylenediamine, 2-beta-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(beta-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-beta-acetamidoethyloxy-para-phenylenediamine, and addition salts thereof with acids are particularly preferred.

[0123] Among the bis(phenyl)alkylenediamines that can be mentioned are, for example, N,N'-bis(beta-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropan-I, N,N'-bis(beta-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(beta-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine-e, 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-dioxaoctane, and addition salts thereof.

[0124] Among the para-aminophenols that can be mentioned are, for example, para-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-(beta-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, as well as its addition salts with acids. Among the ortho-aminophenols that can be mentioned are, for example, 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and its addition salts. Among the heterocyclic bases that can be mentioned are, for example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

[0125] Among the pyridine derivatives that can be mentioned are compounds such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and their addition salts. Other pyridine oxide bases useful in the present disclosure are, for example, the 3-aminopyrazolo[1,5-a]pyridine oxide base or its addition salt described in patent application FR2801308. Examples that can be mentioned are pyrazolo[1,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine, 2-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyrid-3-ylamine, (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine, pyrazolo[1,5-a]pyridine-3,5-diamine, 5-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridine-5-ol, 3-aminopyrazolo[1,5-a]pyridine-4-ol, 3-aminopyrazolo[1,5-a]pyridine-6-ol, 3-aminopyrazolo[1,5-a]pyridine-7-ol, 2- quadrature -hydroxyethoxy-3-amino-pyrazolo[1,5-a]pyridine; 2-(4-dimethylpiperazinium-1-yl)-3-amino-pyrazolo[1,5-a]pyridine; and their addition salts.

[0126] More specifically, from

[0111] , the oxidation bases useful in the present disclosure are selected from 3-aminopyrazolo-[1,5-a]-pyridine and are preferably substituted on the carbon atom in the 2-position as follows: (a) one (di)(C1-C6)(alkyl)amino group, wherein the alkyl group may be substituted with at least one of hydroxy, amino, and imidazolium groups; (b) one heterocycloalkyl group containing a 5- to 7-membered chain and 1 to 3 heteroatoms, which is potentially cationic and is potentially substituted with one or more (C1-C6-alkyl, for example, di(C1-C4)alkylpiperazinium); or (c) one (C1-C6)alkoxy, one or more hydroxy groups, for example, ω-hydroxyalkoxy, and its addition salts, and is potentially substituted therewith.

[0127] Among the pyrimidine derivatives that can be mentioned are 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, and in the case where a tautomeric equilibrium exists, there are these tautomeric forms.

[0128] Among the pyrazole derivatives that can be mentioned are compounds such as 4,5-diamino-1-methyl-pyrazole, 4,5-diamino-1-(beta-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-phenyl-pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(beta-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 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-(beta-hydroxyethyl)amino-1-methylpyrazole, and their addition salts. 4,5-diamino-1-(beta-methoxyethyl)pyrazole can also be used.

[0129]

[0112] Also, pyrazole derivatives that can be mentioned include diamino-N,N-dihydropyrazolopyrazolone, for example, 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-(pyrrolidin-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-di-(2-hydroxyethyl)-1,2-dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one, 4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1,2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-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. 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and / or its salt is preferably used. 4,5-diamino-1-(beta-hydroxyethyl)pyrazole and / or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and / or its salt is preferentially used as the heterocyclic base.

[0130]

[0113] The composition according to the present disclosure may optionally contain one or more couplers advantageously selected from those conventionally used for the dyeing or coloring of keratin fibers. Among these couplers, mention may in particular be made of meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene-based couplers and heterocyclic couplers, and also their addition salts. For example, 2-methyl-5-aminophenol, 5-N-(beta-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-methyl-benzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(beta-hydroxyethyloxy)benzene, 2-amino-4-(beta-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diamino-phenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylamino-benzene, sesamol, 1-beta-hydroxyethylamino-3,4-methylenedioxybenzene, alpha-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(beta-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(J-hydroxyethylamino)toluene, 6-hydroxy-indoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethyl-pyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole and 6-methylpyrazolo[1,5-a]benzimidazole, its addition salts with acids, and mixtures thereof may be mentioned.

[0131]

[0114] Generally, the oxidation-based addition salts and couplers that can be used in the context of the present disclosure are addition salts with acids, for example, hydrochloride, hydrobromide, sulfate, citrate, succinate, tartrate, lactate, tosylate, benzenesulfonate, phosphate and acetate, and are particularly selected therefrom. Each of the oxidation-based(s) preferably corresponds to 0.001% to 10% by weight, preferably 0.005% to 5% by weight, based on the total weight of the composition. Each of the coupler(s), when present, preferably corresponds to 0.001% to 10% by weight, preferably 0.005% to 5% by weight, based on the total weight of the composition of the present disclosure.

[0132]

[0115] The composition according to the present disclosure can 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) No 1223 / 2009 of the European Parliament and of the Council. Examples of suitable direct dyes that may be mentioned are azo direct dyes, alone or as a mixture; (poly)methine dyes such as cyanine, hemicyanine and styryl; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes, and natural direct dyes. Many direct dyes are cationic direct dyes. Hydrazonocational dyes, azocational dyes, and diazocational dyes can be mentioned. Specific examples include Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof: Among others, natural direct dyes that can be used according to the present disclosure include lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechuic aldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or infusions containing these natural dyes, in particular henna-based compresses, or extracts can also be used. If present, the direct dye(s) more specifically correspond to from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight of the total weight of the composition of the present disclosure.

[0133]

[0116] Alkalizing agent

[0117] The hair care composition 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 can be in the range of about 7, 8, or 9 to about 9, 10, 11 or 12. The alkalinity of the hair coloring composition can be derived from one or more alkalizing agents. In some embodiments, the alkalizing agent can be a compound that generates ammonia or ammonia gas and / or an amine or ammonium-based compound in an amount sufficient to make such a composition alkaline. In a further embodiment, the alkalizing agent may be selected from alkanolamines such as monoethanolamine (MEA) and isopropanolamine. The alkalinity may be derived from an ammonium compound (e.g., NH4OH). One or more alkalizing agents can be present in an amount greater than about 0, or 1, 2, 3, 4, 5, 10 to about 5, 10, 13, 15, 18, 20, 25 or 30 wt% of the total composition.

[0134]

[0118] The hair care composition may be in the form of a surfactant cream, aqueous solution, homogeneous dispersion, or suspension, or even in liquid form. Such a composition is phase stable as much as is acceptable and typically has a viscosity in the range 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 the present invention, the viscosity is measured using a Brookfield LVDV-II+ viscometer apparatus at room temperature, 1 rpm, using the corresponding cup and spindle.

[0135]

[0119] The hair care composition of the present invention contains at least one poly(alkyleneoxy)-substituted chromophore colorant. The term "poly(alkyleneoxy)-substituted chromophore colorant" generally refers to a colorant having at least one chromophore moiety attached to at least one oligomeric or polymeric poly(alkyleneoxy) chain, and this chain has at least two repeating units, preferably at least three repeating units. The oligomeric or polymeric substituent can be attached to the chromophore moiety via any suitable means, such as covalent bonding, ionic bonding, or suitable electrostatic interactions. Generally, the polymeric colorant can be characterized by having an absorbance in the range of about 300 nanometers to about 900 nanometers when measured by UV-vis spectroscopy. In one aspect of the present invention, the polymeric colorant has a maximum absorbance in the range of 400 nanometers to 700 nanometers.

[0136]

[0120] As a function of the manufacturing method, the polymeric colorant has a molecular weight typically represented as a molecular weight distribution. Thus, the molecular weight of the polymeric colorant is generally reported as the average molecular weight determined by its molecular weight distribution.

[0137]

[0121] The chromophore moiety of the polymeric colorant can vary widely and can include compounds characterized as dyes or pigments in the art. The actual groups used depend significantly, for example, on the desired color, color fastness, and stability characteristics. The chromophore moiety may be attached to at least one polyalkyleneoxy substituent via a suitable linking moiety such as nitrogen, oxygen, sulfur, etc.

[0138]

[0122] In one aspect, the polymeric colorant may be a neutral or uncharged molecule. In a further aspect, the polymeric colorant may be nonionic, anionic, or cationic. The polymeric colorant may contain chromophore groups having both positive and negative charges. Further, the polymeric colorant may be a zwitterion or ampholyte.

[0139]

[0123] Examples of chromophores include nitroso, nitro, azo (including monoazo, bisazo, trisazo, tetrakisazo, and polyazo), formazan, azomethine and its metal complexes, stilbene, bis-stilbene, biphenyl, oligophenylene, fluorene, coumarin, naphthalamide, diarylmethane, triarylmethane, xanthene, acridine, quinoline, methine (including polymethine), thiazole, indamine, indophenol, azine, thiazine, oxazine, aminoketone, hydroxyketone, anthraquinone (including anthrapyrazoline, anthrone, anthrapyridone, anthrapyridine, flavanthrone, pyranthrone, benzanthrone, perylene, perinone, naphthalimide and other structures formally related to anthraquinone), indigoid (including thioindigoid), phthalocyanine chromophore groups, and mixtures thereof. In one aspect of the invention, the polymeric colorant is an azopolymeric colorant.

[0140]

[0124] An example of a suitable polymer chain is a polyalkyleneoxy chain. The term "polyalkyleneoxy" 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.

[0141]

[0125] Typical of such groups that can be bonded to the chromophore group are polymeric epoxide groups, such as polyalkylene oxide groups and their copolymer groups. Typical polyalkylene oxides and their copolymers that can be used to obtain colorants include those made from alkylene oxide monomers containing 2 to 20 carbon atoms, or more preferably, 2 to 6 carbon atoms. Examples include polyethylene oxide; polypropylene oxide; polybutylene oxide; oxetane; tetrahydrofuran; copolymers of polyethylene oxide, polypropylene oxide, and polybutylene oxide; and other copolymers including block copolymers in which most of the polymer substituents are polyethylene oxide, polypropylene oxide, and / or polybutylene oxide. Further, such polyalkyleneoxy groups may have an average molecular weight in the range of about 132 to about 10,000, preferably about 176 to about 5000.

[0142]

[0126] Since the colorant may or may not be chemically bonded to the raw material components including the hair care composition, it should be understood that the exact chemical identification information of the end groups of the polyalkyleneoxy group cannot be critical as long as the proper function of the colorant in the composition is considered. Taking this into account, certain most preferred colorants with certain end groups specified are defined. The listing of such end groups is in no way to be construed as limiting the present invention in its broader aspects. According to such most preferred embodiments, the colorant may be characterized by: R{A[(alkylene oxide component) n R1] m} x [wherein, R is an organic chromophore group, A is a linking chemical bond (including single, double, and triple bonds) or moiety in the organic chromophore group independently selected from the group consisting of -N=, -O-, -SO2-, -SO2N=, or -CO2-, the alkylene moiety of the alkyleneoxy component contains 2 to about 4 carbon atoms, n is an integer independently selected from 0 to about 230, and on the other hand, at least one n is 2 or more. When A is -O-, -SO2-, -CO2-, m is 1, when A is -N= and -SO2N=, m is 1 or 2, x is an integer from 1 to 5, the sum of all n values is 2 to about 230, R1 is hydrogen, an alkyl group and

[0143]

Chemical formula

[0144] independently selected from the group consisting of

[0127] , R2 is H, an alkyl radical containing up to about 20 carbon atoms, or a carboxy-terminal alkyl radical containing up to about 20 carbon atoms, j and k are OH, OM or OR3, M is the cationic moiety of an alkali metal, alkaline earth metal, transition metal such as nickel, etc., or ammonium, R3 is an alkyl radical containing up to about 20 carbon atoms, and R4 is selected from -CH2-, -CH2CH2-, CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2CH3)-, CH2CH2CH(CH3)-, CH2CH(OR1)(CH2)-].

[0145]

[0128] The oligomeric constituent substances include, but are not limited to, (i) at least two monomers selected from the group consisting of C2 - C 20 alkyleneoxy groups, glycidol groups, and glycidyl groups, or oligomers containing repeating units, (ii) Structure (I):

[0146]

Chemical formula

[0147] An oligomeric constituent material selected from the group consisting of an aromatic or aliphatic oligomeric ester that matches, and (iii) a combination of (i) and (ii) can be any suitable constituent material. In Structure (I), R2 and R3 are independently selected from the group consisting of hydrogen and C1-C 10 alkyl groups, f is an integer between 1 and 10 and including 1 and 10, and g is any positive integer or fraction between 1 and 20 and including 1 and 20. As will be understood by those skilled in the art, the length of the oligomeric constituent material on individual polymer colorant molecules can vary, so suitable values for g include both integers and fractions. Thus, the value for g represents the average length of the ester chain for a given sample or collection of polymer colorant molecules. In certain embodiments, the polymer colorant can include one or more oligomeric constituent materials consisting of two or more ethylene oxide monomer groups.

[0148]

[0129] The polymer colorant may be alkoxylated. Alkoxylation is carried out by procedures well known to those skilled in the art (see, for example, USPN 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).

[0149]

[0130] As exemplary polymer colorants, there are Liquitint® polymer colorants, Cleartint® polymer liquid concentrate colorants, Reactint® polymer colorants, and Palmer® polymer colorants, all of which are available from Milliken Chemical, a division of Milliken & Company of Spartanburg, SC. The Liquitint® polymer colorants are characterized as water-soluble, non-staining colorants. Polymer colorants are widely used in laundry detergents, fabric softeners, and other consumer and industrial cleaning products. The Liquitint® polymer colorants are generally bright liquid colorants, but exhibit different degrees of water solubility depending on the specific colorant. These colorants are generally compatible with other chemicals present in these end-use formulations and can typically be characterized by being easy to handle. The Liquitint® polymer colorants can be used to color both aqueous and solid systems. The Liquitint® polymer colorants provide a weaker stain to skin, fabrics, hard surfaces, devices, etc. due to their unique polymeric nature.

[0150]

[0131] Reactint® polymer colorants are liquid polymer colorants useful for coloring polyurethanes and other thermosetting resins. These colorants are reactive polymer colorants consisting of chromophores chemically bonded to polyols. This arrangement allows the polymer colorant to react to become part of the polyurethane polymer matrix. Unlike pigment paste agents which are dispersions of solid particles in a liquid, Reactint® polymer colorants are 100% homogeneous liquids soluble in polyols and do not settle over time. Due to this pure liquid and easily dispersible nature, it is possible to blend Reactint® colorants in-line and on-the-fly while producing polyurethane foams and resins.

[0151]

[0132] Palmer (registered trademark) polymer colorants are liquid colorants specially developed for washable applications, such as markers, paints, and other technical products. These colorants are free of heavy metals, non-toxic, and have excellent non-staining properties on skin, fabrics, and other surfaces. Palmer (registered trademark) polymer colorants have very good compatibility with aqueous ink formulations and provide bright colors.

[0152]

[0133] In one aspect of the present invention, the chromophore has the structure:

[0153]

Chem.

[0154] [wherein AR1 and AR2 are independently selected from the group consisting of alkenyl groups, substituted alkenyl groups, aryl groups, substituted aryl groups, heteroaryl groups, and substituted heteroaryl groups; and one of the AR1 or AR2 groups can be further substituted with another azo chromophore to form bisazo]. In one aspect, the substituted heteroaryl group is a substituted thiazolium group.

[0155]

[0134] In another aspect of the present invention, the chromophore has the structure:

[0156]

Chem.

[0157] [wherein e and f are independently integers from 0 to 4; each R 20 and R 21 are halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, and substituted heteroaryl group, -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, independently selected from the group consisting of; M is a cation; R5 and R6 are independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group].

[0158]

[0135] In another aspect of the present invention, the chromophore is

[0159]

Chemical formula

[0160] [wherein h, i, and j are independently integers from 0 to 4; provided that in Structure IIIa, h is an integer from 0 to 2. Y 31 is =O, =S, =NR 34 , and =N + R 34 R 35 selected from the group consisting of; R 30 is -O - , -S - , -OR 36 and -NR 36 R 37 selected from the group consisting of. Each R 34 , R 35、 R 36 and R 37 is independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaryl group, a substituted heteroaryl group, an acyl group, -C(O)OR5, -C(O)R5, and -C(O)NR5R6. Each R 31、 R 32 and R 33 groups are halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, and substituted heteroaryl group, -S(O)2OH, -S(O)2O - [M +is independently selected from the group consisting of -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, and R5 and R6 are independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. X 30 , X 31 , X 32 , and X 33 is independently selected from the group consisting of a carbon atom and a nitrogen atom, provided that no more than two of X 30 , X 31 , X 32 , and X 33 are nitrogen atoms]. It has a structure selected from

[0161]

[0136] In another aspect of the present invention, the chromophore has the structure:

[0162]

Chemical formula

[0163] [wherein X 42 is selected from the group consisting of an oxygen atom, a sulfur atom, SiR 45 R 46 , and NR 45 . Y 41 is selected from the group consisting of =O, =S, =NR 46 , and =N + R 45 R 46 . R 45 and R 46 are selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaryl group, a substituted heteroaryl group, -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 42is independently selected from the group consisting of halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, and substituted heteroaryl group, -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)2R 5、 -SR5, -S(O)2NR5R6, and -P(O)2R5; M is a cation; at least one R 42 group is selected from the group consisting of -OR5, -SR5 and -NR5R6. R5 and R6 are independently selected from the group consisting of hydrogen, alkyl group, substituted alkyl group, aryl group, and substituted aryl group.]

[0164]

[0137] In another aspect of the present invention, the chromophore has the structure:

[0165]

Chemical formula

[0166] [wherein, AR 51 is selected from the group consisting of alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, and substituted heteroaryl group; R 52 R 53 and R 54 are independently selected from the group consisting of hydrogen and R 51 . Each R 51 is halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, and substituted heteroaryl group, -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, independently selected, M is a cation, provided that R 51 is not hydrogen; R5 and R6 are independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, and c is an integer from 1 to 10. X 50 , X 51 , X 52 , and X 53 are independently selected from the group consisting of a carbon atom and a nitrogen atom, provided that no more than two of X 50 , X 51 , X 52 , and X 53 are nitrogen atoms; g is an integer from 1 to 4]; Structure V can exist in an ionic form that maintains electrical neutrality by accompanying its counterion.

[0167]

[0138] In another aspect of the present invention, the chromophore has the structure:

[0168]

Chemical formula

[0169] [wherein each R 61 , R 62 , R 63 , and R 64 group is independently selected halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, -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; n, o, p, and q are integers independently selected from 0 to 4. R5 and R6 are independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Q is hydrogen, a metal ion, or a metalloid; A is an anion. x is a positive integer and y is an integer including zero, such that the divalent group -Q x A y - is neutral].

[0170]

[0139] In another aspect of the present invention, the chromophore has the structure:

[0171]

Chemical formula

[0172] [wherein each R 71 , R 72 and R 73 groups are independently selected from hydrogen, halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, -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; n, o, p, and q are integers independently selected from 0 to 4. R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, alkyl group, substituted alkyl group, aryl group, and substituted aryl group, provided that at least one R 72 group is an -OR5 or -NR5R6 group].

[0173]

[0140] In another aspect of the present invention, the chromophore is

[0174]

Chemical formula

[0175] [wherein, X1 and X2 are selected from the group consisting of a carbon atom and a nitrogen atom; a is an integer of 0 to 5, provided that when one of X1 and X2 is a nitrogen atom, a is an integer of 0 to 4, and when both X1 and X2 are nitrogen atoms, a is an integer of 0 to 3; each R1 is independently selected from the group consisting of a halogen, a hydroxy group, a nitro group, a nitrile group, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group, -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 the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group; R2 and R3 are selected from the group consisting of an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group; Y1 is selected from the group consisting of =O, =S, =NR5, and =N + R5R6; and the structure VIII and VIIIa can exist in an ionic form that maintains electrical neutrality by accompanying its counterion.

[0176]

[0141] In another aspect of the present invention, the chromophore has the structure:

[0177]

Chemical formula

[0178] [In the formula, AR 11 is selected from the group consisting of an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group; R 11 and R 14 are independently selected from the group consisting of hydrogen, halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, -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 the group consisting of hydrogen, alkyl group, substituted alkyl group, aryl group, and substituted aryl group; b is an integer from 1 to 10].

[0179]

[0142] In one aspect of the present invention, the colorant has the following structure:

[0180]

Chemical formula

[0181] [In the formula, each R a11 ~R a110 group is independently selected from the group consisting of hydrogen, deuterium, and R v ; each R v is halogen, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, -(CH2) n -O-R x 、-(CH2) n -NR x R y 、-C(O)R x 、-C(O)OR x 、-C(O)O - 、-C(O)NRx 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 R z 、 -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, and is independently selected from the group consisting of; the subscript n is an integer from 0 to 4; R x 、 R y and R z are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, and R u ; R u is an organic group composed of one or more organic monomers having the monomer molecular weight in the range of 28 to 500]. In another aspect of the present invention, R a11 、 R a12 、 and at least one of R a13 is 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 Ry 、 -S(O)2R x 、 -S(O)2OR x 、 -P(O)2R x 、 and -P(O)(OR x )2 groups are electron-withdrawing groups selected from. Further, in a further aspect, R a11 and R a13 groups are -CN groups, and R a12 is a methyl group. In another aspect of the present invention, R a16、 R a17、 R a18、 R a19 、R a110 is independently selected from hydrogen, halogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, 2-butyl group, tert-butyl group, -(CH2) n -O-R x 、-(CH2) n -NR x R y 、-OR x 、and -NR x R y is independently selected from, and at least one of R a16、 R a17、 R a18、 R a19 、R a110 is -OR x 、or -NR x R y 。In a further aspect, in formula I-A, two or more of R a16、 R a17、 R a18、 R a19 ]>[]ID=66]]、R a110 are linked to each other via a covalent bond to form a ring structure fused to the benzene ring. In another aspect, the ring structure fused to the benzene ring in formula I-A is one of naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, indoline, and isoindoline. In another aspect, the ring structure is substituted with one or more R a16 groups. In yet another aspect, R x 、R y 、or R zTwo of them are bonded to the same carbon or nitrogen group to form a ring structure. In a further aspect, the ring structure is one of piperazine, piperidine, and pyrrolidine. In another aspect, the ring structure is further substituted with one or more R a16 groups.

[0182]

[0143] In one aspect of the present invention, the colorant is a thiophene azo colorant having the following structure:

[0183]

Chemical formula

[0184] [wherein each x and y is independently an integer from 0 to 20].

[0185]

[0144] It is also contemplated that other colorants capable of forming the colorant portion of the hair care composition in combination with the polymeric colorant are also within the scope of the present invention. For example, colorants selected from one or more of the following classes may be suitable: acid dyes, basic dyes, direct dyes, solvent dyes, mordant dyes, vat dyes, reactive dyes, disperse dyes, sulfur dyes, fluorescent dyes; pigments, both organic and inorganic; natural colorants, etc. Thus, the colorant of the hair care composition may be composed of a blend or mixture of a polymeric colorant and a non-polymeric colorant. The polymeric colorant and the non-polymeric colorant may have the same chromophore group, or they may have different chromophore groups.

[0186]

[0145] The hair care composition of the present invention is prepared by combining at least one hair care raw material component with at least one polymeric colorant. The hair care composition thus formed can be a substantially homogeneous mixture.

[0187]

[0146] The method for preparing the hair care composition of the present invention consists of the following steps: (a) preparing at least one hair care raw material component; (b) preparing at least one polymeric colorant; and (c) At least one hair care raw material component and at least one polymeric colorant are combined to form a polymeric colorant-containing hair care composition.

[0188]

[0147] A method for applying color to hair according to the present invention comprises the following steps: (a) Preparing a polymeric colorant-containing hair care composition; (b) Applying the polymeric colorant-containing hair care composition to the hair; (c) Contacting the polymeric colorant-containing hair care composition with the hair for a period of time; and (d) Optionally, removing the polymeric colorant-containing hair care composition from the hair.

[0189]

[0148] A method for decolorizing hair and applying a color component according to the present invention comprises the following steps: (a) Preparing a polymeric colorant-containing hair care composition, wherein the composition further contains an oxidizing agent; (b) Applying the composition to the hair; (c) Contacting the composition with the hair for a period of time; and (d) Optionally, removing the composition from the hair.

[0190]

[0149] The hair care composition can be contacted with the hair for a period in the range of 10 seconds to 1 hour, or in the range of 30 seconds to 45 minutes, or in the range of 1 minute to 30 minutes, or in the range of 3 minutes to 15 minutes. The hair may be wetted with water before application of the hair care composition, or the hair may be dry at the time when the hair care composition is applied to the hair.

[0191]

[0150] The hair care composition can be permanent (e.g., 80% of the original color intensity remains visible after 20 washing cycles), semi-permanent (e.g., 80% of the original color intensity is visible up to 20 washing cycles and then becomes invisible), or temporary (e.g., 80% of the original color intensity is visible up to 5 washing cycles and then becomes invisible). The permanence of the hair color on the hair can depend on the specific polymeric colorant contained in the composition and / or the amount of the polymeric colorant contained in the composition. For example, increasing the amount of the polymeric colorant in the hair care composition can result in the color on the hair lasting longer. In contrast, a lower amount of the polymeric colorant contained in the composition can result in the color lasting for a shorter time on the hair. Also, the amount of time the hair care composition remains in contact with the hair during the coloring process can affect the amount of color, the depth of the color and / or shade, and the permanence of the hair color on the hair. For example, leaving the composition on the hair for a longer period during the hair coloring process can result in a deeper shade and / or color and a color that lasts longer on the hair.

[0192]

[0151] In one aspect of the present invention, the amount of the polymeric colorant in the hair cream ranges from 0.0001% to 10% or from 0.1% to 5%.

[0193]

[0152] In one aspect of the present invention, the molecular weight of the polymeric colorant in the hair cream ranges from 100 to 10,000 Daltons or from 200 to 5,000 Daltons or from 300 to 2,000 Daltons.

[0194]

[0153] At least one polymeric colorant described herein can be added to a hair care composition for use in coloring hair. As a result, the present invention also encompasses hair (or keratin-containing materials) containing at least one polymeric colorant. The present invention is a method for bleaching and / or coloring hair (or keratin-containing materials), comprising the steps of preparing the hair, applying and / or depositing the hair care composition described herein on the hair, contacting the composition with the hair for a period of time, and further agitating, rinsing, and / or drying the hair thus treated.

[0195]

[0154] For application in non-oxidative systems, typically a single component is present, which is often a cream agent containing the hair care raw material components previously listed and color components mixed together (but not limited to this). When the single-component cream agent is applied to the hair, the color components are deposited directly onto the hair. Then, when the colored cream agent is rinsed off, the colorant remains on the hair.

[0196]

[0155] For application in oxidative systems, typically two components are present. One component contains an oxidizing species (e.g., hydrogen peroxide). The second component contains other species, typically other species designed to raise the pH, but also contains other oxidizing species, e.g., persulfates. In one aspect of the present invention, the two components are mixed together before application to the hair. The initial application contains the polymeric colorant in the hydrogen peroxide cream agent rather than in the second component. However, it is conceivable to put the polymeric colorant in the second component instead.

[0197] Thus, in one aspect, at least one polymeric colorant is mixed into a cream containing an oxidizing agent. Immediately prior to use, the polymeric colorant / hydrogen peroxide-containing cream is mixed with at least one other component to raise the pH by an amount sufficient to activate the hydrogen peroxide. In an alternative aspect, the polymeric colorant may be added to a second component. In this case, the second component is added immediately prior to use to a non-colored hydrogen peroxide cream.

[0198] The present invention as described herein is primarily directed to hair care compositions containing polymeric colorants, but the invention is not so limited to only these compositions. The compositions may contain a combination of a polymeric colorant and another colorant. Other colorants include, for example, dyes, pigments, and combinations thereof.

[0199]

[0158] Suitable dyes include small molecule dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling within the Color Index (C.I.) 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 are those selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers 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 83, 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; small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers 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 are included.

[0200] Suitable pigments include pigments selected from the group consisting of flavanthrone, indanthrone, indanthrone chloride containing 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide (the imide group may be unsubstituted or substituted with a C1-C3-alkyl or phenyl or heterocyclic radical, and the phenyl and heterocyclic radical may further carry a substituent that does not impart water solubility), anthrapyrimidinecarboxylic acid amide, violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyanine which may contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromochloro-copper phthalocyanine containing up to 14 bromine atoms per molecule, and mixtures thereof.

[0201]

[0160] In one aspect of the present invention, the components of the hair care composition can be prepared by combining the components in any convenient order and mixing the resulting combination of components, for example, by stirring, to form a phase-stable semi-liquid (i.e., cream) composition. In another method for preparing such a composition, a liquid matrix containing at least a major proportion of the liquid components, preferably substantially all of the liquid components, is formed, and the liquid components are sufficiently miscible by applying shear stirring to this combination of liquids. For example, rapid agitation using a mechanical stirrer can be effectively utilized. While the shear stirring is maintained, substantially all of any solid form of the raw material components can be added. The agitation of the mixture is continued, and if necessary, the agitation of the mixture can be intensified at this point to form a solution or a homogeneous dispersion with insoluble solid phase microparticles in the liquid phase. As a variant of the composition preparation procedure described so far, one or more of the solid components may be added to a stirred mixture that is a solution or slurry of particles pre-mixed with one or more minor portions of the liquid components. After all of the composition components have been added, the agitation of the mixture is continued for a time sufficient to form a composition having the required viscosity and phase stability characteristics. In many cases, this involves agitation for about 30 to 60 minutes.

[0202]

[0161] The hair care composition of the present invention can be combined with other molecules, compounds, and / or agents useful for applying the composition to the hair and / or enhancing color performance. Other molecules, compounds, and / or agents include, for example, surfactants, solvents, preservatives, antimicrobial agents, antibacterial agents, perfumes, etc., and combinations thereof.

[0203]

[0162] The hair care composition of the present invention may also contain any number of additional optional raw material components. These include conventional hair coloring composition components, such as skin softening oils, surfactants (which may include nonionic, anionic, cationic, zwitterionic, betaine surfactants), polar solvents, chelating agents, pH adjusters, conditioning agents, and other raw material components. The various optional hair cream composition raw material components, when present in the composition here, should be utilized at concentrations normally used to provide their desirable contributions to the composition and / or the coloring treatment. In many cases, the total amount of such optional hair cream composition raw material components can range from about 0.01% to about 50% by weight of the composition, more preferably from about 0.1% to about 30% by weight.

[0204]

[0163] Example

[0164] The following polymer colorants were prepared and evaluated in various different hair care compositions:

[0165]

[0205]

Table 1-1

[0206]

Table 1-2

[0207]

Table 1-3

[0208]

Table 1-4

[0209]

Table 1-5

[0210]

Table 1-6

[0211]

[0166] All of the above colorants can color hair as shown in the following various application examples. Since these materials are polymeric, there is a distribution around the average number of repeating units; for the materials listed in the above table, the average value of the repeating units is listed.

[0212]

[0167] To prepare a hair care composition containing a polymeric colorant, the polymeric colorant may be mixed with a hair color component, or the colorant may be added to a hair care composition that has already been prepared. For example, the following hair care compositions according to the present invention can be prepared:

[0168] Hair cream preparations 1 to 3

[0169]

[0213]

Table 2

[0214]

[0170] The hair care composition can be prepared by putting water in a beaker attached to a homogenizer mill and heating it to 70 - 75°C. Then, turn on the switch of the homogenizer mill and sprinkle beegum into the beaker. Grind the mixture for 15 minutes. While maintaining the temperature, add ethoxydiglycol, disodium EDTA, erythorbic acid, and methylparaben to the mixture and grind this for about another 15 minutes. In a separate beaker, combine aminomethylpropanol, monoethanolamine, and water, and then add this mixture to the mixture of the other raw material components. Transfer the batch to a turbine / sweep kettle.

[0215] Separately, combine the oil raw material components - oleic acid, cetearyl alcohol, emulsifying wax, oleth-20, oleyl alcohol, and steareth-21 - and heat to 70 - 75°C. Then, combine the oil phase with the other raw material components and mix well while maintaining the temperature at 70 - 75°C. Cool the batch to 35 - 40°C. Add the fragrance oil and color component and mix the composition for an additional 15 minutes. Cool the batch to 25°C.

[0216] Alternatively, the hair care composition according to the present invention can also be prepared by mixing an example of the above polymer colorant with a commercially available hair care composition. These hair care compositions may include a semi-permanent hair coloring cream. Examples of such 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 include After Color Treatment Shampoo (Fanola), Tresemme Pro Pure Micellar Moisture Shampoo (Unilever), Pantene Nutrient Blends Illuminating Color Care Shampoo (P&G), BC Bonacure pH 4.5 Color Freeze Micellar Rich Shampoo (Schwarzkopf), Free & Clear Shampoo for Sensitive Skin (Pharmaceutical Specialties, Inc.), EverPure Blonde Shampoo (L’Oreal), and Schauma 7 Herbs Shampoo (Schwarzkopf). These hair care compositions may also include conditioners, deep conditioners, and conditioning masks. Examples of such 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), Schauma 7 Herbs Conditioner (Schwarzkopf).These hair care compositions may also include various leave-on products, such as leave-on conditioners, hair sprays, mousses, gels, waxes, and the like.

[0217] The polymeric colorants were also evaluated by the following procedure: The polymeric colorant was added to the hair care composition. Each sample was mixed using a SpeedMixer at 1500 rpm and this was continued until a visually homogeneous mixture was obtained (SpeedMixer Inc., Landrum, SC). The colored hair care composition was transferred to a large weighing dish having a hair sample. A specific amount of the mixture was spread over the entire hair and worked into the hair with the fingertips until the mixture was completely and uniformly incorporated throughout the hair. The amount varied based on the type of hair care composition and was specified in each example. The colored hair care composition was left on the hair for a specified amount of time and then the hair sample was thoroughly rinsed with warm water, combed with a comb, and dried in an oven at 60 °C for 45 minutes. The amount of time varied based on the type of hair care composition and was specified in each example. The color of the hair was measured using an X-Rite Color i7 having a 6 mm aperture. The result of each measurement was the L * 、a * 、b * value on a D-65, 10° observer basis. While taking the measurement, the hair was firmly twisted and pushed into the aperture. The average of 6 - 8 measurements was used. The main means of comparing the samples or evaluating the amount of color component deposited on the hair was ΔE calculated as described below, and the yellowness index (YI) calculated as per ASTM Method E313.

[0218]

[0173] Method for calculating ΔE:

[0174] ΔE was used to indicate the efficiency of the polymeric colorant when dyeing hair. L * 、a * 、b * values were taken from the hair before and after coloring. L * 、a * 、b * 、ΔL * 、Δa * 、Δb* The change was calculated and converted to a ΔE value using the following equation:

[0219]

Number

[0220] A higher ΔE value means that there was a greater change in the hair color before and after dyeing, and thus, it is a more efficient hair coloring agent.

[0221]

[0175] Application Example 1

[0176] The polymeric colorant of the present invention was evaluated as a semi-permanent hair colorant by coloring a blond hair sample (blond bleached from dark black). Blond human hair samples are commonly used to evaluate coloring by stylists and are available from many different retailers. The hair care composition in this example was a non-colored semi-permanent hair coloring cream agent, Igora ColorWorx Dilutor (Schwarzkopf). For each colorant, the amount of color in the cream agent was adjusted so that each sample showed the same color intensity. This meant that the amount or absorbance of the chromophore in each cream agent was the same despite different polymer chain lengths. When measured at a path length of 1 cm and a concentration of 1 gram / liter in methanol, the maximum absorbance of the colored cream agent was 0.1. The amount of cream agent used was 1 gram of cream agent per 1 gram of hair. The cream agent was allowed to contact the hair for 20 minutes before rinsing off. To evaluate the amount of color component deposited on yak hair, the ΔE value for the colored hair versus the non-colored hair was used. The results are shown in Table 3. The exemplary compounds from Table 1 not evaluated in Table 3 were evaluated in other tests.

[0222]

[0177]

[0223]

Table 3

[0224]

[0178] Application Example 2

[0179] From Table 3, the polymer chain length appears to affect the deposition onto bleached hair (for example, compare Examples 6 vs. 7, 12 vs. 13, 18 vs. 20, 28 vs. 29). The shorter the polymer length, the more likely it is to result in higher deposition. To further study this effect on different substrates from bleached hair, three different colorants with the same chromophore but different polymer lengths were tested on yak belly hair. The hair care composition in this example was a non-colored semi-permanent hair coloring cream agent, Igora ColorWorx Dilutor (Schwarzkopf). By adjusting the amount of the color component in the cream agent, each sample was made to exhibit the same color intensity. This meant that the amount or absorbance of the chromophore in each cream agent was the same despite the different polymer chain lengths. Similar to Application Example 1, when measured at a path length of 1 cm and a concentration of 1 gram / liter in methanol, the maximum absorbance of the colored cream agent was 0.1. For this experiment, yak belly hair was used as the hair substrate, and the hair was colored using the above procedure. The amount of the cream agent used was 2 grams of the cream agent per 1 gram of hair. The cream agent was allowed to contact the hair for 20 minutes and then rinsed off. To evaluate the amount of the color component deposited on the yak hair, the ΔE value for the colored hair versus the non-colored hair was used. The results are shown in Table 4. The amount of the deposited color component decreased as the polymer chain length increased. As the number of EO units increased, the deposition amount tended to decrease. The results indicate that 5 to 6 EO units are optimal.

[0225]

[0180]

[0226]

Table 4

[0227]

[0181] Application Example 3

[0182] The polymer colorant of the present invention was compared with currently commercially available hair dyes by coloring blond hair (blond decolorized from dark black). A red colorant (Example 16) was added at 1.5% by weight to the Igora ColorWorx diluent cream agent and compared with the current product Igora ColorWorx Red cream agent containing the dyes 4-hydroxypropylamino-3-nitrophenol and 3-nitro-p-hydroxyethylaminophenol. A yellow colorant (Example 35) was similarly added at 1.5% by weight to the Igora ColorWorx diluent cream agent and compared with the current product Igora ColorWorx Yellow cream agent containing the dyes HC Yellow No. 13 and HC Yellow No. 2.

[0228]

[0183] Each colored cream agent was deposited on the hair as outlined above. The amount of cream agent used was 2 grams of cream agent per 1 gram of hair. The cream agent was allowed to contact the hair for 20 minutes and then rinsed off. Then, the L * a * b * color of the hair was measured as outlined above. Then, the hair was washed using Schauma 7 Herbs Shampoo (Schwarzkopf) and dried using a hair dryer using the following procedure. The hair was thoroughly wetted using 40°C tap water. Then, shampoo (0.2 grams of shampoo per 1 gram of hair) was added to the hair and worked in using the fingers for 30 seconds. The hair and shampoo were left standing in a petri dish for another 30 seconds and then rinsed for 30 seconds using 40°C tap water. Then, the hair sample was dried using a hair dryer. The hair was washed and dried twice, and then its L * a * b *The color was measured. Subsequently, the hair was washed and dried two more times, and then measured again. To evaluate the amount of color components deposited on the hair and the amount of color components retained on the hair after each series of washings, the ΔE value for the colored hair relative to the non-colored hair in any particular washing state was used. The ΔE value of the washed hair was divided by the ΔE value of the unwashed, initially deposited hair color component to evaluate the hair color components retained after 2 and 4 washings. A higher value indicates better retention of the hair color component during washing, and a value of 100% means no color loss.

[0229]

[0184] The polymeric colorants showed excellent washing performance compared to the comparative dyes (Igora Red and Igora Yellow). The red polymeric colorant showed that substantially more color components remained after 4 washings than Igora Red. The absolute ΔE number of the polymeric colorant was approximately twice that of the dye product, and the retained color components were approximately 85% compared to only 48% for the dye. The yellow polymeric colorant showed an even greater improvement compared to the yellow dye product. The color components retained for the yellow polymeric colorant were 78% compared to only 37% for the yellow dye.

[0230]

[0185]

[0231]

Table 5

[0232]

[0186] The test results show that reducing the size of the polymer increases deposition, so this behavior exemplified in Table 5 is unexpected. Thus, it would be expected that a dye with virtually zero polymer length would be superior to a polymeric colorant. However, without being bound by theory, the polymer prevents any aggregation of the colorant, so polymeric colorants are thought to exhibit better washing performance compared to dyes, which is very common in dyes (especially in cream formulations that are generally lipophilic as commonly used in hair coloring). Since polymeric colorants do not aggregate and are completely dispersed in the cream formulation, it is believed that polymeric colorants can coat hair fibers more uniformly than dyes that are likely to aggregate. This more uniformly coated hair fiber demonstrated less color loss during washing compared to dyes. This is because the coating of hair fibers with aggregated dyes is less uniform.

[0233]

[0187] Application Example 4

[0188] Polymeric colorants can be widely used in a variety of different hair coloring formulations, such as conventional hair dyes. This was demonstrated by using a single polymeric colorant (Example 10), mixing 0.16% by weight of this into several different commercially available non - coloring semi - permanent hair coloring cream formulations, and applying this to bleached blonde hair. The amount of cream formulation used was 1 gram of cream per 1 gram of hair. The cream formulation was allowed to contact the hair for 20 minutes and then rinsed off. The amount of color component deposited on the hair was evaluated by measuring ΔE of the colored hair relative to the non - colored hair, and this is shown in Table 6.

[0234]

[0189] Four different cream agents were evaluated, and the raw material components in each cream agent were different. Igora ColorWorx Dilutor (Schwarzkopf) contained tap water, cetearyl alcohol, PEG-8-coconut alcohol, ceteareth-20, disodium cocoamphodiacetate, methylparaben, xanthan gum, sulfuric acid, sodium silicate, propylparaben-ethidronic acid, and ethanolamine. Colorista Clear Mixer (L'Oreal) contained tap water, cetearyl alcohol, behentrimonium chloride, amodimethicone, cetyl alcohol, C12-15 alkyl benzoate, isopropyl alcohol, hydroxyethyl-cellulose, trideceth-6, guar hydroxypropyltrimonium chloride, chlorhexidine digluconate, stearyl alcohol, myristyl alcohol, citric acid, cetrimonium chloride, 2-oleamid-1,3-octadecanediol, fumaric acid, and sodium hydroxide. Color Charm Paints Clear (Wella) contained tap water, cetearyl alcohol, propylene glycol, steareth-20, phenoxyethanol, parfum / fragrance, potassium phosphate, hexyl cinnamal, sodium hydroxide, and citric acid. Color Fresh Create Tomorrow Clear (Wella) contained tap water, cetearyl alcohol, propylene glycol, steareth-20, phenoxyethanol, mica, potassium phosphate, titanium dioxide / C177891, sodium hydroxide, and citric acid. The polymeric colorants are extremely effective in all the evaluated cream agents, and these materials demonstrate that they are effective in a wide range of different formulations each having a wide variety of raw material components.

[0235]

[0190]

[0236]

Table 6

[0237]

[0191] Application Example 5

[0192] Hair coloring is often performed using specially designed hair coloring cream agents, but it is also desirable to color or tone hair using other hair care compositions. Shampoo is a commonly used hair care composition that can also be used to deposit color components onto the hair. Hair can be colored in a shampoo formulation using various polymeric colorants. The hair care composition in this example was a shampoo, BC Bonacure pH4.5 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. This meant that the amount or absorbance of the chromophore in each shampoo was the same, despite the different polymer chain lengths and types of chromophores. When measured at a path length of 1 cm and a concentration of 1 gram / liter in methanol, the maximum absorbance of the colored shampoo was 0.25. For this experiment, bleached blonde hair was used as the hair substrate, and the hair was colored using the above procedure. The amount of shampoo used was 0.2 grams of shampoo per gram of hair. The shampoo was allowed to contact the hair for 3 minutes and then rinsed off. To evaluate the amount of color component deposited on the hair, the ΔE value of the hair after shampooing relative to the hair before shampooing was used.

[0238] In addition, the yellowness index (YI) was calculated for hair samples before and after shampooing, and the change in YI (ΔYI) due to the shampoo treatment was calculated. When lightening dark-colored hair, there is preferential destruction of certain melanin pigments, which results in an undesirable warm orange / yellow or "brassy" tone in the lightened hair. The main use of dyes in shampoos is to dull this warm tone to a cooler or more white tone. By evaluating the ΔYI of the hair, the desired effect of toning or dulling the unwanted warm tone can be observed. The greater the reduction in YI, the less yellow or brassy the hair appears. In other words, the more negative the ΔYI of the shampoo treatment, the better the colorant covers the unwanted yellow tone.

[0239] In addition to the polymeric colorants evaluated for the shampoo, commercially available dyes commonly used in shampoos were also included in the comparative samples. External D&C Violet 2 (also known as Acid Violet 43) was formulated to be equal to the polymeric colorant in terms of absorbance per gram of shampoo. Additional mixing and time were required to fully disperse the powdered dye in the shampoo. The results are shown in Table 7. The polymeric colorants exhibit various deposition performances as judged by ΔE. Unexpectedly, some polymeric colorants show greater deposition onto the hair during shampooing than the commonly used dye, Ext. D&C Violet 2. When the shade of the polymeric colorant is appropriate for dulling the yellow tone of the hair (e.g., Examples 10 and 11), the ΔYI is more negative than that of the comparative dye, meaning that these polymeric colorants are more effective at dulling the yellow tone. Some colorants, e.g., Example 30, are not the desired shade for dulling the yellow tone in lightened hair but can be used for other colorings, e.g., yellow, red, pink, etc.

[0240]

[0195]

[0241]

Table 7

[0242]

[0196] Application Example 6

[0197] It is known that shampoo containing a dye cannot be used daily to tone hair that has been decolorized with the shampoo. This is because the dye tends to continuously deposit or increase throughout each washing cycle. Therefore, as the colorant continues to increase, the hair is desirably toned from yellow and inadvertently progresses to purple or blue. Since the physical properties of the polymeric colorant are different from those of the dye, the polymeric colorant can exhibit better leveling behavior, in which case it increases to a certain level depending on the filling amount and then the increase stops. This makes it possible to safely use the shampoo daily and obtain the desired level of toning without unwanted overtoning of the hair or purple / blue shading occurring. A polymeric colorant (Example 10) was incorporated into the shampoo, and the hair was repeatedly washed and dried in multiple cycles. Ext.D&C Violet 2 was used to prepare a comparative shampoo, and the same experiment was conducted using this shampoo.

[0243]

[0198] The shampoo for this example 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 showed the same color intensity. When measured at a path length of 1 cm and a concentration of 1 gram / liter in methanol, the maximum absorbance of the colored shampoo was 0.043. This is a level of colorant loading similar to that of many commercially available toning shampoos. De-colored blonde hair was used as the hair substrate. The amount of shampoo used was 0.2 grams of shampoo per 1 gram of hair. The shampoo was allowed to contact the hair for 3 minutes and then rinsed off. To evaluate the amount of color components deposited on the hair in each wash, the ΔE value of the hair after each shampoo wash relative to the hair before each shampoo wash was used. The results are shown in Table 8. As before, the polymeric colorant deposits more in the first wash than the dye. Both the dye and the polymeric colorant show lower deposition in the second and third washes than in the first wash. Surprisingly, the polymeric colorant shows deposition that decreases with increasing number of washes after the third wash, showing leveling. On the other hand, the dye shows a constant amount of deposition even after the third wash, indicating continued increase of the dye on the hair. In this case, the polymeric colorant shows a desirable behavior: strong initial deposition followed by rapid leveling. This allows the consumer to safely continue using the shampoo after just one or two washes, observing an obvious effect later and not having to worry too much about excessive toning or unwanted coloring in purple or blue.

[0244]

[0199]

[0245]

Table 8

[0246]

[0200] Application Example 7

[0201] Using many different shampoo formulations, polymer colorants can be delivered onto the hair. This was demonstrated by mixing a single polymer colorant (Example 2) at 0.65% by weight into several different commercially available shampoo formulations, which were then applied to bleached blond hair. The amount of shampoo used was 0.2 grams of shampoo per gram of hair. The shampoo was allowed to contact the hair for 3 minutes and then rinsed out. The amount of color component deposited on the hair was evaluated by measuring ΔE of the washed hair compared to unwashed, non-colored hair. This is shown in Table 9.

[0247]

[0202] Seven different shampoos were evaluated, and the raw material components in each shampoo were different. Free&Clear Shampoo for Sensitive Skin (Pharmaceutical Specialties, Inc.) contains purified water, lauryl glucoside, coco-glucoside, acrylate copolymer, disodium coco-glutamate, sodium cocoyl glycinate, glycerin, sucrose cocoate, panthenol, pentylene glycol, 1,2 - hexanediol, sodium coco-glutamate, disodium EDTA, caprylyl glycol, sodium hydroxide, and sodium chloride. After Color Treatment Shampoo (Fanola) contains tap water (water), ammonium lauryl sulfate, sodium myreth sulfate, sodium cocoamphoacetate, sodium chloride, glycol distearate, sodium lauryl sulfate, perfume (fragrance), cocoamid MEA, citric acid, guar hydroxypropyltrimonium chloride, laureth - 10, hydrolyzed wheat protein, triethylene glycol, benzyl alcohol, propylene glycol, tocopheryl acetate, sodium benzoate, phenoxyethanol, methylchloroisothiazolinone methylisothiazolinone, flax (Linum Usitatissimum) seed oil (flaxseed oil), magnesium nitrate, and magnesium chloride. Tresemme Pro Pure Micellar Moisture Shampoo (Unilever) contains water (tap water), cocoamidopropyl betaine, methyl cocoyl taurate sodium, sodium chloride, fragrance (perfume), sodium benzoate, citric acid, coconut acid, polyquaternium - 10, stearamidopropyldimethylamine, disodium EDTA, PPG - 9, benzyl salicylate, hexyl cinnamal, limonene, and linalool.Schauma 7 Herbs Shampoo (Schwarzkopf) contains tap water, sodium lauryl sulfate, sodium chloride, cocoamidopropyl betaine, hydrolyzed soybean protein, niacinamide, magnesium chloride, chamomile (Chamomilla Recutita) flower extract, sage (Salvia Officinalis) leaf extract, lemon balm (Melissa Officinalis) leaf extract, stinging nettle (Urtica Dioica) extract, horsetail (Equisetum Arvense) extract, rosemary (Rosmarinus Officinalis) leaf extract, hops (Humulus Lupulus) extract, jojoba (Simmondsia Chinensis) seed oil, disodium cocoamphodiacetate, coconut fatty acid PEG-7 glyceryl, sodium benzoate, cocoamid MEA, citric acid, glycol distearate, perfume, laureth-4, hydrogenated castor oil, PEG-40 hydrogenated castor oil, polyquaternium-10, linalool, benzyl alcohol, propylene glycol, hexyl cinnamal, CI 47005, CI 42090. Pantene Nutrient Blends Illuminating Color Care Shampoo (P&G) contains water, lauramidopropyl betaine, sodium cocoyl isethionate, sodium lauroyl sarcosinate, sodium citrate, citric acid, fragrance, sodium benzoate, sodium salicylate, polyquaternium-10, dimethiconol, EDTA tetrasodium, panthenol, pantothenyl ethyl ether, histidine, biotin.BC Bonacure pH 4.5 Color Freeze Micellar Rich Shampoo (Schwarzkopf) contains water, sodium lauryl sulfate, lactic acid, cocoamidopropyl betaine, cocoamide MEA, hydrolyzed keratin, steardimonium hydroxypropyl hydrolyzed keratin, Prunus Armeniaca (apricot) kernel oil, panthenol, PEG-12 dimethicone, disodium cocoamphodiacetate, PEG-7 glyceryl cocoate, polyquaternium-10, calcium hydroxide, sodium benzoate, sodium chloride, parfum (fragrance), glycol distearate, PEG-40 hydrogenated castor oil, laureth-4, hydrogenated castor oil, PEG-120 methyl glucose dioleate, PEG-12 allyl ether, benzophenone-4, PEG-12, mica, benzyl salicylate, butylphenyl methylpropional, linalool, limonene, propylene glycol, calcium carbonate, CI77891 (titanium dioxide), CI17200 (Red 33).EverPure Blonde Shampoo (L’Oreal) contains tap water / water / water, coco-betaine, disodium laureth sulfosuccinate, sodium cocoyl isethionate, sodium lauryl sulfoacetate, sodium lauroyl sarcosinate, diglycol distearate, sodium chloride, decyl glucoside, perfume / fragrance, polyquaternium-10, amodimethicone, PPG-5-ceteth-20, propylene glycol, PEG-55 propylene glycol oleate, hydrogenated coconut acid, carbomer, sodium hydroxide, acrylate / beheneth-25 methacrylate copolymer, benzophenone-4, sodium isethionate, butylene glycol, benzoic acid, trideceth-6, linalool, hydroxycitronellal, sodium acetate, cetrimonium chloride, sodium benzoate, isopropyl alcohol, Iris Florentina root extract, Calendula Officinalis flower extract, methylchloroisothiazolinone, CI60730 / EXT, Violet 2, magnesium chloride, methylisothiazolinone, CI17200 / Red 33, and citric acid.

[0248]

[0203] Polymer colorants showed deposition in all shampoos evaluated, demonstrating that these materials function in a wide range of different formulations, each having a diverse range of raw material components. Shampoos have a variety of different surfactants, including some that do not contain sulfates or betaines and various other additives such as cationic additives, silicones, etc. There is some variation in performance across the different formulations, but the relative changes are generally small.

[0249]

[0204]

[0250]

Table 9

[0251]

[0205] Application Example 8

[0206] It is also desirable to color or tone the hair using other hair care compositions. Conditioners are commonly used in hair care compositions that can also be used to deposit color components onto the hair. Various polymeric colorants can be used to color the hair in a conditioner formulation. The hair care composition in this example was a 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. This meant that the amount or absorbance of the chromophore in each conditioner was the same, despite the different polymer chain lengths and types of chromophores. The maximum absorbance of the colored conditioner was 0.25 when measured at a path length of 1 cm and a concentration of 1 gram / liter in methanol. For this experiment, bleached blonde hair was used as the hair substrate, and the hair was colored using the above procedure. The amount of conditioner used was 0.2 grams of conditioner per gram of hair. The conditioner was allowed to contact the hair for 3 minutes and then rinsed off. To evaluate the amount of color component deposited on the hair, the ΔE value for the conditioned hair relative to the unconditioned hair was used.

[0252] In addition, the yellowness index (YI) before and after conditioning was calculated as described above. In addition to the polymeric colorants evaluated against the conditioner, commercially available dyes commonly used in conditioners were also included in the comparative samples. External D&C Violet 2 (also known as Acid Violet 43) was formulated to be equal to the polymeric colorant in terms of absorbance per gram of conditioner. The results are shown in Table 10. Unexpectedly, all of the polymeric colorants evaluated showed greater deposition on the hair than the commonly used dye, Ext. D&C Violet 2, in the conditioner. The ΔYI was also more negative than the comparative dye, meaning that these polymeric colorants are more effective at dulling the yellow tone. Also unexpectedly, some of the polymeric colorants showed much more deposition from the conditioner than from the shampoo. Example 1 shows a 13-fold greater ΔE in the conditioner than in the shampoo (see Table 7); similarly, Example 2 shows a ΔE in the conditioner more than twice that shown in the shampoo. Due to these liquid properties, the polymeric colorants show a very good blend into the conditioner.

[0253]

[0208]

[0254]

Table 10

[0255]

[0209] Application Example 9

[0210] Using a number of different conditioner formulations, the polymeric colorant can be delivered onto the hair. This was demonstrated by mixing a single polymeric colorant (Example 1) at 1% by weight into several different commercially available conditioner formulations, which were applied to bleached blond hair. The amount of conditioner used was 0.2 grams of conditioner per gram of hair. The conditioner was left in contact with the hair for 3 minutes and then rinsed out. The amount of color component deposited onto the hair was evaluated by measuring the ΔE of the conditioned hair compared to unconditioned, non-colored hair, and this is shown in Table 11.

[0256]

[0211] Four different conditioners with different raw material components in each conditioner were evaluated. Pantene Pro-V Classic Clean Conditioner (P&G) contains water, stearyl alcohol, stearamidopropyl dimethylamine, cetyl alcohol, glutamic acid, fragrance, bis-aminopropyl dimethicone, benzyl alcohol, citric acid, disodium EDTA, histidine, panthenol, panthenyl ethyl ether, methylchloroisothiazolinone, and methylisothiazolinone. Pantene Nutrient Blends Illuminating Color Care Conditioner (P&G) contains water, stearyl alcohol, silicone quaternium-26, behentrimonium chloride, cetyl alcohol, fragrance, benzyl alcohol, disodium EDTA, panthenol, panthenyl ethyl ether, histidine, citric acid, sodium hydroxide, biotin, methylchloroisothiazolinone, and methylisothiazolinone. Nutri Care Restructuring Conditioner (Fanola) contains water, stearyl alcohol, silicone quaternium-26, behentrimonium chloride, cetyl alcohol, fragrance, benzyl alcohol, disodium EDTA, panthenol, panthenyl ethyl ether, histidine, citric acid, sodium hydroxide, biotin, methylchloroisothiazolinone, and methylisothiazolinone.EverPure Blonde Conditioner (L’Oreal) contains deionized water / water / Eau, cetearyl alcohol, glycerin, behentrimonium chloride, cetyl esters, isopropyl myristate, propylene glycol quaternium - 80, parfum / fragrance, polysorbate 20, isopropyl alcohol, phenoxyethanol, polyquaternium - 37, paraffin liquidum / mineral oil / Huile Minerale, tocopheryl acetate, butylene glycol, linalool, chlorhexidine dihydrochloride, citric acid, Ppg - 1 trideceth - 6, hexyl cinnamal, hydroxycitronellal, acrylate copolymer, sorbitan oleate, Iris Florentina root extract, Calendula Officinalis flower extract, CI60730 / EXT.Violet 2, CI17200 / Red33, BHT.

[0257]

[0212] In this case, there were some differences in performance among certain conditioners, but the polymer colorants showed strong deposition in all the evaluated conditioners. This demonstrates that these materials function in a wide range of different formulations, each having a diverse range of raw material components.

[0258]

[0213]

[0259]

Table 11

[0260]

[0214] Application Example 10

[0215] The above examples demonstrate unexpected advantages and differences with respect to polymer colorants compared to conventional hair dyes. Assuming that the colorant completely dissolves in the cream, the colorant can be expected to have low stability in certain hair care products, particularly in oxidative hair creams containing hydrogen peroxide. Surprisingly, several examples of this type of polymer colorant that were stable in an oxidative cream containing 12% hydrogen peroxide were discovered as described below.

[0261]

[0216] Several polymer colorants were tested for stability and coloring performance in a commercially available oxidative hair cream. Each sample was added to Fanola 40 Vol Perfumed Cream Developer (available from Fanola of Italy), which contained approximately 12% hydrogen peroxide. The SpeedMixer was used at 1500 rpm to mix each sample, continuing until a visually uniform mixture was obtained (minimum 90 seconds; manufactured by SpeedMixer, Inc., Landrum, SC). The amount of color contained in each sample was adjusted so that each sample exhibited the same color intensity. The maximum absorbance of the colored cream was 0.67 when measured at a 1 cm path length and a concentration of 1 gram / liter in methanol. After mixing, the samples were first stored at room temperature for 7 days and then transferred to an oven at 40 °C. Color stability was evaluated by the number of equivalent days at room temperature required to reach 50% color loss, based on the original color measured in the cream at time zero as measured by UV-VIS. Color loss is fading due to chemical changes from the oxidative cream raw material components containing peroxide. Many of these colorants evaluated were stable in the oxidative emulsion as shown in Table 13 below.

[0262]

[0217] The number of equivalent days at room temperature was calculated by the following equation: Number of equivalent days at room temperature = Days stored at room temperature + Days stored at 40 °C * 3.48

[0218] The equivalent number of days at room temperature for 50% color deterioration was used to conduct the evaluation according to the following table. A value of "1" indicates that the composition is the most stable, while a value of "5" indicates that it is the least stable.

[0263]

[0219]

[0264]

Table 12

[0265]

[0220]

[0266]

Table 13

[0267]

[0221] Application Example 11

[0222] In addition to strongly coloring the hair in bright colors such as blue, red, and yellow, it is also desired to deposit a certain amount of a specific color that is not very prominent in a controllable manner in order to dull the spectrum of the undertone exposed during the hair bleaching or lightening process. For bright brown hair, for example, a yellow undertone will be exposed during bleaching. Therefore, according to the color law, a purple-based toner dulls the yellowish hue, resulting in a platinum or silver blonde shade. The concentration of the toner can also be adjusted so that the lift is not masked by the color deposition. According to the present invention, there is a single-step method using a composition of a hair bleaching agent that can simultaneously lighten the hair and effectively deposit various color shades. This is achieved by including a dye in the bleaching agent composition. As demonstrated above, some blue and purple polymer colorants exhibit good stability in oxidative cream agents. Therefore, a purple colorant can be premixed in an oxidative hair cream, and then while depositing a colorant that dulls the unwanted yellow tone, the hair can be lightened simultaneously. This is demonstrated below.

[0268]

[0223] Material: Blonde hair (lightly bleached dark-colored hair) was cut into strips 3 cm wide and 20 cm long. Fanola Violet Bleach Powder Fanola 40 Vol. (12% peroxide) oxidizing cream developer

[0224] Procedure:

[0225] The hair was first weighed and the amount of cream developer required was calculated (4 grams of cream developer per 1 gram of hair). The color and oxidizing cream developer were mixed as described above. The mixture was checked and remixing was done if necessary to ensure that the color was completely homogeneous. Fanola Violet Bleach Powder (available from Fanola of Italy) was placed in a small weighing dish and weighed (2 parts cream developer and 1 part bleach powder). An appropriate amount of oxidizing cream developer was added to the bleach powder. The wooden end of a cotton swab was used to stir the bleach / cream developer until completely mixed. The bleach / cream developer mixture was transferred to a large weighing dish with the hair sample. The mixture was spread over the entire hair and worked into the hair with fingertips until the mixture was completely and evenly incorporated throughout the hair. The bleach was left on the hair for 15 minutes, then the hair sample was thoroughly rinsed with lukewarm water, combed with a comb, and dried in an oven at 60 °C for 45 minutes. The color of the hair was measured using an X-Rite Color-eye with a 6 mm aperture and D-65 light source. While measuring, the hair was firmly twisted and pushed into the aperture. An average of 6 - 8 measurements were used.

[0269]

[0226] As described previously, the yellowness index (YI) was calculated for each sample. YI is a good measure of how well the hair has been lightened and toned. The initial hair had a whiteness index (YI) of -48.9 due to its yellow color. After treatment, the YI value decreased, indicating that the hair had been lightened. The difference in YI, ΔYI, between the treated hair and the initial hair was recorded. The larger and more negative it is, the better the lightening of the hair is indicated by ΔYI.

[0270]

[0227] The YI and ΔYI values of the initial hair, the depilatory control (without dye), and the depilatory compositions containing External D&C Violet 2 of Example 1 and Comparative Example are shown in Table 14. The depilatory composition using Example 1 provided better brightening than the depilatory control and the depilatory using Comparative Example External D&C Violet 2.

[0271]

[0228]

[0272]

Table 14

[0273]

[0229] All references, including publications, patent applications, and patents cited herein, are hereby incorporated by reference to the extent that each reference is individually and specifically indicated to be incorporated by reference and is as fully described herein as if set forth in its entirety.

[0274] The use of the terms "a", "an", and "the", and similar designations in the context of describing the subject matter of this application (especially in the context of the following claims) are to be construed to include both the singular and the plural forms unless otherwise indicated herein or clearly contradicted by the context. The terms "comprising", "having", "including", and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to") unless otherwise noted. Here, references to ranges of values are intended only to function as a concise way of referring individually to each separate value falling within the range, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by the context. Any examples, or exemplary language presented herein (e.g., "such as") are intended only to clarify the subject matter of this application and do not raise limitations on the scope of the subject matter unless otherwise claimed. No language in this specification should be construed as indicating that any non-claimed element is essential to the practice of the subject matter described herein.

[0275] Preferred embodiments of the subject matter of this application are described herein, including the best mode known to the inventors for carrying out the claimed subject matter. Variations of those preferred embodiments will be apparent to those skilled in the art upon reading the foregoing description. The inventors expect skilled artisans to appropriately utilize such variations, and the inventors intend for the subject matter recited herein to be practiced in a manner different from that specifically described herein. Accordingly, this disclosure includes all modifications and equivalent forms of the subject matter recited in the claims appended hereto as permitted by applicable law. Further, unless otherwise indicated herein or otherwise clearly contradicted by context, all combinations of the above-described elements in all possible variations thereof are included in this disclosure.

Claims

1. A method for coloring human hair or facial hair, comprising the following steps: (a) preparing a hair care composition containing at least one poly(alkyleneoxy)-substituted chromophore colorant; (b) applying the hair care composition to the hair; (c) contacting the hair care composition with the hair for a period of time A method comprising:

2. The method according to claim 1, wherein the hair care composition further contains at least one hair care raw material component.

3. The method according to claim 1, further comprising removing the hair care composition from the hair.

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

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

6. The method according to claim 1, wherein the poly(alkyleneoxy) substitution group of the chromophore colorant is a polymeric group composed of alkylene oxide residues having 2 to 4 carbon atoms.

7. The method according to claim 1, wherein the average molecular weight of the poly(alkyleneoxy) substitution group is 132 to 10,000.

8. The method according to claim 1, wherein the chromophore of the colorant is selected from azo, carbazole, pyrazolone, cyanine, phthalocyanine, anthraquinone, aza[18]annulene, copper formazan complex, nitroso, nitro, diarylmethane, triarylmethane, xanthene, acridine, methine, thiazole, indamine, azine, oxazine, thiazine, quinoline, indigoid, indophenol, lactone, aminoketone, hydroxyketone, naphthalimide, and stilbene chromophores.

9. The chromophore has the structure: 【Chemical 1】 [wherein, AR １ and AR ２ are each independently selected from the group consisting of an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group; said AR １ or AR ２ group is optionally further substituted with another azo chromophore to form a bisazo] The method according to claim 8, having

10. The method according to claim 9, wherein the substituted heteroaryl group is a substituted thiazolium group.

11. The colorant has the following structure: 【Chemical 2】 [In the formula, each R ａ１１ ~R ａ１１０ group is independently selected from the group consisting of hydrogen, deuterium and R ｖ ; each R ｖ is halogen, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, -(CH ２ ) ｎ -O-R ｘ , -(CH ２ ) 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) ２ R ｘ , -S(O) ２ OR ｘ , -S(O) ２ O － , -S(O) ２ , -S(O) ｘ NR 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 R ｚ , -OR ｘ , -NR ｘ R ｙ , -P(O) ２ R ｘ , -P(O)(OR ｘ ) ２ , -P(O)(OR ｘ )O － , and -P(O)(O － ) ２ is independently selected from the group consisting of; the subscript n is an integer from 0 to 4, R ｘ , R ｙ and R ｚ is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, and R ｕ is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, and R ｕ is an organic group composed of one or more organic monomers having the monomer molecular weight in the range of 28 to 500], the method according to claim 8.

12. Said R ａ１１ , R ａ１２ , and R ａ１３ wherein at least one of them is 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) ２ R ｘ , -S(O) ２ OR ｘ , -P(O) ２ R ｘ 、 and -P(O)(OR ｘ ) ２ a method according to claim 11, which is an electron-withdrawing group selected from the group consisting of

13. said R ａ１１ and R ａ１３ groups are -CN groups, and R ａ１２ is a methyl group, the method according to claim 12.

14. R ａ１６、 R ａ１７、 R ａ１８、 R ａ１９ 、 R ａ１１０ is independently selected from hydrogen, halogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, 2-butyl group, tert-butyl group, -(CH ２ ) ｎ -O-R ｘ 、-(CH ２ ) ｎ -NR ｘ R ｙ 、-OR ｘ 、 and -NR ｘ R ｙ is selected independently, and at least one of R ａ１６、 R ａ１７、 R ａ１８、 R ａ１９ 、 R ａ１１０ is -OR ｘ 、 or -NR ｘ R ｙ , the method according to claim 13.

15. R ａ１６、 R ａ１７、 R ａ１８、 R ａ１９ 、 R ａ１１０ The method according to claim 13, wherein two or more of them are linked to each other via a covalent bond to form a ring structure condensed with the benzene ring of formula I.

16. The method according to claim 15, wherein the ring structure condensed to the benzene ring of formula I is one of naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, indoline, and isoindoline.

17. wherein the ring structure is substituted with one or more R ａ１６ groups, the method according to claim 16.

18. R ｘ 、R ｙ 、 or R ｚ wherein two of them are bonded to the same carbon or nitrogen group to form the ring structure, the method according to claim 14.

19. The method according to claim 18, wherein the ring structure is one of piperazine, piperidine, and pyrrolidine.

20. wherein the ring structure is further substituted with one or more R ａ１６ groups, the method according to claim 19.

21. The colorant is the following structure: [Chemical Formula 3] The method according to claim 14, wherein the colorant is a thiophene azo colorant represented by [wherein each x and y is independently an integer from 0 to 20].

22. The chromophore is the structure: [Chemical Formula 4] [wherein, e and f are each independently an integer of 0 to 4, and each R ２０ and R ２１ is independently selected from the group consisting of halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, and substituted heteroaryl group, -S(O) ２ OH, -S(O) ２ O － [M ＋ , -C(O)OR ５ , -C(O)R ５ , -C(O)NR ５ R ６ , -NR ５ C(O)OR ６ , -NR ５ C(O)SR ６ , -OR ５ , -NR ５ R ６ , -S(O) ２ R ５ , -S(O) ２ NR ５ R ６ , and -P(O) ２ R ５ ; M is a cation; R ５ and R ６ are each independently selected from the group consisting of hydrogen, alkyl group, substituted alkyl group, aryl group, and substituted aryl group], the method according to claim 8.

23. The chromophore is 【Chemical Formula 5】 [Wherein, h, i, and j are each independently an integer from 0 to 4; provided that in Structure IIIa, h is an integer from 0 to 2; Y ３１ is =O, =S, =NR ３４ , and =N ＋ R ３４ R ３５ selected from the group consisting of; R ３０ is -O － , -S － , -OR ３６ and -NR ３６ R ３７ selected from the group consisting of; each R ３４ , R ３５、 R ３６ and R ３７ is independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaryl group, a substituted heteroaryl group, an acyl group, -C(O)OR ５ , -C(O)R ５ , and -C(O)NR ５ R ６ selected from the group consisting of; each R ３１、 R ３２ and R ３３ groups are halogen, a hydroxy group, a nitro group, a nitrile group, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group, -S(O) ２ OH, -S(O) ２ O － [M ＋ , -C(O)OR ５ , -C(O)R ５ , -C(O)NR ５ R ６ , -NR ５ C(O)OR ６ , -NR ５ C(O)SR ６ , -OR ５ , -NR ５ R ６ , -S(O) ２ R ５ , -S(O) ２ NR ５ R ６ , and -P(O) ２ R ５ independently selected from the group consisting of; M is a cation; R ５ and R ６ are independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group; X ３０ , X ３１ , X ３２ , and X ３３ are independently selected from the group consisting of a carbon atom and a nitrogen atom, provided that two or less of X ３０ , X ３１ , X ３２ , and X ３３ are nitrogen atoms]; The method according to claim 8, having a structure selected from

24. The chromophore is the structure: [Chemical Formula 6] [wherein, X ４２ is selected from the group consisting of an oxygen atom, a sulfur atom, SiR ４５ R ４６ , and NR ４５ ; Y ４１ is selected from the group consisting of =O, =S, =NR ４６ , and =N ＋ R ４５ R ４６ ; R ４５ and R ４６ are each independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaryl group, a substituted heteroaryl group, -S(O) ２ OH, -S(O) ２ O － [M ＋ , -C(O)OR ５ , -C(O)R ５ , and -C(O)NR ５ R ６ ; l is an integer from 0 to 3, m is an integer from 0 to 4, and each R ４１ and R ４２ is independently selected from the group consisting of halogen, a hydroxy group, a nitro group, a nitrile group, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, a substituted heteroaryl group, -S(O) ２ OH, -S(O) ２ O － [M ＋ , -C(O)OR ５ , -C(O)R ５ , -C(O)NR ５ R ６ , -NR ５ C(O)OR ６ , -NR ５ C(O)SR ６ , -OR ５ , -NR ５ R ６ , -S(O) ２ R ５ , -SR ５ , -S(O) ２ NR ５ R ６ , and -P(O) ２ R ５ independently selected from the group consisting of; M is a cation; at least one R ４２ group is —OR ５ , —SR ５ and —NR ５ R ６ selected from the group consisting of; R ５ and R ６ are independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group]. The method according to claim 8.

25. The chromophore is the structure: 【Chemical Formula 7】 [Wherein, AR ５１ is selected from the group consisting of an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group; R ５２ , R ５３ and R ５４ are independently selected from the group consisting of hydrogen and R ５１ ; each R ５１ is halogen, a hydroxy group, a nitro group, a nitrile group, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group, -S(O) ２ OH, -S(O) ２ O － [M ＋ , -C(O)OR ５ , -C(O)R ５ , -C(O)NR ５ R ６ , -NR ５ C(O)OR ６ , -NR ５ C(O)SR ６ , -OR ５ , -NR ５ R ６ , -S(O) ２ R ５ , -S(O) ２ NR ５ R ６ , and -P(O) ２ R ５ are independently selected, M is a cation, provided that R ５１ is not hydrogen; R ５ and R ６ are independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group; c is an integer from 1 to 10; X ５０ , X ５１ , X ５２ , and X ５３ are independently selected from the group consisting of a carbon atom and a nitrogen atom, provided that X ５０ , X ５１ , X ５２ , and X ５３ two or less of which are nitrogen atoms; g is an integer from 1 to 4]; and the structure V is present in an ionic form that maintains electrical neutrality, optionally with its counterion, according to the method of claim 8.

26. The chromophore is the structure: [Chemical Formula 8] [wherein each R ６１ , R ６２ , R ６３ , and R ６４ group is independently selected from halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, -S(O) ２ OH, -S(O) ２ O － [M ＋ , -C(O)OR ５ , -C(O)R ５ , -C(O)NR ５ R ６ , -NR ５ C(O)OR ６ , -NR ５ C(O)SR ６ , -OR ５ , -NR ５ R ６ , -S(O) ２ R ５ , -S(O) ２ NR ５ R ６ , and -P(O) ２ R ５ ; M is a cation; n, o, p, and q are integers independently selected from 0 to 4; R ５ and R ６ are independently selected from the group consisting of hydrogen, alkyl group, substituted alkyl group, aryl group, and substituted aryl group; Q is hydrogen, a metal ion, or a metalloid; A is an anion; x is a positive integer; y is an integer including zero, whereby the divalent group -Q ｘ A ｙ - is neutral], the method according to claim 8.

27. The chromophore is the structure: 【Chemical Formula 9】 [wherein each R ７１ , R ７２ and R ７３ groups are independently selected from hydrogen, halogen, hydroxy, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, -S(O) ２ OH, -S(O) ２ O － [M ＋ , -C(O)OR ５ , -C(O)R ５ , -C(O)NR ５ R ６ , -NR ５ C(O)OR ６ , -NR ５ C(O)NR ６ NR ７ R ８ , -NR ５ C(O)SR ６ , -OR ５ , -NR ５ R ６ , -S(O) ２ R ５ , -S(O) ２ NR ５ R ６ , and -P(O) ２ R ５ ; M is a cation; n, o, p and q are integers independently selected from 0 to 4; R ５ , R ６ , R ７ and R ８ are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, and substituted aryl, provided that at least one R ７２ group is -OR ５ or -NR ５ R ６ group] The method according to claim 8, having.

28. The chromophore is 【Chemical Formula 10】 [wherein, X １ and X ２ are each independently selected from the group consisting of a carbon atom and a nitrogen atom; a is an integer of 0 to 5, provided that when one of X １ and X ２ is a nitrogen atom, a is an integer of 0 to 4, and when both X １ and X ２ are nitrogen atoms, a is an integer of 0 to 3; each R １ is independently selected from the group consisting of a halogen, a hydroxy group, a nitro group, a nitrile group, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group, -S(O) ２ OH, -S(O) ２ O － [M ＋ , -C(O)OR ５ , -C(O)R ５ , -C(O)NR ５ R ６ , -NR ５ C(O)OR ６ , -NR ５ C(O)SR ６ , -OR ５ , -NR ５ R ６ , -S(O) ２ R ５ , -S(O) ２ NR ５ R ６ , and -P(O) ２ R ５ ; M is a cation; R ５ and R ６ are each independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group; R ２ and R ３ are selected from the group consisting of an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group; Y １ is =O, =S, =NR ５ , and =N ＋ R ５ R ６ selected from the group consisting of]; having a structure selected from; wherein said structures VIII and VIIIa are independently and optionally present in ionic forms that maintain electrical neutrality by being accompanied by their counterions, the method according to claim 8.

29. The chromophore is the structure: 【Chemical 11】 [Wherein, AR １１ is selected from the group consisting of an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group; R １１ and R １４ are independently selected from the group consisting of hydrogen, halogen, hydroxy group, nitro group, nitrile group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, -S(O) ２ OH, -S(O) ２ O － [M ＋ , -C(O)OR ５ , -C(O)R ５ , -C(O)NR ５ R ６ , -NR ５ C(O)OR ６ , -NR ５ C(O)SR ６ , -OR ５ , -NR ５ R ６ , -S(O) ２ R ５ , -S(O) ２ NR ５ R ６ , and -P(O) ２ R ５ ; M is a cation; R ５ and R ６ are independently selected from the group consisting of hydrogen, alkyl group, substituted alkyl group, aryl group, and substituted aryl group; b is an integer from 1 to 10], the method according to claim 8.

30. The method according to claim 8, wherein at least 50 mol% of the poly(alkyleneoxy) substituted chromophore colorant has a molecular weight of less than 5000.

31. The poly(alkyleneoxy) substituted chromophore colorant contains monomer residues, and at least 75% of the monomer residues in the poly(alkyleneoxy) substituent are —CH ２ CH ２ O— and —CH ２ CH(CH ３ )O—, and the method according to claim 30.

32. The method according to claim 8, wherein at least 50 mol% of the poly(alkyleneoxy) substituted chromophore colorant has a molecular weight of less than 2000.

33. The poly(alkyleneoxy)-substituted chromophore colorant contains monomer residues, and at least 75% of the monomer residues in the poly(alkyleneoxy) substituent are —CH ２ CH ２ O—, the method according to claim 32.

34. The method according to claim 1, wherein the hair care composition is a non-oxidative hair coloring cream agent.

35. The method according to claim 34, wherein the non-oxidative hair coloring cream agent is a semi-permanent hair coloring cream agent.

36. The method according to claim 34, wherein the non-oxidative hair coloring cream agent is a temporary hair coloring cream agent.

37. The method according to claim 1, wherein the hair care composition is an oxidative hair coloring cream agent.

38. The method according to claim 37, wherein the oxidative hair coloring cream agent is a semi-permanent hair coloring cream agent.

39. The method according to claim 38, wherein the oxidative hair coloring cream agent is a permanent hair coloring cream agent.

40. The method according to claim 1, wherein the hair care composition is a shampoo.

41. The method according to claim 1, wherein the hair care composition is a conditioner.

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