Oxidative hair cream composition containing polymeric colorant

Abstract

To provide: an oxidative hair cream composition comprising at least one oxidative hair cream ingredient and at least one polymeric colorant; and a method for treating hair.SOLUTION: There is provided an oxidative hair cream composition comprising: at least one polymeric azo colorant; and at least one oxidative hair cream ingredient selected from an oxidizing agent, emollient oil, nonionic, anionic, cationic, amphoteric ion, surfactant that may contain betaine surfactant, polar solvent, chelating agent, pH adjuster, and conditioning agent. Therein the at least one polymeric azo colorant is a dye composed of a monomer according to Formula II.SELECTED DRAWING: None

Description

Technical Field

[0001]

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

[0002]

[0002] Human hair is arbitrarily assigned to scales having different levels representing its darkness (or lightness). Black hair is designated as level 1, medium brown hair as level 5, and light, bright blond as level 10, with several subtle differences in between. Hair bleaching is a chemical treatment in which melanin pigment granules are gradually destroyed by a bleaching agent, resulting in a lighter hair color. Melanin pigments are not all lightened at the same rate. Eumelanin is more easily destroyed than pheomelanin. Due to this property, when dark-colored hair is bleached, preferential destruction of melanin pigments occurs, which visually emphasizes red pigments, resulting in an undesirable, warm-colored orange or "copper-colored" tone being cast on the bleached hair. To tone down the warm color, hair colorants having a toning property are almost always applied during or after the bleaching treatment.

[0003]

[0003] Based on their chemical composition and strength, hair bleaching agents can be classified into two groups designated as Category 1 and Category 2. Category 1 bleaching agents are liquid or cream-based compositions that utilize an alkaline hydrogen peroxide solution as the main oxygen generator to oxidize and bleach hair melanin in combination with a normal hair coloring treatment. Immediately before use, the peroxide is mixed with an alkalizing agent, such as ammonia, and the resulting liquid or cream is applied to the hair for 30 to 60 minutes. Such compositions can lighten hair by up to 4 levels depending on the concentration of hydrogen peroxide used. For example, hair at level 6 can be lightened to level 10 under favorable conditions.

[0004]

[0004] The decolorization of Category 2 is generally in the form of a powder composition, and some are in the form of a cream agent, which is based on persulfate-(ammonium, potassium, sodium) as an auxiliary or booster supply of active oxygen-and silicate and / or carbonate functioning as an alkaline source. Similar to the Category 1 decolorization, these can be mixed with a hydrogen peroxide solution immediately before use to form an effective cream agent that can be applied to the hair. It is possible to incorporate hydrogen peroxide itself in solid form into the powder decolorizer, and all that is required to achieve an effective cream agent is to add water to the powder. In quite a number of cases, a separately packaged third component called decolorizing oil is added to the decolorizer powder and peroxide at the time of use. The decolorizing oil may contain moisturizers and other conditioning agents. The decolorizing agents of Category 2 can provide a lift of over 7 levels, which cannot be achieved with the decolorizing agents of Category 1. The decolorizing agents of Category 2 are usually utilized whenever a lift of over 4 levels is desired, for example, when lifting hair of level 5 or darker colors to a light blonde.

[0005]

[0005] In various levels of decolorization, since the underlying warm - color tones are exposed, toning treatment is generally associated with lightening the hair to dull the warm colors and give the hair a pleasant natural appearance. Toners are classified into three hues: blue - green, blue, and purple. These are generally known as dull or graying hues. These hues, or combinations thereof, are recommended to dull the spectrum of the undertone that is exposed during the lightening process. For example, in the case of light - brown hair, a yellow undertone will be exposed during decolorization. Thus, according to the law of colors, a purple - based toner dulls the yellow - tinged hue, resulting in a platinum or silver - blonde shade. The concentration of the toner should be adjusted so that the lift is not masked by color deposition. Similarly, for medium - brown hair, a significant amount of orange undertone is exposed, so a significant amount of blue - based toner is required. Dark - colored hair, when decolorized, shows a reddish - orange undertone, so a blue - green toner is required.

[0006]

[0006] According to the present invention, there is a single - step method using a composition of a hair - lightening agent that can simultaneously lighten the hair and effectively deposit various color shades. This is achieved by including a dye in the lightening - agent composition. Dyes suitable for this use need to (a) be easily mixed into the oxidizing composition and remain homogeneous, and (b) be stable in the lightening agent.

[0007]

[0007] However, current small - molecule dyes have weaknesses. Dyes are conjugated, rigid organic compounds, and these are often difficult to dissolve in the composition. Undissolved dyes can leave an uneven hue or sometimes color spots on the treated hair. Thus, a liquid - form colorant is much more desirable. In this aspect, polymeric, liquid colorants are superior to conventional hair dyes.

[0008]

[0008] For this use, liquid colorants are preferred, but polymeric dyes have unexpectedly been found to exhibit different and worse stability in many cases compared to these small molecule analogs. Some small molecule dyes were actually not soluble in the composition and were thus presumed to be separated from the oxidizing agent. However, when polymeric colorants were used, they were completely dissolved down to the molecular level and were thus exposed to the bleaching agent. Despite this general behavior, more surprisingly, polymeric dyes containing azo chromophores have been found to be stable in the bleaching agent and provide excellent performance in this use. Brief summary

[0009]

[0009] In one aspect, the present invention relates to an oxidative hair cream composition, wherein the composition comprises at least one polymeric azo colorant and at least one oxidative hair cream raw material component.

[0010]

[0010] In a further aspect, the present invention relates to a method for treating hair, comprising: (a) preparing an oxidative hair cream composition comprising at least one polymeric azo colorant and at least one oxidizing agent; and (b) contacting the oxidative hair cream composition with human hair.

[0011]

[0011] In yet a further aspect, the present invention relates to a method for treating hair, comprising: (a) at least one oxidizing agent and Formula V:

[0012]

Chemical formula

[0013] [wherein each R 56 , R 57 , R 58 , R 59 group is independently selected from hydrogen, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl groups; R 510 is independently selected from the group consisting of hydrogen, deuterium and R v ; each Rv is independently selected from the group consisting of halogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, -C(O)O - , -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)(OR x )O - , and -P(O)(O - ) 2 and is independently selected from the group consisting of; 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, hydroxyethyl, and R u ; R u is an organic group composed of one or more organic monomers, and the monomer molecular weight ranges from 28 to 500]. A method for preparing an oxidative hair cream composition containing at least one azo colorant; (b) contacting the oxidative hair cream composition with human hair. Detailed description

[0014]

[0012] The present invention described herein is an oxidative hair cream composition containing at least one oxidative hair cream raw material component and at least one polymer colorant. The oxidative hair cream containing a polymer colorant is suitable for direct application to hair (such as human hair, animal hair, etc.), and has improved stability and shading compared to conventional hair dyes.

[0015]

[0013] As used herein, the term "hair" is intended to include keratin fibers such as human hair, animal hair, and the like.

[0016]

[0014] When used herein, the term "alkoxy" refers to C 1 ~C 8 alkoxy and repeating units, such as alkoxy derivatives of polyols having butylene oxide, glycidol oxide, ethylene oxide, or propylene oxide, are intended to be included.

[0017]

[0015] When used herein, the terms "polyalkyleneoxy" and "polyoxyalkylene" are used interchangeably herein and generally refer to a molecular structure containing the following repeating units: -CH 2 CH 2 O-, -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 CH 2 CH 2 O-, -CH 2 CH(CH 3 )O-, -CH 2 CH 2 CH(CH 3 )O-, and any combination thereof. Further, the polyoxyalkylene constituent material may be selected from the group consisting of one or more monomers selected from C 2~20 alkyleneoxy groups, glycidol groups, glycidyl groups, or mixtures thereof.

[0018]

[0016] When used herein, unless otherwise specified, the terms "alkyl" and "alkyl-capped" refer to C 2 ~C 100 alkyl groups, C 2 ~C 50 alkyl groups, C 5 ~C 25 alkyl groups, or even C 10 ~C 20 alkyl groups are intended to be included.

[0019] As used herein, unless otherwise specified, the term "aryl" means C 5 ~C 18 aryl groups and, in one aspect, is intended to include C 5 ~C 12 alkyl groups.

[0020]

[0018] As used herein, unless otherwise specified, the term "alkyl" means C 1 ~C 18 alkyl groups and, in one aspect, is intended to include C 1 ~C 6 alkyl groups.

[0021]

[0019] As used herein, unless otherwise specified, the term "alkanoyl" means the formula -C(O)R a (wherein R a is an alkyl group, preferably C 3 ~C 29 alkyl group).

[0022]

[0020] 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.

[0023]

[0021] As used herein, unless otherwise specified, the term "alkenoyl" means the formula -C(O)R b (wherein R b is an alkenyl group, preferably C 3 ~C 29 alkenyl group).

[0024]

[0022] As used herein, unless otherwise specified, the term "aroyl" means the formula -C(O)R c (wherein R cis an aryl group, preferably a monovalent group of C 6 ~C 10 (which is an aryl group).

[0025]

[0023] The terms "ethylene oxide", "propylene oxide", and "butylene oxide" may be denoted herein by their typical names "EO", "PO", and "BO", respectively.

[0026]

[0024] 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.

[0027]

[0025] In the present invention, the oxidative hair cream composition contains at least one oxidative hair cream raw material component. Examples of the oxidative hair cream raw material component include, but are not limited to, an oxidizing agent, a skin softening oil, a surfactant (which may include a nonionic, anionic, cationic, zwitterionic, betaine surfactant), a polar solvent, a chelating agent, a pH adjuster, a conditioning agent, and other raw material components and mixtures thereof. The oxidizing agent may be selected from the group consisting of hydrogen peroxide. Hydrogen peroxide may be present in an amount in the range of 0.01% to 33% by weight of the total composition, or further in the range of 0.1% to 15% by weight of the total composition.

[0028]

[0026] The hair cream composition of the present invention is an aqueous base, generally containing about 0.01 to 99% by weight, preferably about 0.1 to 98% by weight, more preferably about 45 to 95% by weight of water of the total composition.

[0029]

[0027] Skin softening oil

[0028] 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, and mineral oil. Other common examples include cetearyl alcohol, lauryl alcohol, myristyl alcohol, lanolin alcohol, coconut alcohol, and the like.

[0030]

[0029] Surfactant

[0030] The oxidative dye composition may contain one or more surfactants. Suitable surfactants include anionic surfactants, nonionic surfactants, amphoteric surfactants, and the like. 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.

[0031]

[0031] Nonionic surfactant

[0032] 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, the number of repeating units of ethylene oxide is 2 - 30); Laureth 2 - 30 (formed by the reaction of lauryl alcohol and ethylene oxide, the number of repeating units of ethylene oxide is 2 - 30); Oleth 2 - 30 (formed by the reaction of oleyl alcohol and ethylene oxide, 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, 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, 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 an alkoxylated carboxylic acid, which is formed by the reaction of a carboxylic acid with an alkylene oxide or a polymeric ether.

[0032]

[0033] 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.

[0033]

[0034] Anionic surfactant

[0035] 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 oxidizing composition. Suitable anionic surfactants generally include alkyl sulfates and alkyl ether sulfates having the formula ROSO 3 M and RO(C 2 H 4 O) x SO 3 M (wherein R is an alkyl or alkenyl having about 10 to 20 carbon atoms, x is 1 to about 10, and M is a water-soluble cation such as ammonium, sodium, potassium, or triethanolamine cation).

[0034]

[0036] 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: R 1 -SO 3 -M (wherein R 1 is selected from the group consisting of linear or branched, saturated aliphatic hydrocarbon radicals having about 8 to about 24 carbon atoms, preferably 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 8 to 24 carbon atoms, and sulfonating agents such as sulfur trioxide.

[0035]

[0037] Also suitable as the anionic surfactant are reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, or fatty acid reaction products with 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, etc.

[0036]

[0038] In addition, succinates and succinamates are suitable anionic surfactants. This class includes compounds such as sodium dioctyl sulfosuccinate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinate; and esters of sodium sulfosuccinic acid such as dihexyl ester of sodium sulfosuccinic acid, dioctyl ester of sodium sulfosuccinic acid, etc.

[0037]

[0039] 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 does not form a complex, followed by neutralizing the acidic reaction mixture under conditions such that any sultone formed during the reaction hydrolyzes to give the corresponding hydroxy-alkanesulfonate. 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.

[0038]

[0040] Another class of suitable anionic organic surfactants is β-alkoxyalkanesulfonates 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.

[0039]

[0041] Yet another class of anionic surfactants is of the formula: (R 1 is a C 8~24 alkyl or alkenyl radical, preferably C 10~18 ; R 2 is H, C 1~4 alkyl, phenyl, or -CH 2 COOM; R 3 is CX 2 - 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) of N-acyl amino acid surfactants are included. Examples of such surfactants are N-acyl sarcosinates, including lauroyl sarcosinate, myristoyl sarcosinate, cocooyl sarcosinate, and oleoyl sarcosinate, preferably in the form of sodium or potassium.

[0040]

[0042] Cationic, zwitterionic or betaine surfactants

[0043] 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.

[0041]

[0044] 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.

[0042]

[0045] Also suitable amphoteric surfactants are monocarboxylates or dicarboxylates, such as cocoamphocarboxypropionate, cocoamphocarboxylic acid, cocoamphocarboxyglycinate, and cocoamphoacetate.

[0043]

[0046] As another type of amphoteric surfactant, aminoalkanoates of R-NH(CH 2 ) n COOM or of the formula: R-[(CH 2 ) m COOM] 2Iminoalkanates and mixtures thereof (wherein n and m are from 1 to 4 and R is C 8~22 alkyl or alkenyl and M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or an alkanolammonium) may be mentioned. Examples of such amphoteric surfactants include n-alkylaminopropionates and n-alkyliminodipropionates. Zwitterionic surfactants are also suitable for use in the compositions of the present invention and include betaines, for example, 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-carboxyethyl 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.

[0044]

[0047] Polar solvent

[0048] 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, malitol, 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.

[0045]

[0049] Chelating agent

[0050] The oxidative 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 and inactivate metal ions 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. Examples of suitable chelating agents include EDTA and its calcium, sodium, or potassium derivatives, HEDTA, sodium citrate, TEA-EDTA, and the like.

[0046]

[0051] pH adjuster

[0052] It may also be desirable to add a small amount of acid or base to adjust the pH of the oxidative dye composition to the desired pH range. Suitable acids include hydrochloric acid, phosphoric acid, etidronic acid, etc. Suitable bases include sodium hydroxide, ammonium hydroxide, potassium hydroxide, etc. Also suitable are primary, secondary, or tertiary amines or their derivatives, such as aminomethylpropanol, monoethanolamine, etc. Phosphates, such as potassium phosphate, disodium phosphate, etc. can also be used. The suggested range of the pH adjuster is about 0.00001 - 8% by weight of the total composition, preferably about 0.00005 - 6% by weight, more preferably about 0.0001 - 5% by weight.

[0047]

[0053] Conditioning agent

[0054] 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.

[0048]

[0055] Preferred conditioning agents for use herein include cationic surfactants, cationic polymers, insoluble silicone conditioning agents, amino-functionalized silicones and saturated C14 - C22 straight-chain aliphatic alcohols and mixtures thereof.

[0049]

[0056] When present, the insoluble silicone conditioning agent is present at a level of about 0.1 - 10% by weight of the composition, preferably about 0.1% by weight to about 5% by weight, more preferably about 1% by weight to about 3% by weight. Suitable insoluble silicones include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyether silicone copolymers, and mixtures thereof.

[0050]

[0057] Other additional components

[0058] 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, for example, thickeners and diluents. Further, several optional materials can be added to the compositions described herein at levels of from about 0.001 wt% to about 5 wt%, preferably from about 0.01 wt% to about 3 wt%, more preferably from about 0.05 wt% to about 2 wt% of the composition.Such materials include proteins, 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 and 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 modifiers such as magnesium sulfate and other electrolytes; quaternary amine compounds such as distearyl-, dilauryl-, dihydrogenated tallow-, dimethylammonium chloride, cetyl diethylmethyl ammonium sulfate, ditallow dimethyl methyl sulfate ammonium, distearyl dimethyl ammonium chloride and dicoco dimethyl ammonium 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., and water softeners such as sodium citrate, inorganic peroxide oxidants and enzymes are included.

[0051]

[0059] Oxidizing agent composition

[0060] In addition, the aqueous oxidation cream agent composition also contains an oxidizing agent that reacts with the hair and decolorizes it. 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.

[0052]

[0061] Additional suitable oxidizing agents (also referred to herein as "bleaching agents") include, for example, sources of hydrogen peroxide, such as those described in detail in Kirk Othmer’s Encyclopedia of Chemical Technology, 4th Edition (1992, John Wiley & Sons), Volume 4, pages 271 - 300, "Bleaching Agents (Survey)." These sources of hydrogen peroxide include various forms of sodium perborate and sodium percarbonate, including coated and modified forms of these compounds.

[0053]

[0062] 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 sources of hydrogen peroxide can also be used.

[0054]

[0063] 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").

[0055]

[0064] 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 of from about 0.01% to about 0.5% by weight, preferably from about 1% to about 15% by weight, more preferably up to about 10% by weight, and even more preferably up to about 8% by weight of the composition. The bleaching activator, as used herein, is any compound that, when used with hydrogen peroxide, results in the in situ formation of a peracid corresponding to the bleaching activator from the source. 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.

[0056]

[0065] 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 (C 8 -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.

[0057]

[0066] Preferred hydrophobic bleaching activators include nonanoyloxybenzenesulfonate (NOBS); sodium 4-[N-(nonanoyl)aminohexanoyloxy]-benzenesulfonate (NACA-OBS), an example of which 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), but are not limited thereto.

[0058]

[0067] 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 No. 08 / 064,564, all of which are hereby incorporated by reference.

[0059]

[0068] 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.

[0060]

[0069] Useful additional decolorizing agent activators here are amide-substituted as described in U.S. Patent Nos. 5,698,504; 5,695,679; and 5,686,014, each of which is cited hereinabove. Preferred examples of such decolorizing activators include (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.

[0061]

[0070] Other useful activators are disclosed in U.S. Patent Nos. 5,698,504; 5,695,679; and 5,686,014, each of which is cited hereinabove, as well as in U.S. Patent No. 4,966,723 to Hodge et al. Such activators include benzoxazine-type activators, for example, a C 1 )=N- moiety condensed at the 1,2-position with a C 6 H 4 ring.

[0062]

[0071] Nitriles, such as acetonitrile and / or ammonium nitrile and other quaternary nitrogen-containing nitriles, are another class of activators useful here. 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 in European Patent Nos. 790244, 775127, 1017773, and 1017776; and in WO99 / 14302, WO99 / 14296, and WO96 / 40661, all of which are hereby incorporated by reference.

[0063]

[0072] 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.

[0064]

[0073] 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, e.g., 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 herein.

[0065]

[0074] 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 a diacyl peroxide is used, it preferably has a minimal adverse effect on fabric care, including color care.

[0066]

[0075] The compositions and methods of the present invention can also optionally include metal-containing decolorization catalysts, preferably manganese- and cobalt-containing decolorization catalysts.

[0067]

[0076] One type of metal-containing decolorizing catalyst is a catalyst system comprising a transition metal cation having a determined decolorizing catalyst activity (for example, a copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cation), an auxiliary metal cation having little or no decolorizing catalyst activity (for example, a 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.

[0068]

[0077] 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, for example, U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606; and manganese-based catalysts disclosed in European Patent Application Publication Nos. 549,271A1; 549,272A1; 544,440A2; and 544,490A1. Preferred examples of such catalysts include Mn IV 2 (μ-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6 ) 2 、Mn III 2 (μ-O) 1 (μ-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 2 、Mn IV 4 (μ-O) 6 (1,4,7-triazacyclononane) 4 (ClO 4 ) 4 、Mn III Mn IV 4 (μ-O) 1 (μ-OAc)2 -(1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 , Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH 3 ) 3 (PF 6 ) and mixtures thereof are included. Other metal 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.

[0069]

[0078] Cobalt decolorizing catalysts useful herein are known, for example, in 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, pages 1-94. The most preferred cobalt catalysts useful herein are cobalt pentaamine acetate salts having the formula [Co(NH 3 ) 5 OAc]Ty (wherein "OAc" represents an acetate moiety and "Ty" represents an anion), especially cobalt pentaamine acetate chloride [Co(NH 3 ) 5 OAc]Cl 2 ; and [Co(NH 3 ) 5 OAc](OAc) 2 ; [Co(NH 3 ) 5 OAc](PF 6 ) 2 ; [Co(NH 3 ) 5 OAc](SO4 ); [Co(NH 3 ) 5 OAc](BF 4 ) 2 ; and [Co(NH 3 ) 5 OAc](NO 3 ) 2 (herein referred to as "PAC").

[0070]

[0079] 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; Tobe's paper and the references cited therein; and 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), pages 461 - 3; Inorg. Chem., 18, 1497 - 1502 (1979); Inorg. Chem., 21, 2881 - 2885 (1982); Inorg. Chem., 18, 2023 - 2025 (1979); Inorg. Synthesis, pages 173 - 176 (1960); and Journal of Physical Chemistry, 56, 22 - 25 (1952).

[0071]

[0080] 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 per billion by weight and "ppm" represents parts per million by weight).

[0072]

[0081] Examples of transition metal decolorization catalysts of macrocyclic rigid ligands suitable for use in the composition of the present invention include generally known compounds, and are non-limitingly 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) Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) hexafluorophosphate Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) hexafluorophosphate Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(III) hexafluorophosphate Diaquo-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)

[0082] The hair cream composition of the present invention may also contain at least one decolorizing agent. The decolorizing agent may be selected from the group consisting of a decolorizing agent of category 1, a decolorizing agent of category 2, and mixtures thereof.

[0073]

[0083] As a practical matter, and not by way of limitation, the compositions and methods herein can be adjusted to provide an active decolorizing catalyst species on the order of at least 1 part per billion in compositions containing a lipophilic fluid and a decolorizing system, preferably resulting in from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm of active decolorizing catalyst species in compositions containing a lipophilic fluid and a decolorizing system.

[0074]

[0084] 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 source of oxygen bleach to increase the effectiveness of decolorization. Typically, this is accomplished by in situ generation of an active oxygen transfer agent, such as a dioxirane, an oxaziridine, or an oxazirinium. Alternatively, preformed dioxiranes, oxaziridines, and oxaziriniums may be used.

[0075]

[0085] 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:

[0076]

Chemical formula

[0077] [wherein, R 1 ~R 4is an unsubstituted or substituted radical optionally selected from the group consisting of hydrogen, or phenyl, aryl, heterocyclic ring, alkyl, and cycloalkyl radicals] include those of.

[0078]

[0086] Zwitterionic decolorization enhancers are preferably included in the decolorization enhancing compounds, which 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.

[0079]

[0087] 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 generation of peracid anions by reaction of a hydrogen peroxide source with 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.

[0080]

[0088] Pre-formed peracids are also suitable as bleaching agents. The pre-formed peracid compounds, when used herein, are any convenient compounds that are stable and yield an effective amount of peracid or peracid anion under the conditions of use by the consumer. The pre-formed peracid compounds may be selected from the group consisting of percarboxylic acids and their salts, percarbonates 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. Patent No. 5,576,282 to Miracle et al.

[0081]

[0089] One class of suitable organic peroxycarboxylic acids has the general formula:

[0082]

Chemical formula

[0083] [wherein, R is an alkylene or substituted alkylene group containing from 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] and has.

[0084] 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:

[0085]

Chemical formula

[0086] [wherein, Y can be, for example, H, CH 3 , CH 2 Cl, C(O)OH, or C(O)OOH; n is an integer from 0 to 20] and has. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

[0087] [Chemical formula]

[0088] [wherein, Y can be, for example, hydrogen, alkyl, alkyl halogen, halogen, C(O)OH, or C(O)OOH. has

[0089]

[0090] Typical monoperoxy acids useful herein include alkyl and aryl peroxy acids, for example, (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, such as peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o-carboxybenzamide peroxyhexanoic acid (sodium salt); (ii) aliphatic, substituted aliphatic, and arylalkyl monoperoxy acids, such as peroxylauric acid, peroxystearic 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 peroxyladipic acid (NAPAA) may be mentioned.

[0090]

[0091] Typical diperoxy acids useful herein include alkyl diperoxy acids and aryl diperoxy acids, for example, (i) 1,12-diperoxydodecanedioic acid; (ii) 1,9-diperoxyazelaic acid; (iii) diperoxybrassic acid; diperoxysebacic acid, and diperoxyisophthalic acid; (iv) 2-decyldiperoxybutane-1,4-dioic acid; (v) 4,4'-sulfonylbisperoxybenzoic acid may be mentioned.

[0091]

[0092] 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.

[0092]

[0093] Photobleaching may also be suitable for use in the compositions of the present invention and includes, but is not limited to, the photobleaching described in U.S. Patent Nos. 4,217,105 and 5,916,481.

[0093]

[0094] 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.

[0094]

[0095] The compositions and methods of the present invention may utilize another bleaching system, such as ozone and chlorine dioxide. 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 a 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.

[0095]

[0096] Colorant

[0097] 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.

[0096]

[0098] 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.

[0097]

[0099] Among the above-mentioned para-phenylenediamines, para-phenylenediamine, para-tolylenediamine, 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-acetylaminoethyloxy-para-phenylenediamine, and addition salts thereof with acids are particularly preferred.

[0098]

[0100] 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.

[0099]

[0101] 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.

[0100]

[0102] 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 bases or their addition salts 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-ortho-hydroxyethoxy-3-amino-pyrazolo[1,5-a]pyridine; 2-(4-dimethylpiperazin-1-yl)-3-amino-pyrazolo[1,5-a]pyridine; and their addition salts.

[0101]

[0103] More specifically, 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-C 6 )(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-C 6 -alkyl, for example, di(C1-C4)alkylpiperazinium; or (c) one (C1-C6)alkoxy, one or more hydroxy groups, for example, ortho-hydroxyalkoxy, and its addition salts, and is potentially substituted therewith.

[0102] 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 when a tautomeric equilibrium exists, these tautomeric forms.

[0103] 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.

[0104]

[0104] 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 are 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 are preferentially used as the heterocyclic base.

[0105]

[0105] 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.

[0106]

[0106] Generally, the oxidation-based addition salts and couplers that can be used in the context of the present disclosure are addition salts with acids, such as hydrochloride, hydrobromide, sulfate, citrate, succinate, tartrate, lactate, tosylate, benzenesulfonate, phosphate and acetate, and are particularly selected therefrom. Each of the oxidation base(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.

[0107]

[0107] 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 the extracts can also be used. If present, the direct dye(s) more specifically correspond to 0.001% to 10% by weight, preferably 0.005% to 5% by weight of the total weight of the composition of the present disclosure.

[0108]

[0108] Alkalizing agent

[0109] The oxidative hair cream 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 composition can range from about 7, 8, or 9 to about 9, 10, 11, or 12. The alkalinity of the oxidative hair cream 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 can be selected from alkanolamines, such as monoethanolamine (MEA) and isopropanolamine. The alkalinity can also be derived from ammonium compounds (e.g., NH 4 OH). 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 weight % of the total composition.

[0109]

[0110] The oxidative hair cream composition can be in the form of a surfactant cream, an aqueous solution, a homogeneous dispersion, or a suspension, or even in a 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, most preferably 100 to 20,000 cps, and even more preferably 1000 to 10,000 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.

[0110]

[0111] The oxidative hair cream composition of the present invention also contains at least one polymeric colorant. The polymeric colorant may be an azopolymeric colorant. The term "polymeric colorant" generally refers to a colorant having at least one chromophore moiety attached to at least one oligomer or polymer chain, and this chain has at least two repeating units. The oligomeric or polymeric constituent substance can be attached to the chromophore via any suitable means, such as covalent bonding, ionic bonding, or suitable electrostatic interactions. Generally, the polymeric colorant can be characterized as 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 (which may be an azopolymeric colorant in one aspect) can have a maximum absorbance in the range of 400 nanometers to 700 nanometers, or in the range of 470 nanometers to 700 nanometers, or even in the range of 550 nanometers to 700 nanometers.

[0111]

[0112] 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.

[0112]

[0113] 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.

[0113]

[0114] On one side, the chromophore group may be a neutral or uncharged molecule. On a further side, the chromophore group may be nonionic, anionic, or cationic. The polymeric colorant may contain chromophores having both positive and negative charges. Further, the polymeric colorant may contain chromophores that are zwitterionic or amphoteric.

[0114]

[0115] Examples of chromophore groups include nitroso, nitro, azo (including monoazo, diazo, bis-azo, disazo, trisazo, tetrakisazo, polyazo, formazan, azomethine and metal complexes thereof), 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.

[0115]

[0116] Examples of suitable polymer chains are polyalkyleneoxy chains. The term "polyalkyleneoxy" as used herein refers to the following repeating units: -CH 2 CH 2 O-, CH 2 CH 2 CH 2 O-, -CH 2 CH 2 CH 2 CH 2 O-, -CH 2 CH(CH 3 )O-, -CH 2 CH(CH 2 CH 3 )O-CH 2 CH 2CH(CH 3 )O-, CH 2 CH(O-)(CH 2 O-), and any combination thereof, generally refers to a molecular structure containing them.

[0116]

[0117] Typical of such groups that can be attached to a chromophore group are polyalkylene oxides and their copolymers. Typical polyalkylene oxides and their copolymers that can be used to obtain a colorant 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 such as 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.

[0117]

[0118] Since the colorant may or may not be chemically bonded to the raw material components including the oxidative hair cream composition, it should be understood that the exact chemical identification information of the end groups of the polyalkyleneoxy group may not 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 specific end groups defined. The listing of such end groups is in no way to be construed as limiting the present invention in its broader aspects. In accordance with such most preferred embodiments, the colorant can be characterized as follows:

[0119] R{A[(alkylene oxide constituent material) n R 1 m} x [wherein R is an organic chromophore group and A is N, O, SO 2 or CO​2 is a linking moiety of the organic chromophore group selected from the group consisting of, the alkylene moiety of the alkyleneoxy constituent material contains 2 to about 4 carbon atoms, n is an integer from 2 to about 230, and when A is O, SO 2 , CO 2 , when m is 1, when A is N, m is 1 or 2, x is an integer from 1 to 5, and the product (n.m.x) of n times x times m is from 2 to about 230, R 1 is

[0118]

Chemical formula

[0119]

[0120] and is a member of the group consisting of sulfonates and sulfates of each member of said group, R 2 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 OR 3 , M is a cationic moiety of an alkali metal, alkaline earth metal, transition metal such as nickel etc. or ammonium, R 3 is an alkyl radical containing up to about 20 carbon atoms, R 4 is the alkylene moiety of the alkyleneoxy repeating unit].

[0120]

[0121] The oligomeric constituent material includes, but is not limited to, (i) at least two monomers selected from the group consisting of C 2 -C 20 alkyleneoxy groups, glycidol groups, and glycidyl groups, or an oligomer containing repeating units, (ii) Structure (I):

[0121]

Chemical formula

[0122] Any suitable constituent material can include an oligomeric constituent material selected from the group consisting of aromatic or aliphatic oligomeric esters that match, and (iii) combinations of (i) and (ii). In structure (I), R 2 and R 3 are independently selected from the group consisting of hydrogen and C 1 to C 10 alkyl groups, f is an integer between 1 and 10 including 1 and 10, and g is any positive integer or fraction between 1 and 20 including 1 and 20. As 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.

[0123]

[0122] The polymer colorant may be alkoxylated. In one aspect of the invention, the polymer colorant is an alkoxylated azopolymer colorant. 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).

[0124] 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 being 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 varying degrees of water solubility depending on the particular colorant. These colorants are generally compatible with other chemicals present in the formulations for these end uses and may typically be characterized by ease of handling. The Liquitint® polymer colorants can be used to impart color to both aqueous and solid systems. The Liquitint® polymer colorants provide a weaker staining to skin, fabrics, hard surfaces, devices, etc. due to their unique polymeric nature.

[0125]

[0124] Cleartint (registered trademark) polymer liquid concentrate colorants are liquid colorants specially designed for frequent use in coloring transparent polypropylene articles. These colorants can be easily incorporated into polypropylene resins without adversely affecting the transparency of the articles, providing transparent, clear, and brightly colored polypropylene articles. Cleartint (registered trademark) liquid concentrate polymer colorants are oligomeric coloring materials that combine outstanding visual beauty of dyes and migration resistance of pigments. By using these colorants as bright shades, the remaining haze can be masked, or they can be used to obtain deep, rich shades that are impossible with pigment colorants. Cleartint (registered trademark) liquid concentrate polymer colorants enable transparent polypropylene that rivals the beauty of more expensive plastic materials. The technical and physical property merits of transparent polypropylene can be utilized without sacrificing the visual beauty of the product.

[0126]

[0125] Reactint (registered trademark) 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 pastes, which are liquid dispersions of solid particles in a liquid, Reactint (registered trademark) polymer colorants are 100% homogeneous liquids that are soluble in polyols and do not settle over time. Due to this pure liquid and easy-to-disperse nature, it is possible to blend Reactint (registered trademark) colorants in-line and on-the-fly while producing polyurethane foams and resins.

[0127]

[0126] The Palmer (registered trademark) polymer colorant is a liquid colorant 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 the skin, fabrics, and other surfaces. The Palmer (registered trademark) polymer colorant has very good compatibility with aqueous ink formulations and provides bright colors.

[0128]

[0127] In one aspect of the present invention, the oxidative hair cream composition has the formula I:

[0129]

Chemical formula

[0130] [wherein each R 11 ~R 110 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 、-CR x R y R z -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 NR 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 x 、 -OR x 、 -NR x R y 、 -P(O) 2 R x 、 -P(O)(OR x ) 2 、 -P(O)(OR x )O - 、および -P(O)(O - ) 2 independently selected from the group consisting of; the subscript n is an integer from 0 to 4, preferably an integer from 0 to 1, most preferably an integer of 0, and preferably at least one of R 11 、R 12 、およびR 13 is an electron-withdrawing group selected from halogen, nitro, nitrile, nitroso, -C(O)R x 、 -C(O)OR x 、 -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 、および -P(O)(OR x ) 2 ; preferably R 16、 R 17、 R 18、 R 19 、R 110 is independently 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 selected from, where at least one of R 16、 R 17、 R 18、 R 19 、R 110 is -OR x 、or -NR x R y . It contains a polymeric azo colorant according to []. 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 a monomer molecular weight in the range of 28 to 500, preferably 43 to 350, and even more preferably 43 to 250. R 16、 R 17、 R 18、 R 19 、R 110 Among them, two or more can be linked to each other via a covalent bond to form a ring structure. In combination with a benzene ring, this ring can form a structure including, but not limited to, naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, indoline, isoindoline. This ring structure may be further substituted with one or more R 16 groups. R x 、R y 、or R z If two of them are bonded to the same carbon or nitrogen atom, they can also be connected to form a ring structure. Exemplary ring structures include, but are not limited to, piperazine, piperidine, and pyrrolidine. This ring structure may be further substituted with one or more R 16 groups.

[0131]

[0128] In another aspect of the present invention, the oxidative hair cream composition has the formula II:

[0132]

Chem.

[0133] [wherein each R 21 ~R 210 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 、-CR x R y R z 、-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 NR 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 Ry 、 -P(O) 2 R x 、 -P(O)(OR x ) 2 、 -P(O)(OR x )O - 、 and -P(O)(O - ) 2 independently selected from the group consisting of; the subscript n is an integer from 0 to 4, preferably an integer from 0 to 1, most preferably an integer of 0, and preferably R 21 、 R 22 、 R 23、 R 24 、 and R 25 at least one of 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 is an electron-withdrawing group selected from the group, and preferably R 26、 R 27、 R 28、 R 29 、 R 210 is 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 selected from, and R 26、 R 27、 R 28、 R29 , R 210 At least one of which is -OR x or -NR x R x It contains a polymeric azo colorant by]. 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 a monomer molecular weight in the range of 28 to 500, preferably 43 to 350, and even more preferably 43 to 250. R 26、 R 27、 R 28、 R 29 , R 210 Two or more of which can be linked to each other via a covalent bond to form a ring structure. In combination with a benzene ring, this ring can form a structure including, but not limited to, naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, indoline, and isoindoline. This ring structure may be further substituted with one or more R 26 groups. R x , R y , or R z If two of which are attached to the same carbon or nitrogen group, they can also be connected to form a ring structure. Exemplary ring structures include, but are not limited to, piperazine, piperidine, and pyrrolidine. This ring structure may be further substituted with one or more R 26 groups.

[0134]

[0129] In a further aspect, the oxidative hair cream composition is of formula III or IIIa:

[0135]

Chemical formula

[0136] [Wherein each R 31~R 310 The 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 、-CR x R y R z 、-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 NR 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) 2 R x 、-P(O)(OR x ) 2 、-P(O)(OR x )O - 、and -P(O)(O - ) 2Independently selected from the group consisting of; the subscript n is an integer from 0 to 4, preferably an integer from 0 to 1, and most preferably an integer of 0, R 32 and R 33 may be connected to each other to form a condensed ring of 5 or more members, preferably R 36、 R 37、 R 38、 R 39 、R 310 is 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 selected from, and at least one of R 36、 R 37、 R 38、 R 39 、R 310 is -OR x 、or -NR x R y ; 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 a monomer molecular weight in the range of 28 to 500, preferably 43 to 350, and even more preferably 43 to 250]. The polymer azo colorant is contained. R 36、 R 37、 R 38、 R 39 、R 310Two or more of them can be linked to each other via a covalent bond to form a ring structure. In combination with a benzene ring, this ring can form structures including, but not limited to, naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, indoline, and isoindoline. This ring structure may be further substituted with one or more R 36 groups. If two of R x , R y , or R z are attached to the same carbon or nitrogen atom, they can also be connected to form a ring structure. Exemplary ring structures include, but are not limited to, piperazine, piperidine, and pyrrolidine. This ring structure may be further substituted with one or more R 36 groups.

[0137]

[0130] In yet another aspect of the present invention, the oxidative hair cream composition contains a polymeric azo colorant of formula IV:

[0138]

Chemical formula

[0139] [wherein each x and y is independently an integer from 0 to 20, or alternatively each x and y is independently an integer from 0 to 20 provided that at least one of x and y is greater than or equal to 1].

[0140]

[0131] In one aspect of the present invention, the oxidative hair cream composition has the formula V:

[0141]

Chemical formula

[0142] [wherein R 56 , R 57 , R 58 , R 59 , and R 510The groups are independently selected from hydrogen, halogen, 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 、-CR x R y R z 、-C(O)O - 、-NR x C(O)R y 、-NR x C(O)OR y 、-NR x C(O)SR y 、-NR x C(O)NR x R y 、-OR x 、-NR x R y 、-P(O)(OR x )O - 、and -P(O)(O - ) 2 ; R 56、 R 57、 R 58、 R 59 、R 510 among two or more of them can be linked to each other via a covalent bond to form a ring structure; 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 a monomer molecular weight in the range of 28 to 500, preferably 43 to 350, and even more preferably 43 to 250]. It contains an azo colorant according to ]. R 56、 R 57、 R 58、 R 59 、R 510Two or more of them can be linked to each other via covalent bonds to form a ring structure. When combined with a benzene ring, this ring can form structures including, but not limited to, naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, indoline, and isoindoline. This ring structure can be further substituted with one or more groups such as R 56 and the like. R x , R y , or two of R z can also be connected to form a ring structure when bonded to the same carbon or nitrogen group. Exemplary ring structures include, but are not limited to, piperazine, piperidine, and pyrrolidine. This ring structure can be further substituted with one or more R 56 groups.

[0143]

[0132] Other colorants that can form the colorant portion of the oxidative hair cream composition in combination with the polymeric colorant are also envisioned to be 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, substantive dyes, indigoid dyes, reactive dyes, disperse dyes, sulfur dyes, fluorescent dyes; pigments, both organic and inorganic; natural colorants, etc. Thus, the colorant of the oxidative hair cream 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 groups or they may have different chromophore groups.

[0144]

[0133] The oxidative hair cream composition of the present invention is prepared by combining at least one oxidizing agent with at least one polymeric colorant. The oxidative hair cream composition thus formed can be a substantially homogeneous mixture.

[0145]

[0134] The method for preparing the oxidative hair cream composition of the present invention consists of the following steps: (a) Preparing at least one oxidizing agent; (b) Preparing at least one polymer colorant; and (c) Combining at least one oxidizing agent and at least one polymer colorant to form a polymer colorant-containing oxidative hair cream.

[0146]

[0135] A method for applying color to hair according to the present invention consists of the following steps: (a) Preparing a polymer colorant-containing oxidative hair cream; (b) Applying the polymer colorant-containing oxidative hair cream to the hair; (c) Contacting the hair cream with the hair for a period of time; and (d) Removing the hair cream from the hair.

[0147]

[0136] A method for decolorizing and applying color to hair according to the present invention consists of the following steps: (a) Preparing a polymer colorant-containing oxidative hair cream; (b) Applying the polymer colorant-containing oxidative hair cream to the hair; (c) Contacting the hair cream with the hair for a period of time; and (d) Removing the hair cream from the hair.

[0148]

[0137] The oxidative hair cream 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 cream, or the hair may be dry at the time when the hair cream is applied to the hair.

[0149]

[0138] The oxidative hair cream can be permanent (for example, 80% of the original color intensity remains visible after 20 washing cycles), semi-permanent (for example, 80% of the original color intensity is visible up to 20 washing cycles and then becomes invisible), or temporary (for example, 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 hair cream and / or the amount of the polymeric colorant contained in the hair cream. For example, increasing the amount of the polymeric colorant in the hair cream can result in the color on the hair lasting longer. In contrast, a lower amount of the polymeric colorant contained in the hair cream can result in a shorter duration of the color on the hair. Also, the amount of time the oxidative hair cream 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 hair cream 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.

[0150]

[0139] 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%.

[0151]

[0140] In one aspect of the present invention, the molecular weight of the polymeric colorant in the hair cream ranges from 100 to 10000 or from 200 to 5000 or from 300 to 2000.

[0152]

[0141] At least one of the polymeric colorants described herein can be added to an oxidative hair cream 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 oxidative hair cream composition described herein on the hair, contacting the oxidative hair cream composition with the hair for a period of time, and further agitating, rinsing, and / or drying the thus-treated hair.

[0153]

[0142] Typically, two components are present in these types of oxidative systems. 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 prior to application to the hair. The initial application contains the polymeric colorant in a hydrogen peroxide cream agent rather than in the second component. However, alternatively, it is conceivable to place the polymeric colorant in the second component.

[0154]

[0143] Thus, in one embodiment, at least one polymeric colorant is mixed into a cream agent containing an oxidizing agent. Immediately prior to use, the cream agent containing the polymeric colorant / hydrogen peroxide is mixed with at least one other component to raise the pH by an amount sufficient to activate the hydrogen peroxide. In an alternative embodiment, the polymeric colorant may be added to the second component. In this case, the second component is added to the non-colored hydrogen peroxide cream agent immediately prior to use.

[0155] The present invention described herein is mainly directed to oxidative hair creams containing polymeric colorants, but the invention is not limited to only these compositions. The oxidative hair cream may contain a combination of a polymeric colorant and another colorant. Other colorants include, for example, dyes, pigments, and combinations thereof.

[0156]

[0145] 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 include 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.

[0157]

[0146] Suitable dyes include 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 C 1 ~C 3 -alkyl or phenyl or a heterocyclic radical, and the phenyl and heterocyclic radicals may further carry substituents that do not confer water solubility), anthrapyrimidinecarboxylic acid amide, violanthrone, isoviolanthrone, dioxazine dyes, copper phthalocyanine which may contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromo-chloro-copper phthalocyanine containing up to 14 bromine atoms per molecule, and dyes selected from the group consisting of mixtures thereof.

[0158]

[0147] In one aspect of the present invention, the components of the oxidative 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 is formed that contains at least a major proportion of the liquid components, preferably substantially all of the liquid components, and the liquid components are thoroughly 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 stirring of the mixture is continued, and if necessary, the stirring of the mixture can be intensified at this point to form a solution or a homogeneous dispersion by the 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 stirring of the mixture is continued for a time sufficient to form a composition having the required viscosity and phase stability characteristics. Often, this involves stirring for about 30 to 60 minutes.

[0159]

[0148] The oxidative hair cream of the present invention can be combined with other molecules, compounds, and / or agents useful for applying the oxidative hair cream 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.

[0160]

[0149] The oxidative hair cream 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 alkalizing agents (e.g., ammonia), alkaline sources (e.g., silicates and / or carbonates), humectants, conditioning agents, thickeners, non-coloring dyes, detergency builders, enzymes, enzyme stabilizers, foam inhibitors, pH adjusters, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, opacifying agents, perfumes, and coloring agents. Various optional oxidative hair cream composition raw material components, when present in the composition here, should be utilized in concentrations customarily used to provide their desired contributions to the composition or the hair bleaching agent and / or coloring method. In many cases, the total amount of such optional oxidative 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.

[0161]

[0150] Example ​​

[0151] Several polymer and monomer colorants were tested for their 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 (manufactured by SpeedMixer, Inc., Landrum, SC) was used at 1500 rpm to mix each sample for at least 90 seconds until a visually uniform mixture was obtained. 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 agent was 0.67 when measured at a concentration of 10 grams / liter in methanol with a 1 cm path length. After mixing, the samples were first stored at room temperature for 7 days and then transferred to an oven at 40 °C. The 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 agent at time zero as measured by UV-VIS. Color loss is fading due to chemical changes from the oxidative cream agent raw material components containing peroxide.

[0162]

[0152] 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 The number of equivalent days at room temperature for 50% deterioration of the color was used to conduct the evaluation according to Table 1. A rating of "1" means the most stable, while a rating of "5" means the least stable.

[0163]

[0153]

[0164]

Table 1

[0165]

[0154] The results of the colorant and stability tests of the present invention are shown in Table 2A. The comparative colorant and stability test results are shown in Table 2B.

[0166]

[0155]

[0167]

Table 2

[0168]

[0156]

[0169]

Table 3

[0170]

[0157] The test results indicate that not all polymeric triarylmethane dyes were stable (Comparative Examples 1 - 5). Other polymeric dye classes, such as cyanine (Comparative Example 6), methine (Comparative Example 7), and anthraquinone (Comparative Examples 8 and 9), were also not stable. Monomeric anthraquinone dyes, such as External D&C Violet 2 (Comparative Example 10) and Solvent Violet 13 (Comparative Example 11), are difficult to blend into the cream agent, but were found to have better stability compared to their polymeric equivalents (Comparative Examples 8 and 9).

[0171]

[0158] Color performance evaluation

[0159] Materials: Blonde hair (lightly bleached dark hair) was cut into strips 3 cm wide and 20 cm long. Fanola Violet Bleach Powder Fanola 40 Vol. (12% peroxide) oxidizing cream agent

[0160] Procedure:

[0161] The hair was first weighed and the amount of cream agent required was calculated (4 grams of cream agent per 1 gram of hair). The color and oxidative cream developer were mixed as described above. The mixture was checked and remixed 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 of cream agent and 1 part of bleaching agent powder). An appropriate amount of oxidative cream agent was added to the bleaching agent powder. The wooden end of a cotton swab was used to stir the bleaching agent / cream agent until completely mixed. The bleaching agent / cream agent mixture was transferred to a large weighing dish with the hair sample. The mixture was spread over the entire hair and rubbed into the hair with the fingertips until the mixture was completely and uniformly incorporated over the entire hair. The bleaching agent 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.

[0172]

[0162] CIE WI is a good measure of how well the hair has been lightened. The original hair had a whiteness index (WI) of -76.6 due to its yellow color. After treatment, the WI value increased, indicating that the hair had been lightened. The difference in WI, ΔWI, between the treated hair and the original hair was recorded. A larger ΔWI indicates better lightening of the hair.

[0173]

[0163] The WI and ΔWI values of the original hair, the bleaching agent control (without dye), and the bleaching agent compositions containing Example 1 and Comparative Example 10 (External D&C Violet 2) are shown in Table 3. The bleaching agent composition using Example 1 resulted in better lightening than the bleaching agents using the bleaching agent control and Comparative Example 10.

[0174]

[0164]

[0175]

Table 4

[0176]

[0165] When dark-colored hair is decolorized, the melanin pigment is destroyed, whereby the red pigment is visually emphasized, and an undesirable, warm-colored orange or “true brown” tone is cast on the decolorized hair. This true brown tone is typically corrected by the application after the decolorization of violet or blue dyes. Blue or violet is complementary to the orange and yellow true brown tones, making this tone effectively duller. This dye can be delivered in a shampoo, conditioner, mask, hair cream, or the like. It is preferable to add a violet or blue colorant to the decolorizing cream agent so that the true brown tone is directly dulled during the decolorization process, thus eliminating the need for additional color treatment. The problem is that oxidative cream agents are generally in an aggressive state and many colorants fade. The present invention relates to a specific subset of dyes that are stable in oxidative cream agents during storage and also correct the color to make the true brown tone duller.

[0177] Unexpectedly, the polymeric colorant deposits more strongly than the comparative dyes. It is conventional to expect that the dyes have better deposition than the polymeric colorant. This is because the colorant has a larger molecular weight and the polymer should improve the water solubility of the colorant which can reduce deposition. However, without being bound by theory, the dyes tend to show strong aggregation in the more lipophilic cream agent, while the polymeric colorant is considered to be essentially completely dispersed in the cream agent due to a better energy match to the cream agent medium and the steric hindrance of the polymer chains which limits the ability of the colorant to self-associate. Thus, these dye aggregates are much larger in size than the polymeric colorant, even though the individual dyes have a small molecular weight. The polymeric colorant which is smaller in size and completely dispersed can deposit very uniformly along the length of the hair fiber, while the dye aggregates have limited deposition uniformity and overall coverage due to their relatively larger size. Thus, the polymeric colorant with a larger molecular weight deposits much more strongly on the hair than the dyes, completely unexpectedly.

[0178] All references, including publications, patent applications, and patents cited herein are hereby incorporated by reference to the extent that each reference is specifically and individually indicated to be incorporated by reference and is as fully described herein.

[0179]

[0168] 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 that range, unless otherwise indicated herein, 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 and all 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.

[0180] 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 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. An oxidative hair cream composition, said composition comprising at least one polymeric azo colorant and at least one oxidative hair cream ingredient.

2. 2. The oxidative hair cream composition of claim 1, wherein said at least one polymeric azo dye is alkoxylated.

3. 2. The oxidative hair cream composition of claim 1, wherein the composition is a liquid.

4. 2. The oxidative hair cream composition of claim 1, wherein said composition comprises at least one bleaching agent.

5. 5. The oxidative hair cream composition of claim 4, wherein said at least one bleaching agent is a category 1 bleaching agent.

6. 5. The oxidative hair cream composition of claim 4, wherein said at least one bleaching agent is a category 2 bleaching agent.

7. 2. The oxidative hair cream composition of claim 1, wherein said at least one oxidative hair cream ingredient is hydrogen peroxide.

8. 8. The oxidative hair cream composition of claim 7, wherein the composition contains from 0.01% to 33% hydrogen peroxide.

9. 8. An oxidative hair cream composition according to claim 7, wherein the composition contains from 0.1% to 15% hydrogen peroxide.

10. 2. The oxidative hair cream composition of claim 1, wherein said at least one polymeric azo colorant has a maximum absorbance in the range of from 400 nm to 700 nm.

11. 2. The oxidative hair cream composition of claim 1, wherein said at least one polymeric azo colorant has a maximum absorbance in the range of from 470 nm to 700 nm.

12. 2. The oxidative hair cream composition of claim 1, wherein said at least one polymeric azo colorant has a maximum absorbance in the range of from 550 nm to 700 nm.

13. The at least one polymeric azo colorant is represented by Formula I: 【Chemistry 1】 [Wherein, each R １１ ~R １１０ The group is selected from hydrogen, deuterium and R ｖ each R ｖ is a 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 N.R. 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) ２ R ｘ , -P(O)(OR ｘ ) ２ , -P(O)(OR ｘ ) O － , and -P(O)(O － ) ２ the subscript n is an integer from 0 to 4; R ｘ , R ｙ and R ｚ is 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, the molecular weight of the monomer being in the range of 28 to 500.

14. The R １１ , R １２ , and R １３ At least one of the following 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 14. The oxidative hair cream composition of claim 13, wherein the electron-withdrawing group is selected from the group:

15. R １６、 R １７、 R １８、 R １９ , R １１０ is 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 independently selected from R １６、 R １７、 R １８、 R １９ , R １１０ At least one of the groups is -OR ｘ or -NR ｘ R ｙ 14. The oxidative hair cream composition according to claim 13, wherein

16. R １６、 R １７、 R １８、 R １９ , R １１０ 14. The oxidative hair cream composition of claim 13, wherein two or more of are linked to each other via a covalent bond to form a ring structure.

17. The at least one polymeric azo colorant has Formula II: 【Chemistry 2】 [Wherein, each R ２１ ~R ２１０ The group is selected from hydrogen, deuterium and R ｖ each R ｖ is a 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 N.R. 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) ２ R ｘ , -P(O)(OR ｘ ) ２ , -P(O)(OR ｙ ) O － , and -P(O)(O － ) ２ the subscript n is an integer from 0 to 4; R ｘ , R ｙ and R ｚ is 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, the molecular weight of the monomer being in the range of 28 to 500.

18. The R ２１ , R ２２ , R ２３、 R ２４ , and R ２５ At least one of the following is halogen, nitro, nitrile, nitroso, -C(O)R ｘ , -C(O)OR ｘ , -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 18. The oxidative hair cream composition of claim 17, wherein the electron-withdrawing group is selected from the group:

19. R ２６、 R ２７、 R ２８、 R ２９ , R ２１０ is 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 from R ２６、 R ２７、 R ２８、 R ２９ , R ２１０ At least one of the groups is -OR ｘ or -NR ｘ R ｙ 18. The oxidative hair cream composition according to claim 17, wherein

20. R ２６、 R ２７、 R ２８、 R ２９ , R ２１０ 20. The oxidative hair cream composition of claim 17, wherein two or more of are linked to each other via a covalent bond to form a ring structure.

21. The at least one polymeric azo colorant has the formula III or IIIa: 【Chemistry 3】 [Wherein, each R ３１ ~R ３１０ The group is selected from hydrogen, deuterium and R ｖ each R ｖ is a 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 N.R. 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) ２ R ｘ , -P(O)(OR ｘ ) ２ , -P(O)(OR ｘ ) O － , and -P(O)(O － ) ２ the subscript n is an integer from 0 to 4; R ｘ , R ｙ and R ｚ is 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, the molecular weight of the monomer being in the range of 28 to 500.

22. R ３２ and R ３３ 22. The oxidative hair cream composition of claim 21, wherein: are connected to each other to form a fused ring having 5 or more members.

23. R ３６、 R ３７、 R ３８、 R ３９ , R ３１０ is 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 from R ３６、 R ３７、 R ３８、 R ３９ , R ３１０ At least one of the groups is -OR ｘ or -NR ｘ R ｙ 22. The oxidative hair cream composition of claim 21, wherein

24. R ３６、 R ３７、 R ３８、 R ３９ , R ３１０ 22. The oxidative hair cream composition of claim 21, wherein two or more of are linked together via a covalent bond to form a ring structure.

25. The at least one polymeric azo colorant has Formula IV: 【Chemistry 4】 2. The oxidative hair cream composition of claim 1, wherein the dye is of the formula: wherein each of x and y is independently an integer from 0 to 20.

26. 1. A method for treating hair, comprising: (a) providing an oxidative hair cream composition comprising at least one polymeric azo colorant and at least one oxidizing agent; (b) contacting said oxidative hair cream composition with human hair. and

27. 1. A method for treating hair, comprising: (a) at least one oxidizing agent and a compound of formula V: 【Chemistry 5】 [Wherein, each R ５６ , R ５７ , R ５８ , R ５９ groups are independently selected from hydrogen, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl groups; R ５１０ is hydrogen, deuterium and R ｖ each R ｖ is halogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, -C(O)O － , -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)(OR ｘ ) O － , and -P(O)(O － ) ２ R ｘ , R ｙ and R ｚ is hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, hydroxyethyl, and R ｕ R ｕ is an organic group composed of one or more organic monomers, the molecular weight of said monomers being in the range of 28 to 500; (b) contacting said oxidative hair cream composition with human hair. and

28. R ５６、 R ５７、 R ５８、 R ５９ , R ５１０ 28. The method of claim 27, wherein two or more of are linked to each other via a covalent bond to form a ring structure.

29. 29. The method of claim 28, wherein the ring structure is one of naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, indoline, and isoindoline.

30. The ring structure is one or more R ５６ 30. The method of claim 29, wherein said alkyl group is substituted with a aryl group.

31. R ｘ , R ｙ , or R ｚ 29. The method of claim 28, wherein two of are attached to the same carbon or nitrogen group to form the ring structure.

32. 29. The method of claim 28, wherein the ring structure is one of piperazine, piperidine, and pyrrolidine.

33. The ring structure is one or more R ５６ The method of claim 32, further substituted with a group.

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