Oxidative hair cream composition containing thiophene azo colorant

Abstract

To provide a hair cream composition with advantages such as better lifting and better hue.SOLUTION: An oxidative hair cream composition is provided which comprises at least one thiophene azo colorant and at least one oxidative hair cream ingredient component.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 thiophene azo 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 blond as level 10, with some 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. All melanin pigments are not 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, whereby red pigments are visually emphasized, and an undesirable, warm-colored orange or "ginger-colored" tone is cast on the bleached hair. To dull the warm color, hair colorants having dull color properties 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 ordinary 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 four levels depending on the concentration of hydrogen peroxide used. For example, level 6 hair 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 Category 1 decolorization, these are mixed with 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 many cases, a separately packaged third component called decolorizing oil is added to the decolorizer powder and peroxide during use. The decolorizing oil may contain moisturizing agents and other conditioning agents. The decolorizing agents of Category 2 can provide a lift of more than 7 levels, which cannot be achieved with the decolorizing agents of Category 1. The decolorizing agents of Category 2 are usually used whenever a lift of more than 4 levels is desired, for example, when lifting hair of level 5 or darker colors to a light blonde.

[0005]

[0005] In decolorization at various levels, since the underlying warm - toned hues are exposed, toning treatments are 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 ashy hues. These hues, or combinations thereof, are recommended to dull the spectrum of undertones 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 laws of color, 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.

[0006]

[0006] According to the present invention, there is a single-step method using a composition of a hair bleaching agent that can simultaneously lighten hair and effectively deposit various color shades. This is achieved by including a dye in the bleaching agent composition. Dyes suitable for this use should (a) have a blue-violet hue desirable for dulling yellowish hues, (b) be stable in the bleaching agent, (c) have a good toxicity profile, and (d) be easily mixed into the oxidizing composition and remain homogeneous. Therefore, there continues to be a need for improved colorants for this use. The thiophene azo dyes disclosed herein and oxidizing hair care compositions containing them offer advantages beyond past efforts in this area, such as better lifting, better hue, better mixing with hair cream compositions, and an improved toxicity profile. Brief Summary

[0007]

[0007] In one aspect, the present invention relates to an oxidizing hair cream composition, wherein the composition contains at least one thiophene azo colorant and at least one oxidizing hair cream raw material component.

[0008]

[0008] In a further aspect of the present invention, the thiophene azo colorant has the formula I:

[0009]

Chemical formula

[0010] [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, -(CH2) n -O-R x 、-(CH2) n -NR x R y, -C(O)R x , -C(O)OR x , -C(O)O - , -C(O)NR x R y , -OC(O)R x , -OC(O)OR x , -OC(O)NR x R y , -S(O)2R x , -S(O)2OR x , -S(O)2O - , -S(O)2NR x R y , -NR x C(O)R y , -NR x C(O)OR y , -NR x C(O)SR y , -NR x C(O)NR y R z , -OR x , -NR x R y , -P(O)2R x 、 -P(O)(OR x )2, -P(O)(OR x )O - , and -P(O)(O - )2 are independently selected from the group consisting of; the exponent n is an integer from 0 to 4, and R x , R y and R z are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, and R u ; R u is an organic group composed of one or more organic monomers having the monomer molecular weight in the range of 28 to 500) is a dye.

[0011]

[0009] In yet a further aspect of the present invention, at least one thiophene azo colorant has the following structure:

[0012]

Chemical formula

[0013] It is a dye represented by [[wherein each x and y is independently an integer from 0 to 20]].

[0014]

[0010] In another aspect, the present invention is a method for treating hair, comprising: (a) preparing an oxidative hair cream composition, the composition containing at least one thiophene azo colorant and at least one oxidative hair cream raw material component; and (b) contacting the oxidative hair cream composition with human hair. Detailed description

[0015]

[0011] The present invention described herein is an oxidative hair cream containing at least one oxidative hair cream raw material component and at least one colorant containing a thiophene azo chromophore. The oxidative hair cream containing the thiophene azo 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.

[0016]

[0012] As used herein, the term "hair" is intended to include keratin fibers, such as human hair, animal hair, etc.

[0017]

[0013] As used herein, the term "alkoxy" is intended to include C1 - C8 alkoxy and alkoxy derivatives of polyols having repeating units such as butylene oxide, glycidol oxide, ethylene oxide, or propylene oxide.

[0018] As used herein, the terms "polyalkyleneoxy" and "polyoxyalkylene" are used interchangeably and generally refer to a molecular structure containing the following repeating units: -CH2CH2O-, -CH2CH2CH2O-, -CH2CH2CH2CH2O-, -CH2CH(CH3)O-, -CH2CH2CH(CH3)O-, and any combination thereof. Further, the polyoxyalkylene constituent material may be selected from the group consisting of one or more monomers selected from alkyleneoxy groups, glycidol groups, glycidyl groups, or mixtures thereof. 2~20 It may be selected from the group consisting of one or more monomers selected from alkyleneoxy groups, glycidol groups, glycidyl groups, or mixtures thereof.

[0019]

[0015] As used herein, unless otherwise specified, the terms "alkyl" and "alkyl-capped" are intended to include C2-C 100 alkyl groups, C2-C 50 alkyl groups, C5-C 25 alkyl groups, or even C 10 -C 20 alkyl groups.

[0020]

[0016] As used herein, unless otherwise specified, the term "aryl" is intended to include C5-C 18 aryl groups and, in one aspect, C5-C 12 alkyl groups.

[0021]

[0017] As used herein, unless otherwise specified, the term "alkyl" is intended to include C1-C 18 alkyl groups and, in one aspect, C1-C6 alkyl groups.

[0022]

[0018] As used herein, unless otherwise specified, the term "alkanoyl" refers to a monovalent group of the formula -C(O)R a (wherein R a is an alkyl group, preferably a C3-C 29 alkyl group).

[0023] As used herein, unless otherwise specified, the term "alkenyl" refers to 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" refers to an acyclic hydrocarbon containing one or more carbon-carbon double bonds.

[0024]

[0020] As used herein, unless otherwise specified, the term "alkenoyl" refers to the formula -C(O)R b (wherein R b is an alkenyl group, preferably a C3 - C 29 alkenyl group).

[0025]

[0021] As used herein, unless otherwise specified, the term "aroyl" refers to the formula -C(O)R c (wherein R c is an aryl group, preferably a C6 - C 10 aryl group).

[0026]

[0022] The terms "ethylene oxide", "propylene oxide", and "butylene oxide" may be referred to herein by their typical names "EO", "PO", and "BO", respectively.

[0027]

[0023] 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.

[0028]

[0024] 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, or 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.

[0029]

[0025] The hair cream composition of the present invention is generally an aqueous base 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.

[0030]

[0026] Skin softening oil

[0027] If desired, the hair cream composition may contain one or more skin softening oils. Such oils provide a conditioning effect on the hair. If 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. Various animal, plant, or mineral oils or synthetic oils derived from plants or animals are also suitable. 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.

[0031]

[0028] Surfactant

[0029] 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.

[0032]

[0030] Nonionic surfactant

[0031] Examples of nonionic surfactants include alkoxylated alcohols or ethers, alkoxylated carboxylic acids, sorbitan derivatives, and the like. 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); Ceteas 1 - 45 (formed by the reaction of cetyl alcohol and ethylene oxide, the number of repeating units of ethylene oxide is 1 - 45), and the like. 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.

[0033]

[0032] Also preferred are various types of alkoxylated sorbitans and alkoxylated sorbitan derivatives. For example, alkoxylation of sorbitan, particularly ethoxylation, results in polyalkoxylated sorbitan derivatives. Esterification of polyalkoxylated sorbitan results in sorbitan esters, such as polysorbates. Examples of such raw material components include polysorbates 20 - 85, sorbitan oleate, sorbitan palmitate, sorbitan sesquioleate, sorbitan stearate, and the like. In a preferred embodiment, polysorbate 20 is preferred.

[0034]

[0033] Anionic surfactants

[0034] The hair cream composition may optionally contain one or more anionic surfactants. The preferred range of the anionic surfactant is about 0.01 - 25% by weight, preferably 0.5 - 20% by weight, more preferably 1 - 15% by weight of the total oxidative composition. Suitable anionic surfactants include those of the formula ROSO3M and RO(C2H4O) x SO3M (wherein R is an alkyl or alkenyl having about 10 - 20 carbon atoms, x is 1 - about 10, and M is a water-soluble cation, such as ammonium, sodium, potassium, or triethanolamine cation), including alkyl sulfates and alkyl ether sulfates.

[0035]

[0035] Another type of anionic surfactant that can be used in the compositions of the present invention is the water-soluble salt of an organic, sulfuric acid reaction product of the general formula: R1-SO3-M (wherein R1 is selected from the group consisting of linear or branched, saturated aliphatic hydrocarbon radicals having about 8 - about 24 carbon atoms, preferably 12 - 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 - 24 carbon atoms, and sulfonating agents, such as sulfur trioxide.

[0036]

[0036] Similarly suitable are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, or fatty acid reaction products with alkanolamines or ammonium hydroxide. The fatty acids may be derived from, for example, coconut oil. Examples of fatty acids also include lauric acid, stearic acid, oleic acid, palmitic acid, and the like.

[0037]

[0037] In addition, succinates and succinamates are suitable anionic surfactants. This class includes compounds such as sodium dioctadecyl sulfosuccinate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinate; and esters of sodium sulfosuccinate, such as the dihexyl ester of sodium sulfosuccinate, the dioctyl ester of sodium sulfosuccinate, and the like.

[0038]

[0038] 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 is hydrolyzed 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.

[0039]

[0039] 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.

[0040]

[0040] As yet another class of anionic surfactants, the formula: (R1 is C8~24 is an alkyl or alkenyl radical, preferably C 10~18 ; R2 is H, C 1~4 alkyl, phenyl, or -CH2COOM; R3 is CX2- or C 1~2 alkoxy, each X being independently H or C 1~6 alkyl or alkyl ester, n is from 1 to 4, and M is H or a salt-forming cation as described above), and salts thereof (alkali, alkaline earth, and ammonium salts). Examples of such surfactants are N-acylsarcosinates, including lauroylsarcosinate, myristoylsarcosinate, cocoylsarcosinate, and oleoylsarcosinate, preferably in the form of sodium or potassium.

[0041]

[0041] Cationic, zwitterionic or betaine surfactants

[0042] Certain types of amphoteric, zwitterionic, or cationic surfactants can also be used as amphiphilic surfactant materials. A description of such surfactants is provided in U.S. Patent No. 5,843,193, which is hereby incorporated by reference in its entirety.

[0042]

[0043] 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 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.

[0043]

[0044] Also suitable amphoteric surfactants are monocarboxylates or dicarboxylates, such as cocoamphocarboxypropionate, cocoamphocarboxylic acid, cocoamphocarboxyglycinate, and cocoamphoacetate.

[0044]

[0045] As other types of amphoteric surfactants, R-NH(CH2) n amino alkanoates of COOM or of the formula: R-[(CH2) m COOM]2 iminodiacanoates 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 these 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-carboxylethyl betaine, and mixtures thereof. Also suitable are sulfo- and amide-betaines, for example, coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine and the like. Particularly preferred is cocamidopropyl betaine.

[0045]

[0046] Polar solvent

[0047] The hair cream composition may also contain various non-aqueous polar solvents other than water, including monohydric, dihydric, or polyhydric alcohols, and similar water-soluble raw material components. When present, such polar solvents may be in the range of about 0.01 to 25% by weight, preferably about 0.05 to 15% by weight, more preferably about 0.1 to 10% by weight of the first composition of the polar solvent. Examples of suitable monohydric alcohols include ethanol, isopropanol, benzyl alcohol, butanol, pentanol, ethoxyethanol, and the like. Examples of dihydric or polyhydric alcohols, as well as sugars and other types of humectants that can be used, include glycerin, glucose, fructose, mannose, mannitol, maltitol, lactitol, inositol, and the like. Examples of suitable glycols include propylene glycol, butylene glycol, ethylene glycol, polyethylene glycol, ethoxydiglycol, and the like having 4 to 250 repeating ethylene glycol units.

[0046]

[0048] Chelating agent

[0049] 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 metal ions and inactivate them to prevent these harmful effects on the stability or action of the composition. In particular, the chelating agent chelates metal ions found in water and prevents these ions from interfering with the deposition and reaction of the dye on the hair fiber surface. Examples of suitable chelating agents include EDTA and its calcium, sodium, or potassium derivatives, HEDTA, sodium citrate, TEA-EDTA, and the like.

[0047]

[0050] pH adjuster

[0051] It may also be desirable to add a small amount of acid or base to adjust the pH of the oxidative dye composition to a desired pH range. Suitable acids include hydrochloric acid, phosphoric acid, etidronic acid, and the like. Suitable bases include sodium hydroxide, ammonium hydroxide, potassium hydroxide, and the like. Also suitable are primary, secondary, or tertiary amines or their derivatives, such as aminomethylpropanol, monoethanolamine, and the like. Phosphates, such as potassium phosphate, disodium phosphate, and the like, can also be used. The suggested range of the pH adjuster is about 0.00001 to 8% by weight, preferably about 0.00005 to 6% by weight, more preferably about 0.0001 to 5% by weight of the total composition.

[0048]

[0052] Conditioning agent

[0053] 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.

[0049]

[0054] 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.

[0050]

[0055] When present, the insoluble silicone conditioning agent is present at a level of about 0.1 to 10% by weight, preferably about 0.1% by weight to about 5% by weight, more preferably about 1% by weight to about 3% by weight of the composition. Suitable insoluble silicones include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyether siloxane copolymers, and mixtures thereof.

[0051]

[0056] Other additional components

[0057] The composition of the present invention typically further comprises several other ingredients commonly used in hair care compositions, such as shampoos, conditioners, styling aids and colorants, which are well known to those skilled in the art, such as thickeners and diluents. Further, several optional materials can be added to the compositions described herein at levels of from about 0.001% to about 5% by weight of the composition, preferably from about 0.01% to about 3% by weight, more preferably from about 0.05% to about 2% by weight.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, sodium dithionite 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 hydroxybenzoates; 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 dimethylmethyl sulfate ammonium, soy dimethylammonium chloride and coco dimethylammonium chloride; enzyme stabilizers such as water-soluble sources of calcium or borate species; TiO2 and TiO2-coated mica; perfumes and perfume solubilizers; and zeolites and their derivatives and metal ion scavengers such as polycarboxylates, aminopolycarboxylates, polyphosphonates, aminopolyphosphonates, etc., and water softeners such as sodium citrate, inorganic peroxide oxidants and enzymes are included.

[0052]

[0058] Oxidizing agent composition In addition, the aqueous oxidation cream 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.

[0053]

[0059] 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.

[0054]

[0060] 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 equivalent percarbonate, sodium pyrophosphate hydroperoxide, urea hydroperoxide, or sodium peroxide can be used here. Sources of available oxygen, such as persulfate bleaching agents (e.g., OXONE made by DuPont), are also useful. Sodium perborate monohydrate, sodium percarbonate, sodium persulfate, and potassium persulfate are particularly preferred. Mixtures of any convenient source of hydrogen peroxide can also be used.

[0055]

[0061] 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").

[0056]

[0062] 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 of the composition, preferably from about 1% to about 15% by weight, more preferably up to about 10% by weight, and most preferably up to about 8% by weight. 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.

[0057]

[0063] Preferred activators are tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulfonate (C 10 -OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS), perhydrolyzable esters, and mixtures thereof, most preferably selected from the group consisting of benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleaching activators in the pH range of about 8 to about 11 are selected from those having an OBS or VL leaving group.

[0058]

[0064] Preferred hydrophobic bleaching activators include nonanoyloxybenzenesulfonate (NOBS); sodium 4-[N-(nonanoyl)aminohexanoyloxy]-benzenesulfonate (NACA-OBS) this example is described in U.S. Patent No. 5,523,434; dodecanoyloxybenzenesulfonate (LOBS or C 12-OBS); 10-undecenoyl oxybenzenesulfonate (UDOBS or C11-OBS having an unsaturation at the 10-position); and decanoyl oxybenzoic acid (DOBA), but are not limited thereto.

[0059]

[0065] 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.

[0060]

[0066] 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.

[0061]

[0067] Useful additional decolorizer activators herein are amide-substituted as described in U.S. Patent Nos. 5,698,504; 5,695,679; and 5,686,014, each of which is cited hereinabove. Preferred examples of such decolorizing activators include (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.

[0062]

[0068] 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 C6H4 ring condensed at the 1,2-position with a --C(O)OC(R 1 )=N- moiety.

[0063]

[0069] Nitriles, such as acetonitrile and / or ammonium nitrile and other quaternary nitrogen-containing nitriles, are another class of activators useful herein. Non-limiting examples of such nitrile decolorizing activators are described in U.S. Patent Nos. 6,133,216; 3,986,972; 6,063,750; 6,017,464; 5,958,289; 5,877,315; 5,741,437; 5,739,327; and 5,004,558; and European Patent Nos. 790 244, 775 127, 1 017 773, and 1 017 776; and WO99 / 14302, WO99 / 14296, and WO96 / 40661, all of which are hereby incorporated by reference.

[0064]

[0070] 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.

[0065]

[0071] 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.

[0066]

[0072] 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.

[0067]

[0073] The compositions and methods of the present invention can also optionally include a metal-containing decolorization catalyst, preferably a manganese and cobalt-containing decolorization catalyst.

[0068]

[0074] One type of metal-containing decolorizing catalyst is a catalyst system comprising a transition metal cation having a determined decolorizing catalytic activity (e.g., copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cation), an auxiliary metal cation having little or no decolorizing catalytic activity (e.g., 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.

[0069]

[0075] 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 manganese-based catalysts disclosed in U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Patent Application Publication Nos. 549,271A1; 549,272A1; 544,440A2; and 544,490A1. Preferred examples of these catalysts include Mn IV 2(μ-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mn III 2(μ-O)1(μ-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(ClO4)2, Mn IV 4(μ-O)6(1,4,7-triazacyclononane)4(ClO4)4, Mn III Mn IV 4(μ-O)1(μ-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2(ClO4)3, Mn IV(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH3)3(PF6), and mixtures thereof. Other metal-based decolorization 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.

[0070]

[0076] Cobalt decolorization 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, pp. 1-94. The most preferred cobalt catalysts useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc]Ty (wherein "OAc" represents an acetate moiety and "Ty" represents an anion), especially cobalt pentaamine acetate chloride [Co(NH3)5OAc]Cl2; and [Co(NH3)5OAc](OAc)2; [Co(NH3)5OAc](PF6)2; [Co(NH3)5OAc](SO4); [Co(NH3)5OAc](BF4)2; and [Co(NH3)5OAc](NO3)2 (herein "PAC").

[0071]

[0077] 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).

[0072]

[0078] 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).

[0073]

[0079] Examples of transition metal decolorizing catalysts of macrocyclic rigid ligands suitable for use in the compositions of the present invention include generally known compounds, but are non - 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) Diaco-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) hexafluorophosphate Diaco-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) hexafluorophosphate Aco-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(III) hexafluorophosphate Diaco-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) tetrafluoroborate Dichloro-5,12-dimethyl-1,5,8,12 tetraazabicyclo[6.6.2]hexadecane manganese(III) hexafluorophosphate Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(III) hexafluorophosphate Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane manganese(II) Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane manganese(II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane manganese(II)

[0080] 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.

[0074]

[0081] In practice, and not by way of limitation, the compositions and methods herein can be adjusted such that the active decolorizing catalyst species are on the order of at least one part per billion in a composition comprising a lipophilic fluid and a decolorizing system, and preferably yield from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm of active decolorizing catalyst species in a composition comprising a lipophilic fluid and a decolorizing system.

[0075]

[0082] 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 peroxide decolorization to increase the effectiveness of decolorization. Typically, this is accomplished by in situ generation of an active oxygen transfer agent, such as dioxirane, oxaziridine, or oxaziridinium. Alternatively, preformed dioxirane, oxaziridine, and oxaziridinium may be used.

[0076]

[0083] 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 the 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:

[0077]

Chemical formula

[0078] [wherein, R 1 ~R 4 may be hydrogen, or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl, and cycloalkyl radicals] and the like are included.

[0079]

[0084] Zwitterionic decolorization enhancing agents are preferably included in the decolorization enhancing compounds, which are described in U.S. Patent Nos. 5,576,282 and 5,718,614. Other decolorization enhancing compounds include those described in U.S. Patent Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 5,482,515; and 5,550,256; and cationic decolorization enhancing agents described in WO95 / 13351, WO95 / 13352, and WO95 / 13353.

[0080]

[0085] 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 the use conditions by the consumer. The oxygen source may include a source of hydrogen peroxide, in situ generation of peroxy anions by the reaction of a hydrogen peroxide source and a decolorization activator, a preformed peracid compound, or a mixture of suitable oxygen sources. Of course, those skilled in the art will recognize that other sources of oxygen may be utilized without departing from the scope of the present invention. The decolorization enhancing compound, if present, is preferably utilized with the oxygen source in the decolorizing system of the present invention.

[0081]

[0086] Preformed peracids are also suitable as decolorizing agents. The preformed peracid compound, as used herein, is any convenient compound that is stable and produces an effective amount of peracid or peroxy anion under the use conditions by the consumer. The preformed peracid compound 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.

[0082]

[0087] One class of suitable organic percarboxylic acids has the general formula:

[0083]

Chemical formula

[0084] [Wherein, R is an alkylene or substituted alkylene group containing 1 to about 22 carbon atoms, or a phenylene or substituted phenylene group, Y is hydrogen, halogen, alkyl, aryl, -C(O)OH, or -C(O)OOH] has.

[0085] 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:

[0086]

Chemical formula

[0087] [Wherein, Y can be, for example, H, CH3, CH2Cl, C(O)OH, or C(O)OOH; n is an integer from 0 to 20] has. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

[0088]

Chemical formula

[0089] [Wherein, Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C(O)OH, or C(O)OOH] has.

[0090]

[0088] Typical monoperoxyacids useful here include alkyl and aryl peroxyacids, for example, (i) Peroxybenzoic acid and ring-substituted peroxybenzoic acids, such as peroxy-α-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o-carboxybenzamidoperoxyhexanoic acid (sodium salt); (ii) Aliphatic, substituted aliphatic, and arylalkyl monoperoxy acids, such as peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-(3-octylsuccinoyl)aminoperoxycaproic acid (SAPA), and N,N-phthaloylaminoperoxycaproic acid (PAP); (iii) Amidoperoxy acids, such as the monononylamide of peroxysuccinic acid (NAPSA) or peroxoadipic acid (NAPAA) may be mentioned.

[0091]

[0089] Typical diperoxy acids useful here include alkyl diperoxy acids and aryl diperoxy acids, such as (i) 1,12-diperoxydodecanedioic acid; (ii) 1,9-diperoxyazelaic acid; (iii) Diperoxybrassic acid; diperoxysebacic acid, and diperoxyisophthalic acid; (iv) 2-decyldiperoxybutane-1,4-dioic acid; (v) 4,4'-sulfonylbisperoxybenzoic acid may be mentioned.

[0092]

[0090] 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. A persulfate compound, 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.

[0093]

[0091] 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.

[0094]

[0092] 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 a substrate therefor). Such an enzyme system is disclosed in European Patent Application No. 91202655.6 filed on October 9, 1991.

[0095]

[0093] The compositions and methods of the present invention may utilize another bleaching system, such as ozone and chlorine dioxide, etc. Bleaching using 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.

[0096]

[0094] Colorant

[0095] 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.

[0097] 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.

[0098] 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 an acid are particularly preferred.

[0099] 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.

[0100] 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.

[0101] Among the pyridine derivatives that can be mentioned are compounds such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and their addition salts. Other pyridine oxide bases useful in the present disclosure are, for example, the 3-aminopyrazolo[1,5-a]pyridine oxide base or its addition salt described in patent application FR2801308. Examples that can be mentioned are pyrazolo[1,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine, 2-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyrid-3-ylamine, (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine, pyrazolo[1,5-a]pyridine-3,5-diamine, 5-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridine-5-ol, 3-aminopyrazolo[1,5-a]pyridine-4-ol, 3-aminopyrazolo[1,5-a]pyridine-6-ol, 3-aminopyrazolo[1,5-a]pyridine-7-ol, 2- quadrature -hydroxyethoxy-3-amino-pyrazolo[1,5-a]pyridine; 2-(4-dimethylpiperazinium-1-yl)-3-amino-pyrazolo[1,5-a]pyridine; and their addition salts.

[0102] More specifically, from

[0101] , the oxidation bases useful in the present disclosure are selected from 3-aminopyrazolo-[1,5-a]-pyridine, preferably substituted on the carbon atom at the 2-position by the following: (a) one (di)(C1-C6)(alkyl)amino group, wherein the alkyl group may be substituted with at least one of hydroxy, amino, and imidazolium groups; (b) a 5- to 7-membered chain and one heterocycloalkyl group containing 1 to 3 heteroatoms, which is potentially cationic and potentially substituted with one or more (C1-C6-alkyl, for example, di(C1-C4)alkylpiperazinium); or (c) one (C1-C6)alkoxy, one or more hydroxy groups, for example, ortho-hydroxyalkoxy, and its addition salts, potentially substituted.

[0103] Among the pyrimidine derivatives that can be mentioned are compounds such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and their addition salts, and in the case of tautomeric equilibria, their tautomeric forms.

[0104] 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.

[0105]

[0102] 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.

[0106]

[0103] 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.

[0107]

[0104] 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.

[0108]

[0105] 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 can be mentioned are azo direct dyes, alone or as a mixture; (poly)methine dyes, such as cyanine, hemicyanine and styryl; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes, and natural direct dyes. Many direct dyes are cationic direct dyes. Hydrazonocational dyes, azocational dyes, and diazocational dyes can be mentioned. Specific examples include Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof: Among others, natural direct dyes that can be used according to the present disclosure include lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechuic aldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or infusions containing these natural dyes, in particular henna-based compresses, or extracts can also be used. If present, the direct dye(s) more specifically correspond to from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight of the total weight of the composition of the present disclosure.

[0109]

[0106] Alkalizing agent

[0107] 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 render such a composition alkaline. In a further embodiment, the alkalizing agent can be selected from alkanolamines, such as monoethanolamine (MEA) and isopropanolamine. The alkalinity may be derived from an ammonium compound (e.g., NH4OH). One or more alkalizing agents can be present in an amount greater than about 0, or 1, 2, 3, 4, 5, 10 to about 5, 10, 13, 15, 18, 20, 25, or 30 wt% of the total composition.

[0110]

[0108] The oxidative hair cream composition may be in the form of a surfactant cream, an aqueous solution, a homogeneous dispersion, or a suspension, or even a liquid. 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.

[0111] [

[0109] ]The oxidative hair cream composition of the present invention also contains at least one colorant which is a thiophene azo chromophore. Generally, thiophene azo colorants can be characterized as having an absorbance in the range of about 400 nanometers to about 700 nanometers when measured by UV-vis spectroscopy. In one aspect of the present invention, the thiophene azo colorant can have a maximum absorbance in the range of 500 nanometers to 650 nanometers, or a maximum absorbance in the range of 540 nanometers to 700 nanometers, or further a range of 540 nanometers to 630 nanometers.

[0112] [

[0110] ]As a function of the manufacturing method, the thiophene azo colorant has a molecular weight typically represented as a molecular weight distribution. Thus, the molecular weight of the thiophene azo colorant is generally reported as the average molecular weight determined by its molecular weight distribution.

[0113] [

[0111] ]In one aspect, the thiophene azo colorant may be a neutral or uncharged molecule. In a further aspect, the colorant may be nonionic, anionic, or cationic. The thiophene azo colorant may contain a chromophore having both a positive charge and a negative charge. Further, the thiophene azo colorant may contain a chromophore that is a zwitterion or ampholyte.

[0114] [

[0112] ]The thiophene azo colorant may be alkoxylated. Alkoxylation is carried out by procedures well known to those skilled in the art (see, for example, USPN 4,137,243; 5,082,938; 5,135,972; 5,591,833; 6,593,483; 7,587,857; 9,056,963; and 9,068,081).

[0115] [

[0113] ]In one aspect of the present invention, the oxidative hair cream composition has the formula I:

[0116] [[Chemical formula]]

[0117] [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, -(CH2) n -O-R x 、-(CH2) 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)2R x 、-S(O)2OR x 、-S(O)2O - 、-S(O)2NR x R y 、-NR x C(O)R y 、-NR x C(O)OR y 、-NR x C(O)SR y 、-NR x C(O)NR y R x 、-OR x 、-NR x R y 、-P(O)2R x 、-P(O)(OR x )2、-P(O)(OR x )O - 、and -P(O)(O - )2 and is independently selected from the group consisting of; the subscript n is an integer from 0 to 4, preferably an integer from 0 to 1, most preferably an integer of 0, preferably R 11 、R 12 、and R 13At least one of which 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)2R x , -S(O)2OR x , -P(O)2R x , and -P(O)(OR x )2 group is an electron-withdrawing group selected from, 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, -(CH2) n -O-R x , -(CH2) n -NR x R y , -OR x , and -NR x R y selected from, R 16、 R 17、 R 18、 R 19 , R 110 at least one of which is -OR x , or -NR x R y is] contains a thiophene azo colorant. 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、 R18、 R 19 、R 110 Among two or more of them, they 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. If two of R x 、R y 、or R z 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.

[0118]

[0114] In one aspect of the present invention, the oxidative hair cream composition has the formula V:

[0119]

Chemical formula

[0120] [wherein, the R 56 、R 57 、R 58 、R 59 、and R 510 groups are hydrogen, halogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, -(CH2) n -O─R x 、-(CH2) 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 、-NRx 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 independently selected from; 56、 R 57、 R 58、 R 59 , R 510 Two or more of can be linked together via a covalent bond to form a ring structure. ]. x , R y and R z is hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, and R u independently selected from the group consisting of: R u R is an organic group composed of one or more organic monomers having the monomer molecular weight in the range of 28 to 500, preferably 43 to 350, and even more preferably 43 to 250. 56、 R 57、 R 58、 R 59 , R 510 Two or more of may be linked together via a covalent bond to form a ring structure. In combination with the benzene ring, the ring may form structures including, but not limited to, naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, indoline, and isoindoline. The ring structure may be joined with one or more groups, such as R 56 It may be further substituted with R x , R y , or R z When two of R 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. The ring structure can be formed by adding one or more R 56It may be further substituted with a group.

[0121]

[0115] In yet another aspect of the present invention, the oxidative hair cream composition contains a thiophene azo colorant of formula IV:

[0122]

Chemical formula

[0123] [wherein each x and y is independently an integer from 0 to 20].

[0124]

[0116] It is contemplated that other colorants capable of forming the colorant portion of the oxidative hair cream composition in combination with the thiophene azo colorant are also within the scope of the present invention. For example, colorants selected from one or more of the following classes may be suitable: acid dyes, basic dyes, direct dyes, solvent dyes, mordant dyes, substantive dyes, indigoid dyes, reactive dyes, disperse dyes, sulfur dyes, fluorescent dyes; dyes, both organic and inorganic; natural colorants, etc.

[0125]

[0117] The oxidative hair cream composition of the present invention is prepared by combining at least one oxidizing agent with at least one thiophene azo colorant. The oxidative hair cream composition thus formed can be a substantially homogeneous mixture.

[0126]

[0118] 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 thiophene azo colorant; and (c) Combining at least one oxidizing agent with at least one thiophene azo colorant to form a thiophene azo colorant-containing oxidative hair cream.

[0127]

[0119] The method for applying color to hair according to the present invention consists of the following steps: (a) Preparing an oxidative hair cream containing a thiophene azo colorant; (b) Applying the oxidative hair cream containing a thiophene azo colorant 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.

[0128]

[0120] A method for decolorizing and applying color to hair according to the present invention comprises the following steps: (a) Preparing an oxidative hair cream containing a thiophene azo colorant; (b) Applying the oxidative hair cream containing a thiophene azo colorant 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.

[0129]

[0121] 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.

[0130]

[0122] 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 thiophene azo colorant contained in the hair cream and / or the amount of the thiophene azo colorant contained in the hair cream. For example, increasing the amount of the thiophene azo colorant in the hair cream can result in the color on the hair lasting longer. In contrast, when the amount of the thiophene azo colorant contained in the hair cream is small, the time the color lasts on the hair can be shortened. 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.

[0131]

[0123] In one aspect of the present invention, the amount of the thiophene azo colorant in the hair cream ranges from 0.0001% to 10% or from 0.1% to 5%.

[0132]

[0124] In one aspect of the present invention, the molecular weight of the thiophene azo colorant in the hair cream ranges from 100 to 10000 or from 200 to 5000 or from 300 to 2000.

[0133]

[0125] At least one of the thiophene azo 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 thiophene azo 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 onto the hair, contacting the oxidative hair cream composition with the hair for a period of time, and further agitating, rinsing, and / or drying the hair thus treated.

[0134]

[0126] 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 thiophene azo colorant in the hydrogen peroxide cream agent rather than in the second component. However, alternatively, it is conceivable to place the thiophene azo colorant in the second component.

[0135]

[0127] Thus, in one embodiment, at least one thiophene azo colorant is mixed into a cream agent containing an oxidizing agent. Immediately prior to use, the cream agent containing the thiophene azo 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 thiophene azo 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.

[0136] The present invention described herein is mainly directed to oxidative hair creams containing thiophene azo colorants, but the invention is not limited to only these compositions. The oxidative hair cream may contain a combination of a thiophene azo colorant and another colorant. Other colorants include, for example, dyes, pigments, and combinations thereof.

[0137]

[0129] 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; and 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.

[0138] Suitable pigments include pigments selected from the group consisting of flavanthrone, indanthrone, indanthrone chloride containing 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide (the imide group may be unsubstituted or substituted with C1-C3-alkyl or phenyl or a heterocyclic radical, and the phenyl and heterocyclic radical may further carry a substituent that does not impart water solubility), anthrapyrimidinecarboxylic acid amide, violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyanine which may contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromochloro-copper phthalocyanine containing up to 14 bromine atoms per molecule, and mixtures thereof.

[0139]

[0131] In one aspect of the invention, the components of the oxidative hair care composition are 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 agent) 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 admixed by imparting 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 particles 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.

[0140]

[0132] 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.

[0141]

[0133] 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. The various optional oxidative hair cream composition raw material components, when present in the composition here, should be utilized at concentrations that customarily provide their desired contributions to the composition or the hair bleaching 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.

[0142]

[0134] Example ​​

[0135] Several 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. Using a SpeedMixer at 1500 rpm, each sample was mixed for a minimum of 90 seconds until a visually homogeneous mixture was obtained. (SpeedMixer, Inc., Landrum, SC). The amount of color contained in each sample was adjusted so that each sample exhibited the same color intensity. The maximum absorbance of the colored cream 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.

[0143]

[0136] 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 Using the number of equivalent days at room temperature for 50% deterioration of the color, the ratings were made according to Table 1. A rating of "1" means the most stable, while a rating of "5" means the least stable.

[0144]

[0137]

[0145]

Table 1

[0146]

[0138] The results of the colorant and stability tests of the present invention are shown in Table 2A. The results of the comparative colorant and stability tests are shown in Table 2B.

[0147]

[0139]

[0148]

Table 2A

[0149]

[0140]

[0150]

Table 2B

[0151]

[0141] 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).

[0152]

[0142] Color performance evaluation

[0143] 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) oxidative cream agent

[0144] Procedure:

[0145] 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 tip 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-i 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 measured values were used.

[0153]

[0146] CIE WI is a good measure of how well the hair has been lightened. The initial 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 initial hair was recorded. A larger ΔWI indicates better lightening of the hair.

[0154]

[0147] The WI and ΔWI values of the initial hair, the bleaching agent control (without dye), and the bleaching agent compositions containing Example 1, Example 2, and Comparative Example 10 (External D&C Violet 2) are shown in Table 3. The bleaching agent compositions using Example 1 and Example 2 resulted in better lightening than the bleaching agents using the bleaching agent control and Comparative Example 10.

[0155]

[0148]

[0156]

Table 3

[0157]

[0149] 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 middle color” tone is cast on the decolorized hair. This true middle color 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 middle color tones, making this tone into an effectively dull color. This dye can be delivered by 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 middle color 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 that also correct the color to dull the true middle color tone.

[0158]

[0150] All references, including publications, patent applications, and patents cited herein, are hereby incorporated by reference in their entirety to the same extent as if each reference were individually and specifically indicated to be incorporated by reference.

[0159]

[0151] 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 serve as a concise way of referring individually to each distinct value falling within that range, unless otherwise indicated herein, and each distinct value is incorporated herein as if 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.

[0160] Here, preferred embodiments of the subject matter of this application are described, 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 described herein to be practiced in a form 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, wherein the composition comprises at least one thiophene azo colorant and at least one oxidative hair cream raw material component.

2. The oxidative hair cream composition according to claim 1, wherein the composition is liquid.

3. The oxidative hair cream composition according to claim 1, wherein the composition comprises at least one depigmenting agent.

4. The oxidative hair cream composition according to claim 4, wherein the at least one depigmenting agent is a depigmenting agent of Category 1.

5. The oxidative hair cream composition according to claim 4, wherein the at least one depigmenting agent is a depigmenting agent of Category 2.

6. The oxidative hair cream composition according to claim 1, wherein the at least one oxidative hair cream raw material component is hydrogen peroxide.

7. The oxidative hair cream composition according to claim 6, wherein the composition contains 0.01% to 33% hydrogen peroxide.

8. The oxidative hair cream composition according to claim 6, wherein the composition contains 0.1% to 15% hydrogen peroxide.

9. The oxidative hair cream composition according to claim 1, wherein the at least one thiophene azo colorant has a maximum absorbance in the range of 540 nm to 700 nm.

10. The thiophene azo colorant is of Formula I: 【Chemical 1】 [Wherein each R １１ ~R １１０ groups are independently selected from the group consisting of hydrogen, deuterium, and R ｖ ; each R ｖ is halogen, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, -(CH ２ ) ｎ -O-R ｘ , -(CH ２ ) ｎ -NR ｘ R ｙ , -C(O)R ｘ , -C(O)OR ｘ , -C(O)O － , -C(O)NR ｘ R ｙ , -OC(O)R ｘ , -OC(O)OR ｘ , -OC(O)NR ｘ R ｙ , -S(O) ２ R ｘ , -S(O) ２ OR ｘ , -S(O) ２ O － , -S(O) ２ , -S(O) ｘ NR ｙ , -NR ｘ C(O)R ｙ , -NR ｘ C(O)OR ｙ , -NR ｘ C(O)SR ｙ , -NR ｘ C(O)NR ｙ R ｚ , -OR ｘ , -NR ｘ R ｙ , -P(O) ２ R ｘ , -P(O)(OR ｘ ) ２ , -P(O)(OR ｘ )O － , and -P(O)(O － ) ２ are independently selected from the group consisting of; the subscript n is an integer from 0 to 4, R ｘ , R ｙ and R ｚ is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, and R ｕ ; R ｕ is an organic group composed of one or more organic monomers, and the monomer molecular weight is in the range of 28 to 500] is a dye according to the oxidative hair cream composition of claim 1.

11. Said R １１ and R １２ and at least one of R １３ is a group selected from 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 and is an electron-withdrawing group selected from the groups, the oxidative hair cream composition according to claim 10.

12. Said R １１ and R １３ groups are -CN groups, and R １２ is a methyl group. The oxidative hair cream composition according to claim 10.

13. R １６、 R １７、 R １８、 R １９ 、R １１０ is independently selected from hydrogen, halogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, 2-butyl group, tert-butyl group, -(CH ２ ), ｎ -O-R ｘ 、-(CH ２ ), ｎ -NR ｘ R ｙ 、-OR ｘ 、and -NR ｘ R ｙ is independently selected from, at least one of R １６、 R １７、 R １８、 R １９ 、R １１０ is -OR ｘ 、or -NR ｘ R ｙ ; the oxidative hair cream composition according to claim 10

14. R １６、 R １７、 R １８、 R １９ 、 R １１０ The oxidative hair cream composition according to claim 10, wherein two or more of them are linked to each other via a covalent bond to form a ring structure condensed with the benzene ring of formula I.

15. The oxidative hair cream composition according to claim 14, wherein the ring structure condensed to the benzene ring of Formula I is one of naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, indoline, and isoindoline.

16. wherein the ring structure is substituted with one or more R １６ groups, the oxidative hair cream composition according to claim 15.

17. R ｘ , R ｙ , or R ｚ wherein two of them are bonded to the same carbon or nitrogen group to form the ring structure, the oxidative hair cream composition according to claim 14.

18. The oxidative hair cream composition according to claim 17, wherein the ring structure is one of piperazine, piperidine, and pyrrolidine.

19. wherein the ring structure is further substituted with one or more R １６ groups, the oxidative hair cream composition according to claim 18.

20. The at least one thiophene azo colorant is of the following structure: [[Chemical Formula 2]] [wherein each x and y is independently an integer from 0 to 20] is a dye according to claim 10.

21. A method for treating hair, comprising: (a) preparing the oxidative hair cream composition according to claim 20; and (b) contacting the oxidative hair cream composition with human hair. ​

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