Oxidative hair cream compositions containing thiophene azo colorants

Abstract

The present invention relates to an oxidative hair cream composition comprising at least one oxidative hair cream ingredient and at least one thiophene azo colorant. The present invention also relates to a method for treating hair, the method comprising the steps of: (a) providing an oxidative hair cream composition, wherein the composition comprises at least one thiophene azo colorant and at least one oxidative hair cream ingredient, and (b) contacting the oxidative hair cream composition with human hair.

Description

Technical Field

[0001] The present invention relates to an oxidative hair cream composition comprising at least one oxidative hair cream ingredient and at least one thiophene azo colorant. Background Art

[0002] Human hair is arbitrarily assigned a scale with varying degrees of severity describing its darkness (or lightness). Black hair is assigned a grade of one, medium brown hair a grade of five, and light blonde hair a grade of ten, with several subtle differences between them. Bleaching hair is a chemical process by which melanin particles are gradually destroyed by bleaching agents, thereby producing lighter hair colors. Melanins do not all lighten at the same rate. Eumelanin breaks down more easily than pheomelanin. Due to this property, dark hair, when bleached, preferentially undergoes the destruction of melanin, which results in a visual enhancement of the red pigment and an undesirable warm orange-red or "brassy" hue projected onto the bleached hair. In order to neutralize this warm color, a hair dye of a gloomy nature is almost always applied during or after the bleaching process.

[0003] Based on their chemical composition and their strength, hair bleaching agents can be divided into two groups, designated as Class 1 and Class 2. Class 1 bleaches are liquid or cream-based compositions that utilize alkaline hydrogen peroxide solutions as the primary oxygen generator to oxidize and bleach hair melanin, usually in conjunction with a hair dyeing process. Just 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 30-60 minutes. Depending on the concentration of hydrogen peroxide used, such compositions can lighten hair by up to 4 levels. For example, under favorable conditions, level 6 hair can be lightened to level 10.

[0004] Class 2 bleaches are usually powder compositions, some in the form of creams, based on persulfates (ammonium, potassium, sodium) as an auxiliary or synergistic supply of active oxygen and silicates and / or carbonates as a source of alkalinity. Similar to Class 1 bleaches, they are mixed with a hydrogen peroxide solution before use to form a workable cream that can be applied to the hair. The hydrogen peroxide itself can be incorporated into the powder bleach in solid form, and all that is required to obtain a workable cream is to add water to the powder. Typically, a third separately packaged component called bleaching oil is added to the bleaching powder and peroxide at the time of use. The bleaching oil may contain a humectant and other conditioning agents. Class 2 bleaches can lighten more than seven levels, which cannot be achieved with Class 1 bleaches. They are generally used when more than four levels of lightening are required, for example when lightening level 5 hair or darker hair to a light yellow.

[0005] Due to the basic warm tones exposed at various bleaching levels, a toning process that neutralizes the warm tones and gives the hair a pleasant natural appearance is usually accompanied by hair lightening. Toners are divided into three shades: blue-green, blue and purple, commonly referred to as drabbing or graying shades. These shades or combinations thereof are recommended for neutralizing the spectrum of the base color exposed during the lightening process. For example, light brown hair will expose a yellow base color when bleached. Therefore, according to color laws, a purple-based toner will neutralize the light yellow hue to produce a white-gold or silver-gold tone. The concentration of the toner should be adjusted so that the lightening is not masked by color deposition.

[0006] According to the present invention, there is a single-step process using a hair bleach composition that can simultaneously lighten the hair and effectively deposit a variety of shades of color. This is achieved by including a dye in the bleaching composition. Suitable dyes for this application need to: (a) have the desired blue-purple hue to neutralize the yellowish hue, (b) be stable in the bleach, (c) have a good toxicity profile, and (d) be easily mixed into and remain homogeneous in the oxidizing composition.

[0007] Therefore, there is a continuing need for improved colorants for this application. The thiophene azo dyes and oxidative hair care compositions containing the dyes disclosed herein offer advantages over previous efforts in this area, such as better lifting, better hue, better mixing with hair cream compositions, and improved toxicity profiles. Summary of the invention

[0008] In one aspect, the present invention is directed to an oxidative hair cream composition, wherein the composition comprises at least one thiophene azo colorant and at least one oxidative hair cream ingredient.

[0009] In another aspect, the thiophene azo colorant is a dye according to formula I:

[0010]

[0011] Each R 11 To R 110 The groups are independently selected from hydrogen, deuterium and R v ; Each R v independently selected from halogen, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, -(CH2) n -OR 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 ) - and -P(O)(O - )2, wherein the index n is an integer from 0 to 4; and wherein R x , R y and R z R is independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, and u ; R u It is an organic group composed of one or more organic monomers, wherein the molecular weight of the monomers is 28 to 500.

[0012] In another aspect, the at least one thiophene azo colorant is a dye according to the following structure:

[0013]

[0014] wherein each x and y is independently an integer from 0 to 20.

[0015] In another aspect, the present invention is directed to a method for treating hair comprising the steps of: (a) providing an oxidative hair cream composition, wherein the composition comprises at least one thiophene azo colorant and at least one oxidative hair cream ingredient, and (b) contacting the oxidative hair cream composition with human hair. DETAILED DESCRIPTION

[0016] The present invention describes an oxidative hair cream comprising at least one oxidative hair cream ingredient and at least one colorant comprising a thiophene azo chromophore. The oxidative hair cream comprising the thiophene azo colorant is suitable for direct application to hair (e.g., human hair, animal hair, etc.) and provides improvements in stability and hue over prior art hair dyes.

[0017] As used herein, the term "hair" is intended to include keratin fibers such as human hair, animal hair, and the like.

[0018] 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, glycidyl oxide, ethylene oxide, or propylene oxide.

[0019] As used herein, the terms "polyalkyleneoxy" and "polyoxyalkylene" used interchangeably herein generally refer to a molecular structure comprising the following repeating units: -CH2CH2O-, -CH2CH2CH2O-, -CH2CH2CH2CH2O-, -CH2CH(CH3)O-, -CH2CH2CH(CH3)O-, and any combination thereof. In addition, the polyoxyalkylene component may be selected from one or more selected from C 2-20 Monomers of alkyleneoxy, glycidyl, glycidyl or mixtures thereof.

[0020] As used herein, unless otherwise indicated, the terms "alkyl" and "alkyl-terminated" are intended to include C2-C 100 Alkyl, C2-C 50 Alkyl, C5-C 25 Alkyl or even C 10 -C 20 alkyl.

[0021] As used herein, unless otherwise indicated, the term "aryl" is intended to include C5-C 18 Aryl, and in one aspect, comprises C5-C 12 alkyl.

[0022] As used herein, unless otherwise indicated, the term "alkyl" is intended to include C1-C 18 Alkyl, and in one aspect, comprises C1-C6 alkyl.

[0023] Unless otherwise indicated, the term "alkanoyl" as used herein refers to a group of the formula -C(O)R a A monovalent group, where R a is an alkyl group, preferably C3-C 29 alkyl.

[0024] As used herein, unless otherwise indicated, the term "alkenyl" refers to a monovalent group derived from an acyclic olefin by removing a hydrogen atom from any carbon atom. In the context of this definition, the term "acyclic olefin" refers to an acyclic hydrocarbon containing one or more carbon-carbon double bonds.

[0025] Unless otherwise indicated, the term "alkenoyl" as used herein refers to a group of the formula -C(O)R b A monovalent group, where R b is alkenyl, preferably C3-C 29 Alkenyl.

[0026] As used herein, unless otherwise indicated, the term "aroyl" refers to a radical of the formula -C(O)R c A monovalent group, where R c is aryl, preferably C6-C 10 Aryl.

[0027] The terms "ethylene oxide," "propylene oxide," and "butylene oxide" may be referred to herein by their typical names "EO," "PO," and "BO," respectively.

[0028] 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.

[0029] In the present invention, the oxidative hair cream composition comprises at least one oxidative hair cream ingredient. Oxidative hair cream ingredients include, for example but not limited to, oxidants, lubricating oils, surfactants (which may include nonionic, anionic, cationic, zwitterionic, betaine surfactants), polar solvents, chelating agents, pH adjusters, conditioners, and other ingredients and mixtures thereof. The oxidant may be selected from hydrogen peroxide. Hydrogen peroxide may be present in an amount of 0.01% to 33% by weight of the total composition, or even 0.1% to 15% by weight of the total composition.

[0030] The hair cream compositions of the present invention are typically water-based, comprising from about 0.01 to about 99%, preferably from about 0.1 to about 98%, more preferably from about 45 to about 95% by weight of the total composition of water.

[0031] lubricating oil

[0032] If desired, the hair cream composition may include one or more lubricating oils. Such oils will provide conditioning effects for hair. If present, such oils may account for about 0.001-45% by weight of the total composition, preferably about 0.01-40% by weight, more preferably about 0.1-35% by weight. Suitable oils include polysiloxanes such as dimethicone, phenyl polysiloxane, fatty alkyl polysiloxanes such as cetyl or stearyl dimethicone, or polysiloxane surfactants, which are commonly referred to as dimethicone copolyols or cetyl dimethicone copolyols. Also suitable are various animals, plants or mineral oils derived from plants or animals, or synthetic oils. Examples include oils from sunflower, castor seeds, orange, lemon, jojoba, mineral oil, etc. Common other examples include cetearyl alcohol, lauryl alcohol, myristyl alcohol, lanolin alcohol, coconut alcohol, etc.

[0033] Surfactants

[0034] The oxidative dye composition may include one or more surfactants. Suitable surfactants include anionic surfactants, nonionic surfactants, amphoteric surfactants, etc. If present, the surfactant may account for about 0.001-50% by weight of the first composition, preferably about 0.005-45% by weight, and more preferably about 0.1-40% by weight.

[0035] Nonionic surfactants

[0036] Examples of nonionic surfactants include alkoxylated alcohols or ethers, alkoxylated carboxylic acids, sorbitan derivatives, etc. Alkoxylated alcohols or ethers are formed by the reaction of an alcohol with an alkylene oxide, typically ethylene oxide or propylene oxide. Preferably, the alcohol is a fatty alcohol having 6 to 30 carbon atoms and a linear or branched, saturated or unsaturated carbon chain. Examples of such ingredients include steareth 2-30, which is formed by reacting stearyl alcohol and ethylene oxide, wherein the number of ethylene oxide repeating units is 2 to 30; laureth 2-30, which is formed by reacting lauryl alcohol and ethylene oxide, wherein the number of ethylene oxide repeating units is 2 to 30; oleth 2-30, which is formed by reacting oleyl alcohol and ethylene oxide, wherein the number of ethylene oxide repeating units is 2 to 30; ceteareth 2-100, which is formed by reacting a mixture of cetyl alcohol and stearyl alcohol with ethylene oxide, wherein the number of ethylene oxide repeating units in the molecule is 2 to 100; ceteth 1-45, which is formed by reacting cetyl alcohol with ethylene oxide, wherein the number of ethylene oxide repeating units is 1 to 45; etc. It is particularly preferred that the nonionic surfactant is steareth-20 or ceteth-20. Also suitable are alkoxylated carboxylic acids which are formed by reaction of carboxylic acids with alkylene oxides or with polymeric ethers.

[0037] Various types of alkoxylated sorbitan and alkoxylated sorbitan derivatives are also suitable. For example, alkoxylation of sorbitan, particularly ethoxylation provides polyalkoxylated sorbitan derivatives. Esterification of polyalkoxylated sorbitan provides sorbitan esters such as polysorbates. Examples of such ingredients include polysorbate 20-85, sorbitan oleate, sorbitan palmitate, sorbitan sesquiisostearate, sorbitan stearate, and the like. In a preferred embodiment, polysorbate 20 is preferred.

[0038] Anionic surfactants

[0039] The hair cream composition may optionally contain one or more anionic surfactants. The preferred range of anionic surfactants is about 0.01-25% by weight, preferably 0.5-20% by weight, more preferably 1-15% by weight of the total oxidizing composition. Suitable anionic surfactants include those generally having the formula ROSO3M and RO(C2H4O) x Alkyl and alkyl ether sulfates of SO3M wherein R is an alkyl or alkenyl group of about 10 to about 20 carbon atoms, x is 1 to about 10, and M is a water-soluble cation such as an ammonium, sodium, potassium or triethanolamine cation.

[0040] Another type of anionic surfactant useful in the compositions of the present invention is a water-soluble salt of an organic sulfuric acid reaction product of the general formula: R1-SO3-M, wherein R1 is selected from a straight or branched chain saturated aliphatic hydrocarbon radical having from about 8 to about 24 carbon atoms, preferably from 12 to about 18 carbon atoms; and M is a cation. Examples of such anionic surfactants are salts of organic sulfuric acid reaction products of hydrocarbons such as normal paraffins having from 8 to 24 carbon atoms and a sulfonating agent such as sulfur trioxide.

[0041] Also suitable as anionic surfactants are the reaction products of fatty acids esterified with isethionate and neutralized with sodium hydroxide, or fatty acids reacted with alkanolamines or ammonium hydroxide. For example, the fatty acids can be derived from coconut oil. Examples of fatty acids also include lauric acid, stearic acid, oleic acid, palmitic acid, and the like.

[0042] In addition, succinic acid esters and succinimide esters are suitable anionic surfactants. Such compounds include, for example, disodium N-octadecyl sulfosuccinate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinate; and esters of sodium sulfosuccinate, such as dihexyl ester of sodium sulfosuccinate, dioctyl ester of sodium sulfosuccinate, and the like.

[0043] Other suitable anionic surfactants include olefin sulfonates having from about 12 to 24 carbon atoms. The term "olefin sulfonate" refers to compounds that can be prepared by sulfonating an alpha-olefin with uncomplexed sulfur trioxide and then neutralizing the acid reaction mixture under conditions such that any sultone formed in the reaction is hydrolyzed to yield the corresponding hydroxyalkane sulfonate. The alpha-olefin from which the olefin sulfonate is derived is a monoolefin having from about 12 to 24 carbon atoms, preferably from about 14 to 16 carbon atoms.

[0044] Other types of suitable anionic organic surfactants are β-alkoxy alkane sulfonates or water-soluble soaps thereof, such as C 10-20 Salts of fatty acids, for example soaps based on coconut and tallow. Preferred salts are the ammonium, potassium and sodium salts.

[0045] Another class of anionic surfactants includes N-acyl amino acid surfactants and their salts (alkali metal, alkaline earth metal and ammonium salts) having the following formula: wherein R1 is C 8-24 Alkyl or alkenyl, preferably C 10-18 ; R2 is H, C 1-4 Alkyl, phenyl or -CH2COOM; R3 is CX2- or C 1-2 Alkoxy, wherein each X is independently H or C 1-6 Alkyl or alkyl ester, n is 1-4, M is H or a salt-forming cation as described above. Examples of such surfactants are N-acyl sarcosinates, including lauroyl sarcosinate, myristoyl sarcosinate, cocoyl sarcosinate and oleoyl sarcosinate, preferably in sodium or potassium form.

[0046] Cationic, zwitterionic or betaine surfactants

[0047] Certain types of amphoteric, zwitterionic or cationic surfactants may also be used as amphiphilic surface-active materials. A description of such surfactants is listed in U.S. Patent No. 5,843,193, which is incorporated herein by reference in its entirety.

[0048] Amphoteric surfactants useful in the compositions of the present invention are generally described as derivatives of secondary or tertiary aliphatic amines in which one aliphatic group is a straight or branched chain alkyl group of 8 to 18 carbon atoms and the other aliphatic group contains an anionic group such as carboxyl, sulfonate, sulfate, phosphate or phosphonate.

[0049] Likewise suitable amphoteric surfactants are mono- or dicarboxylates, for example cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, cocoamphocarboxyglycinate and cocoamphoacetate.

[0050] Other types of amphoteric surfactants include those of the formula R-NH(CH2) nCOOM aminoalkanoate or iminodialkanoate of the following formula: R—[(CH2) m COOM]2 and mixtures thereof, wherein n and m are 1-4, R is C 8-22 Alkyl or alkenyl, M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium. Examples of such amphoteric surfactants include n-alkylamino propionate and n-alkyliminodipropionate. Zwitterionic surfactants are also suitable for use in the composition of the present invention, and include betaines, such as higher alkyl betaines, such as coconut dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl α-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl γ-carboxyethyl betaine, and mixtures thereof. Also suitable are sulfobetaines and amidobetaines, such as coconut dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, etc. Particularly preferred is cocoamidopropyl betaine.

[0051] Polar solvents

[0052] The hair cream composition may also contain various non-aqueous polar solvents other than water, including monohydric alcohols, dihydric alcohols or polyhydric alcohols, and similar water-soluble ingredients. If present, such polar solvents may be about 0.01-25% by weight of the first composition, preferably about 0.05-15% by weight, and more preferably about 0.1-10% by weight of the polar solvent. Examples of suitable monohydric alcohols include ethanol, isopropanol, benzyl alcohol, butanol, amyl alcohol, ethoxyethanol, and the like. Examples of usable dihydric or polyhydric alcohols and sugars and other types of humectants include glycerol, glucose, fructose, mannose, mannitol, malitol, lactitol, inositol, and the like. Suitable glycols include propylene glycol, butylene glycol, ethylene glycol, polyethylene glycols having 4 to 250 ethylene glycol repeating units, ethoxydiglycol, and the like.

[0053] Chelating agents

[0054] The oxidative dye composition may optionally contain 0.0001-5%, preferably 0.0005-3%, more preferably 0.001-2% of one or more chelating agents which are capable of complexing with and inactivating metal ions to prevent them from adversely affecting the stability or effectiveness of the composition. In particular, the chelating agent will chelate metal ions in the water, preventing these ions from interfering with the deposition of the dye and reaction with the surface of the hair fiber. Suitable chelating agents include EDTA and its calcium, sodium or potassium derivatives, HEDTA, sodium citrate, TEA-EDTA, and the like.

[0055] pH Adjusters

[0056] It may also be necessary to add a small amount of acid or base to adjust the pH of the oxidative dye composition to the desired pH range. Suitable acids include hydrochloric acid, phosphoric acid, etidronic acid, etc. Suitable bases include sodium hydroxide, ammonium hydroxide, potassium hydroxide, etc. Primary, secondary or tertiary amines or their derivatives such as aminomethyl propanol, monoethanolamine, etc. are also suitable. Phosphates such as potassium phosphate, disodium hydrogen phosphate, etc. can also be used. The recommended range of pH adjusters is about 0.00001-8% by weight of the total composition, preferably about 0.00005-6% by weight, and more preferably about 0.0001-5% by weight.

[0057] Conditioning Agents

[0058] 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, nonvolatile hydrocarbons, nonvolatile hydrocarbon esters, and mixtures thereof.

[0059] Preferred conditioning agents for use herein include cationic surfactants, cationic polymers, insoluble silicone conditioning agents, amino functional silicones and saturated C 14 -C 22 Straight chain fatty alcohols and mixtures thereof.

[0060] When present, the insoluble silicone conditioning agent is present at a level of from about 0.1% to 10% by weight of the composition, preferably from about 0.1% to about 5%, more preferably from about 1% to about 3%. Suitable insoluble silicones include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof.

[0061] Other additional components

[0062] The compositions of the present invention also typically contain a number of other components commonly used in hair care compositions, such as shampoos, conditioners, styling aids and colorants, such as thickeners and diluents, which are well known to those skilled in the art. In addition, a variety of optional materials can be added to the compositions described herein at a level of about 0.001% to about 5% by weight of the composition, preferably about 0.01% to about 3% by weight, and more preferably about 0.05% to about 2% by weight. Such materials include proteins and polypeptides and their derivatives; water-soluble or solubilizable 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 naphthol, benzoic acid, sodium benzoate and 2-phenoxyethanol; antioxidants, such as sodium sulfite, hydroquinone, sodium bisulfite, sodium metabisulfite and thioglycolic acid, sodium dithionite, isoascorbic acid and other mercaptans; H2O2 stabilizers, such as tin compounds such as sodium stannate, tin hydroxide and stannous octoate, acetanilide, phenazone ... cetin, colloidal silica, such as magnesium silicate, oxyquinoline sulfate, sodium phosphate and tetrasodium pyrophosphate; and hydroxybenzoic acid esters; humectants, such as hyaluronic acid, chitosan and starch-grafted sodium polyacrylate and methylcellulose, starch, higher fatty alcohols, paraffin oil, fatty acids, etc.; solvents; antimicrobial agents; low temperature phase modifiers, such as ammonium ion sources (such as NH4Cl); viscosity control agents such as magnesium sulfate and other electrolytes; quaternary ammonium compounds, such as distearyl-, dilauryl-, dihydrogenated tallow-, dimethyl ammonium chloride, dicetyl diethyl ammonium methylsulfate, ditallow dimethyl ammonium methylsulfate, disoybean oil dimethyl ammonium chloride (disoya dimethylammonium chloride) and dicocodimethylammonium chloride; enzyme stabilizers, such as water-soluble sources of calcium or borate materials; TiO2 and TiO2-coated mica; fragrances and fragrance solubilizers; and zeolites and their derivatives, and metal ion chelators such as polycarboxylates, aminopolycarboxylates, polyphosphonates, aminopolyphosphonates, etc., and water softeners such as sodium citrate, inorganic peroxy oxidants and enzymes.

[0063] Oxidant composition

[0064] In addition, the aqueous oxidizing cream composition also contains an oxidizing agent that will react with the hair bleaching agent. The most commonly used aqueous oxidizing agent is hydrogen peroxide, but other peroxides or oxidizing agents such as calcium peroxide may also be used. Preferably, the concentration of hydrogen peroxide in the aqueous oxidizing agent composition is about 10-40 volumes, i.e., the amount of hydrogen peroxide present in the composition based on volume.

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

[0066] Preferred sources of hydrogen peroxide for use herein may be any convenient source, including hydrogen peroxide itself. For example, perborates such as sodium perborate (any hydrate, but preferably monohydrate or tetrahydrate), sodium carbonate peroxyhydrate or equivalent percarbonate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or sodium peroxide may be used herein. Available oxygen sources are also useful, such as persulfate bleach (e.g., OXONE manufactured by DuPont). Monohydrated sodium perborate, sodium percarbonate, sodium persulfate and potassium persulfate are particularly preferred. Any convenient mixture of hydrogen peroxide sources may also be used.

[0067] The compositions of the present invention may also contain chlorine-type bleaching materials as bleaching agents. Such agents are well known in the art and include, for example, sodium dichloroisocyanurate ("NaDCC").

[0068] In one aspect of the invention, the peroxygen bleach component in the composition is formulated with an activator (peracid precursor). The content of the activator is about 0.01% by weight of the composition, preferably about 0.5% by weight, more preferably about 1% by weight to about 15% by weight, preferably to about 10% by weight, and more preferably to about 8% by weight. The bleach activator used herein is any compound that causes the in-situ generation of a peracid corresponding to the bleach activator when used in combination with a hydrogen peroxide source. Various non-limiting examples of activators are disclosed in U.S. Patent Nos. 5,576,282, 4,915,854 and 4,412,934. Other typical bleaches and activators that can be used in the present invention are also shown in U.S. Patent No. 4,634,551.

[0069] Preferred activators are selected from tetraacetylethylenediamine (TAED), benzoyl caprolactam (BzCL), 4-nitrobenzoyl caprolactam, 3-chlorobenzoyl caprolactam, benzoyloxybenzene sulfonate (BOBS), nonanoyloxybenzene sulfonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzene sulfonate (C 10-OBS), benzoyl valerolactam (BzVL), octanoyloxybenzene sulfonate (C8-OBS), perhydrolyzable esters and mixtures thereof, with benzoyl caprolactam and benzoyl valerolactam being most preferred. Particularly preferred bleach activators for a pH range of from about 8 to about 11 are those selected having an OBS or VL leaving group.

[0070] Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulfonate (NOBS); 4-[N-nonanoylaminocaproyloxy]-benzenesulfonic acid sodium salt (NACA-OBS), an example of which is described in U.S. Pat. No. 5,523,434; dodecanoyloxybenzenesulfonate (LOBS or C 12 -OBS); 10-undecylenoyloxybenzenesulfonate (UDOBS or C 11 -OBS, with unsaturation at position 10); and decanoyloxybenzoic acid (DOBA).

[0071] Preferred bleach activators are those described in: U.S. Pat. No. 5,998,350 to Burns et al.; U.S. Pat. No. 5,698,504 to Christie et al.; U.S. Pat. No. 5,695,679 to Christie et al.; U.S. Pat. No. 5,686,401 to Willey et al.; U.S. Pat. No. 5,686,014 to Hartshorn et al.; U.S. Pat. No. 5,405,412 to Willey et al.; U.S. Pat. No. 5,405,413 to Willey et al.; U.S. Pat. No. 5,130,045 to Mitchel et al.; and U.S. Pat. No. 4,412,934 to Chung et al., and co-pending patent application Ser. No. 08 / 064,564, all of which are incorporated herein by reference.

[0072] A quaternary substituted bleach activator may also be included. The compositions of the present invention preferably include a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP, preferably a quaternary substituted percarboxylic acid or a quaternary substituted peroxyimidic acid); more preferably the former. Preferred QSBA structures are further described in U.S. Pat. Nos. 5,686,015 to Willey et al.; 5,654,421 to Taylor et al.; 5,460,747 to Gosselink et al.; 5,584,888 to Miracle et al.; 5,578,136 to Taylor et al.; all of which are incorporated herein by reference.

[0073] Other bleach activators useful herein are amide substituted, as described in U.S. Pat. Nos. 5,698,504; 5,695,679; and 5,686,014, each of which is cited above. Preferred examples of such bleach activators include: (6-octanamidohexanoyl)oxybenzenesulfonate, (6-nonanamidohexanoyl)oxybenzenesulfonate, (6-decanamidohexanoyl)oxybenzenesulfonate, and mixtures thereof.

[0074] Other useful activators are disclosed in U.S. Pat. Nos. 5,698,504; 5,695,679; 5,686,014, each of which is cited above; and in U.S. Pat. No. 4,966,723 to Hodge et al. These activators include benzoxazine-type activators, such as -C(O)OC(R) fused at the 1,2-position. 1 )=N-part of the C6H4 ring.

[0075] 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 bleach activators are described in U.S. Pat. Nos. 6,133,216; 3,986,972; 6,063,750; 6,017,464; 5,958,289; 5,877,315; 5,741,437; 5,739,327; 5,004,558; and European Patent Nos. 790244, 775127, 1017773, 1017776; and WO 99 / 14302, WO 99 / 14296, WO 96 / 40661, all of which are incorporated herein by reference.

[0076] Depending on the activator and the exact application, good bleaching results can be obtained using a bleaching system with a pH of about 6 to about 13, preferably about 9.0 to about 11.5. Typically, for example, activators with electron-withdrawing moieties are used in the near-neutral or sub-neutral pH range. Bases and buffers can be used to ensure this pH.

[0077] Acyl lactam activators, such as those described in U.S. Pat. Nos. 5,698,504; 5,695,679 and 5,686,014, each of which is cited above, may also be used in the present invention, particularly acyl caprolactams (see, e.g., WO 94-28102A) and acyl valerolactams (see U.S. Pat. No. 5,503,639 to Willey et al., which is incorporated herein by reference).

[0078] Organic peroxides, especially diacyl peroxides, are also suitable for use. These are extensively described in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982, pp. 27-90, especially pp. 63-72, all of which are incorporated herein by reference. If diacyl peroxides are used, those that have the least adverse effect on fabric care (including color care) are preferred.

[0079] The compositions and methods of the present invention may also optionally include a metal-containing bleach catalyst, preferably a manganese and cobalt-containing bleach catalyst.

[0080] One class of metal-containing bleach catalysts is a catalyst system comprising a transition metal cation having defined bleach catalytic activity (e.g., copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations), an auxiliary metal cation having little or no bleach catalytic activity (e.g., zinc or aluminum cations), and a chelating agent having defined stability constants for the catalytic metal cation and the auxiliary metal cation, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in Bragg, U.S. Pat. No. 4,430,243.

[0081] If desired, the compositions herein can be catalyzed by manganese compounds. Such compounds and amounts of use are well known in the art and include, for example, manganese-based catalysts disclosed in U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; 5,114,606; and European Patent Application Publication Nos. 549,271A1; 549,272A1; 544,440A2; 544,490A1. Preferred examples of these catalysts include Mn IV 2(uO)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mn III 2(uO)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(ClO4)2、Mn IV 4(uO)6(1,4,7-triazacyclononane)4(ClO4)4, Mn III Mn IV 4(uO)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2(ClO4)3、Mn IV(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH3)3(PF6) and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. Nos. 4,430,243 and 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following: U.S. Pat. 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.

[0082] Cobalt bleach catalysts useful herein are known and are described, for example, in U.S. Patent Nos. 5,597,936; 5,595,967; 5,703,030; and ML Tobe, "Base Hydrolysis of Transition-Metal Complexes," Adv.Inorg.Bioinorg.Mech. , (1983), 2, pp. 1-94. The most preferred cobalt catalyst for use in the present invention is a catalyst having the formula [Co(NH3)5OAc]T y Pentaamine cobalt acetate salts wherein "OAc" represents the acetate moiety and "Ty" is the anion, particularly pentaamine cobalt chloride acetate, [Co(NH3)5OAc]Cl2; as well as [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 (referred to herein as "PAC").

[0083] These cobalt catalysts are readily prepared by known methods, such as taught in: U.S. Pat. Nos. 6,302,921; 6,287,580; 6,140,294; 5,597,936; 5,595,967; and 5,703,030; and 5,703,030; the Tobe article and references cited therein; and U.S. Pat. No. 4,810,410; J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, WL Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg.Chem. , 18 ,1497-1502(1979); Inorg.Chem. , 21 ,2881-2885(1982); Inorg.Chem. ,18 ,2023-2025(1979); Inorg.Synthesis,173-176(1960); and Journal of Physical Chemistry , 56 ,22-25(1952).

[0084] The compositions herein may also suitably comprise a transition metal complex of a macropolycyclic rigid ligand as a bleach catalyst. The amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably about 0.05 ppm to about 500 ppm (wherein "ppb" means parts per billion by weight and "ppm" means parts per million by weight).

[0085] Transition metal bleach catalysts of macrocyclic rigid ligands suitable for use in the compositions of the present invention may generally include known compounds, exemplified by, but not limited to, any of the following:

[0086] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0087] Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0088] 5,12-Dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II) dihydrate

[0089] Hexafluorophosphate

[0090] 5,12-Diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II) dihydrate

[0091] Hexafluorophosphate

[0092] Hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(III) hexafluorophosphate

[0093] 5,12-Dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II) dihydrate

[0094] Tetrafluoroborate

[0095] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(III)

[0096] Hexafluorophosphate

[0097] Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(III) hexafluorophosphate

[0098] Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0099] Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0100] Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0101] Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0102] Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II).

[0103] The hair cream composition of the present invention may further comprise at least one bleaching agent. The bleaching agent may be selected from the group consisting of Class 1 bleaching agents, Class 2 bleaching agents, and mixtures thereof.

[0104] In practice, but not by way of limitation, the compositions and methods herein can be adjusted to provide about at least one part per hundred million of active bleach catalyst material in a composition comprising a lipophilic fluid and a bleaching system, and will preferably provide about 0.01 ppm to about 25 ppm, more preferably about 0.05 ppm to about 10 ppm, and most preferably about 0.1 ppm to about 5 ppm of bleach catalyst material in a composition comprising a lipophilic fluid and a bleaching system.

[0105] The compositions herein may contain one or more bleach boosting compounds. Bleach boosting compounds provide increased bleaching effectiveness in lower temperature applications. Bleach boosters work with conventional peroxygen bleaching sources to provide increased bleaching effectiveness. This is typically achieved by in situ formation of active oxygen transfer agents such as dioxirane, oxaziridine or oxaziridinium salts. Alternatively, preformed dioxirane, oxaziridine and oxaziridinium salts may be used.

[0106] Suitable bleach boosting compounds for use according to the present invention are cationic imines, zwitterionic imines, anionic imines and / or polyionic imines having a net charge of from about +3 to about -3, and mixtures thereof. These imine bleach boosting compounds of the present invention include those having the following general structure:

[0107]

[0108] Where R 1 -R 4 It may be hydrogen or an unsubstituted or substituted group selected from phenyl, aryl, heterocycle, alkyl and cycloalkyl.

[0109] Among the preferred bleach boosting compounds are zwitterionic bleach boosters, which are described in U.S. Pat. Nos. 5,576,282 and 5,718,614. Other bleach boosting compounds include cationic bleach boosters described in U.S. Pat. Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO95 / 13351, WO95 / 13352 and WO95 / 13353.

[0110] Peroxygen sources are well known in the art and can be used in the present invention. The peroxygen sources include any of these well known sources, including peroxygen compounds and compounds that provide an effective amount of peroxygen in situ under consumer use conditions. The peroxygen source can include a hydrogen peroxide source, a peracid anion formed in situ by reaction of a hydrogen peroxide source and a bleach activator, a preformed peracid compound, or a mixture of suitable peroxygen sources. Of course, one of ordinary skill in the art will recognize that other peroxygen sources can be used without departing from the scope of the present invention. When a bleach boosting compound is present, it is preferably used in the bleaching system of the present invention together with a peroxygen source.

[0111] Also suitable as bleaching agents are preformed peracids. Preformed peracid compounds used herein are any convenient compounds that are stable and provide an effective amount of peracid or peracid anion under consumer use conditions. Preformed peracid compounds may be selected from percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof. Examples of these compounds are described in U.S. Patent No. 5,576,282 to Miracle et al.

[0112] One class of suitable organic peroxycarboxylic acids has the general formula:

[0113]

[0114] wherein R is an alkylene or substituted alkylene group containing 1 to about 22 carbon atoms, or a phenylene or substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl, -C(O)OH, or -C(O)OOH.

[0115] Organic peroxyacids suitable for use in the present invention may contain one or two peroxy groups and may be aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the following general formula:

[0116]

[0117] wherein Y can be, for example, H, CH3, CH2Cl, C(O)OH or C(O)OOH; and n is an integer from 0 to 20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

[0118]

[0119] wherein Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C(O)OH or C(O)OOH.

[0120] Typical monoperoxyacids useful herein include the alkyl and aryl peroxyacids, for example:

[0121] (i) Peroxybenzoic acid and ring-substituted peroxybenzoic acids, for example peroxy-α-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate) and o-carboxybenzoylaminoperoxycaproic acid (sodium salt);

[0122] (ii) aliphatic, substituted aliphatic and aralkyl monoperoxyacids, for example peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-(3-octylsuccinyl)aminoperoxycaproic acid (SAPA) and N,N-phthalamidoperoxycaproic acid (PAP);

[0123] (iii) Acylamino peroxyacids, for example the monononylamide of peroxysuccinic acid (NAPSA) or the monononylamide of peroxyadipic acid (NAPAA).

[0124] Typical diperoxy acids useful herein include alkyl diperoxy acids and aryl diperoxy acids, for example:

[0125] (i) 1,12-diperoxydodecanedioic acid;

[0126] (ii) 1,9-diperoxyazelaic acid;

[0127] (iii) diperoxytridecanedioic acid; diperoxysebacic acid and diperoxyisophthalic acid;

[0128] (iv) 2-decyldiperoxybutane-1,4-dioic acid;

[0129] (v) 4,4'-Sulfonylbisperoxybenzoic acid.

[0130] Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781 to Hartman and U.S. Pat. No. 4,634,551 to Burns et al.; European Patent Application No. 0,133,354 to Banks et al.; and U.S. Pat. No. 4,412,934 to Chung et al. Sources also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No. 4,634,551 to Burns et al. Persulfate compounds, such as OXONE commercially produced by EI DuPont de Nemours of Wilmington, Germany, can also be used as a suitable source of peroxymonosulfuric acid. PAP is disclosed, for example, in U.S. Pat. Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757 and 5,132,431.

[0131] Photobleaches are also suitable for use in the compositions of the present invention and include, but are not limited to, those described in US Pat. Nos. 4,217,105 and 5,916,481.

[0132] Enzyme systems can be used as bleaching agents. Hydrogen peroxide can also be present by adding an enzyme system (i.e. an enzyme and its substrate) capable of producing hydrogen peroxide. Such enzyme systems are disclosed in EP patent application 91202655.6 filed on October 9, 1991.

[0133] The compositions and methods of the present invention may employ other bleaching systems such as ozone, chlorine dioxide, etc. Bleaching with ozone may be accomplished by providing an ozone content of about 20 to about 300 g / m 3 This is accomplished by introducing an ozone-containing gas into the solution in contact with the hair. The gas:liquid ratio in the solution should be maintained at about 1:2.5 to about 1:6. U.S. Patent No. 5,346,588, incorporated herein by reference, describes a process utilizing ozone as an alternative to conventional bleaching systems.

[0134] Colorants

[0135] The coloring composition of the present disclosure may optionally contain one or more colorants different from the polymer colorant. These coloring compounds can be selected from oxidative dye precursors, direct dyes, pigments and mixtures thereof. Oxidative dyes are generally selected from one or more oxidation bases optionally combined with one or more color formers. For example, the oxidation base is selected from p-phenylenediamines, bis(phenyl)alkylenediamines, p-aminophenols, o-aminophenols and heterocyclic bases, and addition salts thereof.

[0136] Among the p-phenylenediamines, mention may be made of, for example, p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-p-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 2-fluoro-p-phenylenediamine. 2-isopropyl-p-phenylenediamine, N-(β-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-3-methyl-p-phenylenediamine, N-ethyl-N-(β-hydroxyethyl)-p-phenylenediamine, N-(β,γ-dihydroxypropyl)-p-phenylenediamine, N-(4'-aminophenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-β-hydroxyethoxy-p-phenylenediamine, 2-β-acetylaminoethoxy-p-phenylenediamine, N-(β-methoxyethyl)-p-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-p-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4'-aminophenyl)pyrrolidine, and acid addition salts thereof.

[0137] Among the above-mentioned p-phenylenediamines, p-phenylenediamine, p-toluenediamine, 2-isopropyl-p-phenylenediamine, 2-β-hydroxyethyl-p-phenylenediamine, 2-β-hydroxyethoxy-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, N,N-bis(β-hydroxyethyl)-p-phenylenediamine, 2-chloro-p-phenylenediamine and 2-β-acetylaminoethoxy-p-phenylenediamine, and addition salts thereof with acids are particularly preferred.

[0138] Among the bis(phenyl)alkylenediamines, mention may be made of, for example, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine, N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(4-methylaminophenyl)tetramethylenediamine, N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and addition salts thereof.

[0139] Among the p-aminophenols, there can be mentioned, for example, p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and addition salts thereof with acids. Among the o-aminophenols, there can be mentioned, for example, 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and addition salts thereof. Among the heterocyclic bases, there can be mentioned, for example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

[0140] Among the pyridine derivatives, mention may be made of compounds such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and addition salts thereof. Other pyridine oxidation bases that may be used in the present disclosure are 3-aminopyrazolo[1,5-a]pyridine oxidation bases or addition salts thereof, such as described in patent application FR 2801308. Examples that may be mentioned include pyrazolo[1,5-a]pyridine-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyridine-3-ylamine, 2-morpholin-4-ylpyrazolo[1,5-a]pyridine-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyridine-3-ylamine, (3-aminopyrazolo[1,5-a]pyridine-7-yl)methyl alcohol, 2-(3-aminopyrazolo[1,5-a]pyridin-5-yl)ethanol, 2-(3-aminopyrazolo[1,5-a]pyridin-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyridin-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-morpholine- 4-aminopyrazolo[1,5-a]pyridine-3-ylamine, pyrazolo[1,5-a]pyridine-3,5-diamine, 5-morpholin-4-ylpyrazolo[1,5-a]pyridine-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyridine-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[1,5-a]pyridine-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridine-7-yl)(2-hydroxyethyl)amino]ethanol, oxazolo[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-tetrahydroxyethoxy-3-amino-pyrazolo[1,5-a]pyridine; 2-(4-dimethylpiperazinium-1-yl)-3-amino-pyrazolo[1,5-a]pyridine; and addition salts thereof.

[0141] More particularly, the oxidation bases useful in the present disclosure are selected from 3-aminopyrazolo-[1,5-a]-pyridine and are preferably substituted on carbon atom 2 by the following groups:

[0142] (a) a (di)(C1-C6)(alkyl)amino group, wherein the alkyl group may be substituted with at least one hydroxyl, amino, or imidazolium group;

[0143] (b) a heterocycloalkyl group containing 5 to 7 chain members and 1 to 3 heteroatoms, which is potentially cationic and potentially substituted by one or more (C1-C6)alkyl groups, such as di(C1-C4)alkylpiperazine; or

[0144] (c) a (C1-C6)alkoxy group potentially substituted by one or more hydroxy groups, such as quadrature-hydroxyalkoxy, and addition salts thereof.

[0145] Among the pyrimidine derivatives, when tautomeric equilibrium exists, mention may be made of 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 addition salts thereof and tautomeric forms thereof.

[0146] Among the pyrazole derivatives, mention may be made of compounds such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diamino-pyrazole, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-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-(β-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-(β-hydroxyethyl)amino-1-methylpyrazole and addition salts thereof. 4,5-diamino-1-(β-methoxyethyl)pyrazole can also be used.

[0147] Pyrazole derivatives that may also be mentioned include diamino-N,N-dihydropyrazolopyrazolones, for example the following compounds and their addition salts: 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazolin-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazolin-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H,5H- Pyrazolo[1,2-a]pyrazolin-1-one, 2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazolin-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydropyrazolin-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazolin-3-one, 4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazoline -3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazolin-1-one, 2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazolin-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyrazolo[1,2-a]pyrazolin-1-one, 4-amino-1,2-diethyl-5-( Preferably, the heterocyclic base is 1-(4-(2-(4-pyrrolidin-1-yl)-1,2-dihydropyrazolin-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazolin-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazolin-1-one, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazolin-1-one and / or salts thereof. Preferably, 4,5-diamino-1-(β-hydroxyethyl)pyrazole and / or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazolin-1-one and / or salts thereof are used as heterocyclic bases.

[0148] The composition according to the present disclosure may optionally comprise one or more couplers, advantageously chosen from those conventionally used for dyeing or coloring keratin fibers. Among these couplers, mention may be made in particular of metaphenylenediamines, metaaminophenols, metadiphenols, naphthyl couplers and heterocyclic couplers, and addition salts thereof. Mention may be made, for example, of 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 5-amino-6-chloro-o-cresol (3-amino-2-chloro-6-methylphenol), 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethoxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylamino-benzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-(β-hydroxyethylamino)-1-methoxybenzene. -Hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylene-dioxybenzene, 2,6-bis(J-hydroxyethylamino)toluene, 6-hydroxy-indoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazolin-5-one, 1-phenyl-3-methylpyrazolin-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, their acid addition salts and mixtures thereof.

[0149] Usually, the addition salt of oxidation color base and color former that can be used in the context of the present disclosure is particularly selected from the addition salt with acid, for example hydrochloride, hydrobromide, sulfate, citrate, succinate, tartrate, lactate, toluenesulfonate, benzenesulfonate, phosphate and acetate.Oxidation color base each advantageously accounts for 0.001 weight % to 10 weight % relative to the total weight of the composition, and preferably 0.005 weight % to 5 weight % relative to the total weight of the composition of the present disclosure.If there is a color former, then the color former each advantageously accounts for 0.001 weight % to 10 weight % relative to the total weight of the composition, and preferably 0.005 weight % to 5 weight % relative to the total weight of the composition of the present disclosure.

[0150] The composition according to the present disclosure may contain b) one or more synthetic or natural direct dyes or pigments. Suitable dyes or pigments include, but are not limited to, those listed in Appendix IV of the European Department of Cosmetics Regulation 1223 / 2009 of the European Parliament and the Council of the European Union. Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly) methine dyes, such as anthocyanins, hemicyanins and styryl dyes; carbonyl dyes; azine dyes; nitro (hetero) aryl dyes; tri (hetero) arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, which are used alone or as a mixture. Many direct dyes are cationic direct dyes. Hydrazo cationic dyes, azo cationic dyes and diazo cationic dyes may be mentioned. Specific examples include Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof. Among the natural direct dyes that can be used according to the present disclosure, it is possible to mention hennaquinone, juglone, alizarin, purpurin, carminic acid, carminic acid, erythropogonin, protocatechuic aldehyde, indigo, isatin, curcumin, spinulosin, apigenin and orcin. It is also possible to use extracts or decoctions comprising these natural dyes, particularly henna pastes or extracts. When they are present, direct dyes more particularly account for 0.001% to 10% by weight and preferably 0.005% to 5% by weight of the gross weight of the composition of the present disclosure.

[0151] Alkalizing agent

[0152] The oxidative hair cream composition may have an alkaline pH. Exemplary pHs include 7, 8, 9, 10, 11, 12, 13, or 14. In some embodiments, the pH of the composition may be from about 7, 8, or 9 to about 9, 10, 11, or 12. The alkalinity of the oxidative hair cream composition may come from one or more alkalizing agents. In some embodiments, the alkalizing agent may be ammonia or a compound that generates ammonia gas and / or an amine or ammonium-based compound in an amount sufficient to make such a composition alkaline. In other embodiments, the alkalizing agent may be selected from alkanolamines, such as monoethanolamine (MEA) and isopropanolamine. Alkalinity may also come from ammonium compounds (e.g., NH4OH). The one or more alkalizing agents may 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% by weight of the total composition.

[0153] The oxidative hair cream composition may be in the form of a cream, an aqueous solution, a uniform dispersion or suspension of a surfactant, or even a liquid. Such compositions are acceptably phase stable and typically have a viscosity 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 10000 cps. For purposes of the present invention, viscosity is measured at room temperature using a Brookfield LVDV-II+ viscometer apparatus with the corresponding cup and spindle at 1 rpm.

[0154] The oxidative hair cream composition of the present invention also comprises at least one colorant comprising a thiophene azo chromophore. Typically, the thiophene azo colorant may be characterized by having an absorbance in the range of about 400 nanometers to about 700 nanometers, as measured by UV-visible spectroscopy. In one aspect of the present invention, the thiophene azo colorant has a maximum absorbance in the range of 500 nanometers to 650 nanometers, or has a maximum absorbance in the range of 540 nanometers to 700 nanometers, or even has a maximum absorbance in the range of 540 nanometers to 630 nanometers.

[0155] Depending on their method of manufacture, thiophene azo colorants have molecular weights that are often expressed as a molecular weight distribution.Thus, the molecular weight of a thiophene azo colorant is often reported as an average molecular weight, as determined by its molecular weight distribution.

[0156] In one aspect, the thiophene azo colorant can be a neutral or uncharged molecule. In another aspect, the colorant can be nonionic, anionic or cationic. The thiophene azo colorant can contain a chromophore having both a positive charge and a negative charge. In addition, the thiophene azo colorant can contain a zwitterionic or amphoteric chromophore.

[0157] The thiophene azo colorants may be alkoxylated. Alkoxylation is performed by methods well known to those skilled in the art (see, for example, USPNs 4,137,243; 5,082,938; 5,135,972; 5,591,833; 6,593,483; 7,587,857; 9,056,963; and 9,068,081).

[0158] In one aspect of the invention, the oxidative hair cream composition comprises a thiophene azo colorant according to formula I:

[0159]

[0160] Each R 11 To R 110 The groups are independently selected from hydrogen, deuterium and R v ; Each R vindependently selected from halogen, nitro, nitrile, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, -(CH2) n -OR 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 ) - and -P(O)(O - )2, wherein the index n is an integer from 0 to 4, preferably from 0 to 1, most preferably 0; preferably R 11 , R 12 and R 13 At least one of them is selected from halogen, nitro, nitrile, nitroso, -C(O)R x 、-C(O)OR x 、-C(O)NR x R y 、-OC(O)R x 、-OC(O)OR x 、-OC(O)NR x Ry 、-S(O)2R x 、-S(O)2OR x 、-P(O)2R x AND-P(O)(OR x )2 group of electron withdrawing group, preferably R 16 , R 17 , R 18 , R 19 , R 110 independently selected from hydrogen, halogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, tert-butyl, -(CH2) n -OR x 、-(CH2) n -NR x R y 、-OR x , and -NR x R y , and R 16 , R 17 , R 18 , R 19 , R 110 At least one of -OR x or -NR x R y . R x , R y and R z R is independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, and u ; R u is an organic group consisting of one or more organic monomers having a molecular weight of 28 to 500, preferably 43 to 350, even more preferably 43 to 250. Two or more R 16 , R 17 , R 18 , R 19 , R 110 The ring structure can be connected to each other by covalent bonds. The ring can be combined with the benzene ring to form structures including but not limited to naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, indoline, and isoindoline. The ring structure can be further connected by one or more R 16 Group substitution. x , R y or R z When two of them are connected 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. The ring structure can be further replaced by one or more R 16 Group substitution.

[0161] In one aspect of the invention, the oxidative hair cream composition comprises a thiophene azo colorant according to Formula V:

[0162]

[0163] Where R 56 , R 57 , R 58 , R 59 and R 510 The groups are independently selected from hydrogen, halogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, -(CH2) n -OR 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 、-NR x C(O)SR y 、-NR x C(O)NR x R y 、-OR x 、-NR x R y 、-P(O)(OR x ) - and -P(O)(O - )2; two or more R 56 , R 57 , R 58 , R 59 , R 510 They can be connected to each other by covalent bonds to form a ring structure. x , R y and R z R is independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, alkynyl, substituted alkynyl, and u ; R u is an organic group consisting of one or more organic monomers having a molecular weight of 28 to 500, preferably 43 to 350, even more preferably 43 to 250. Two or more R 56 , R 57 , R 58 , R 59 , R 510The ring structure can be connected to each other by covalent bonds. When the ring is combined with the benzene ring, it can form a structure including but not limited to naphthalene, tetrahydroquinoline, tetrahydroisoquinoline, indoline, and isoindoline. The ring structure can be further replaced by one or more groups such as R 56 Replace. x , R y or R z When two of them are connected 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. The ring structure can be further replaced by one or more R 56 Group substitution.

[0164] In another aspect of the invention, the oxidative hair cream composition comprises a thiophene azo colorant according to Formula IV:

[0165]

[0166] wherein each x and y is independently an integer from 0 to 20.

[0167] It is also contemplated within the scope of the present invention that other colorants may be combined with the thiophene azo colorants to form the colorant portion of the oxidative hair cream composition. For example, colorants selected from one or more of the following categories may be suitable: acid dyes, basic dyes, direct dyes, solvent dyes, vat dyes, mordant dyes, indigoid dyes, reactive dyes, disperse dyes, sulfur dyes, fluorescent dyes; organic and inorganic pigments; natural colorants, etc.

[0168] 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.

[0169] The method for preparing the oxidative hair cream composition of the present invention comprises the following steps:

[0170] (a) providing at least one oxidizing agent;

[0171] (b) providing at least one thiophene azo colorant; and

[0172] (c) combining the at least one oxidizing agent and at least one thiophene azo colorant to form an oxidative hair cream comprising a thiophene azo colorant.

[0173] The method for applying color to hair according to the invention comprises the following steps:

[0174] (a) providing an oxidative hair cream comprising a thiophene azo colorant;

[0175] (b) applying the oxidative cream comprising the thiophene azo colorant to the hair;

[0176] (c) allowing the cream to contact the hair for a period of time; and

[0177] (d) removing the pomade from the hair.

[0178] The method for bleaching hair and applying color to hair according to the present invention comprises the following steps:

[0179] (a) providing an oxidative hair cream comprising a thiophene azo colorant;

[0180] (b) applying the oxidative cream comprising the thiophene azo colorant to the hair;

[0181] (c) allowing the cream to contact the hair for a period of time; and

[0182] (d) Removing hair cream from the hair.

[0183] The oxidative cream composition may be left in contact with the hair for a period of 10 seconds to 1 hour, or 30 seconds to 45 minutes, or 1 minute to 30 minutes, or 3 minutes to 15 minutes. The hair may be wetted with water prior to application of the cream, or the hair may be dry when the cream is applied to the hair.

[0184] The oxidative hair cream may be permanent (e.g., 80% of the original color intensity is still visible after 20 washing cycles), semi-permanent (e.g., 80% of the original color intensity is visible up to 20 washing cycles but not after 20 washing cycles), or temporary (e.g., 80% of the original color intensity is visible up to 5 washing cycles but not after 5 washing cycles). The permanence of the hair color on the hair may depend on the specific thiophene azo colorant included in the hair cream and / or the amount of thiophene azo colorant included in the hair cream. For example, increasing the amount of thiophene azo colorant in the hair cream may result in the color lasting longer on the hair. Conversely, including less thiophene azo colorant in the hair cream may result in the color lasting less time on the hair. Furthermore, the amount of time that the oxidative hair cream remains in contact with the hair during the coloring process may affect the amount of color on the hair, the depth of color and / or hue, and the permanence of the hair color. For example, during the hair coloring process, leaving the cream on the hair for a longer period of time can result in a greater hue and / or depth of color and a color that lasts longer on the hair.

[0185] In one aspect of the present invention, the amount of thiophene azo colorant in the hair cream is 0.0001%-10% or 0.1%-5%.

[0186] In one aspect of the present invention, the molecular weight of the thiophene azo colorant in the hair cream is 100-10000 or 200-5000 or 300-2000.

[0187] At least one thiophene azo colorant as described herein may be added to an oxidative cream composition for dyeing hair. Thus, the present invention also includes hair (or keratin-containing material) comprising at least one thiophene azo colorant. The present invention also includes a method for bleaching and / or coloring hair (or keratin-containing material), the method comprising the steps of providing hair, applying and / or depositing an oxidative cream composition as described herein onto the hair, contacting the oxidative cream composition with the hair for a period of time, and further agitating, rinsing and / or drying the hair thus treated.

[0188] There are usually two components in these types of oxidative systems. One component contains the oxidizing material (e.g., hydrogen peroxide). The second component contains other materials, usually designed to increase the pH, but may also contain other oxidizing materials such as persulfates. In one aspect of the invention, the two components are mixed together before application to the hair. Initial applications include the thiophene azo colorant in a hydrogen peroxide cream rather than in the second component. However, it is conceivable to place the thiophene azo colorant in the second component.

[0189] Thus, in one embodiment, at least one thiophene azo colorant is mixed into a cream containing an oxidizing agent. Immediately before use, the cream containing the thiophene azo colorant / hydrogen peroxide is mixed with at least one other component that increases the pH in an amount sufficient to activate the hydrogen peroxide. In another alternative embodiment, the thiophene azo colorant can be added to a second component. In this case, the second component is added to an uncolored hydrogen peroxide cream just before use.

[0190] Although the invention described herein is primarily directed to oxidative hair creams containing thiophene azo colorants, it is not limited to these compositions. The oxidative hair creams may contain a combination of a thiophene azo colorant and another colorant. Other colorants include, for example, dyes, pigments, and combinations thereof.

[0191] Suitable dyes include small molecule dyes. Suitable small molecule dyes include dyes selected from the color index (CI) classification of direct blue, direct red, direct violet, acid blue, acid red, acid violet, basic blue, basic violet and basic red, or small molecule dyes of their mixtures. Examples of small molecule dyes include those selected from the color index (Society of Dyers and Colourists, Bradford, UK) number: 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 violet 51, acid violet 52, acid violet 53, acid violet 54, acid violet 55, acid violet 56, acid violet 57, acid violet 58, acid violet 59, acid violet 60, acid violet 61, acid violet 62, acid violet 63, acid violet 64, acid violet 65, acid violet 66, acid violet 67, acid 68, acid 69, acid 60, acid 61, acid 62, acid 63, acid 64, acid 65, acid 66, acid 67, acid 68, acid 69 ... 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 3, basic violet 4, basic violet 10, basic violet 35, basic blue 3, basic blue 16, basic blue 22, basic blue 47, basic blue 66, basic blue 75, basic blue 159, selected from small molecule dyes of the color index (Society of Dyers and Colourists, Bradford, UK): acid violet 17, acid violet 43, acid red 52, acid red 73, acid red 88, acid red 150, acid blue 25, acid blue 29, acid blue 45, acid blue 113, acid black 1, direct blue 1, direct blue 71.

[0192] Suitable pigments include pigments selected from the group consisting of flavanthrones, indanthrone, chlorinated indanthrone containing 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimides, where the imide groups can be unsubstituted or substituted by C1-C3-alkyl or phenyl or heterocyclic groups, and where the phenyl and heterocyclic groups can additionally carry substituents which do not impart solubility in water, anthrapyrimidinecarboxylic acid amides, violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyanine containing up to 2 chlorine atoms per molecule, polychlorocopper phthalocyanines or polybromochlorocopper phthalocyanines containing up to 14 bromine atoms per molecule, and mixtures thereof.

[0193] In one aspect of the present invention, the components of the oxidative hair care composition can be prepared by combining the components in any convenient order and by mixing, for example, stirring the resulting component combination to form a phase-stable semi-liquid (i.e., cream) composition. In another method of preparing such a composition, a liquid matrix comprising at least a major proportion, preferably substantially all liquid components, is formed, and the liquid components are fully mixed by applying shear stirring to the liquid composition. For example, a mechanical stirrer can be used for rapid stirring. While maintaining shear stirring, substantially all of any solid form ingredients can be added. The mixture is continued to be stirred, and if necessary, stirring can be increased at this time to form a solution or uniform dispersion of insoluble solid phase particles in the liquid phase. As a variant of the composition preparation method described above, one or more solid components can be added to the stirred mixture in the form of a solution or slurry of particles premixed with a small portion of one or more liquid components. After all composition components are added, the mixture is continued to be stirred for a period of time sufficient to form a composition having a desired viscosity and phase stability characteristics. This generally involves stirring for about 30-60 minutes.

[0194] The oxidative creams of the present invention may be combined with other molecules, compounds and / or agents for applying the oxidative cream to the hair and / or for enhancing color performance. Other molecules, compounds and / or agents include, for example, surfactants, solvents, preservatives, antimicrobial agents, antibacterial agents, fragrances, etc. and combinations thereof.

[0195] The oxidative hair cream compositions of the present invention may also contain any number of other optional ingredients. These include conventional hair dye composition components such as ... alkalizing agents (e.g., ammonia), alkalinity sources (e.g., silicates and / or carbonates), humectants, conditioners, thickeners, non-coloring dyes, detergency builders, enzymes, enzyme stabilizers, foam suppressors, pH adjusters, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structurants, opacifiers, fragrances, and colorants. The various optional oxidative hair cream composition ingredients, if present in the compositions herein, should be used in conventionally used concentrations to bring their desired contribution to the composition or to the bleaching and / or coloring process. Typically, the total amount of such optional oxidative hair cream composition ingredients may range from about 0.01% to about 50% by weight of the composition, more preferably from about 0.1% to about 30% by weight.

[0196] Example

[0197] Several colorants were tested for stability and coloring performance in commercially available oxidative hair creams. Each sample was added to a Fanola 40 Vol Perfumed Cream Developer (purchased from Fanola, Italy) containing about 12% hydrogen peroxide. Each sample was mixed with a high-speed mixer at 1500 rpm for a minimum of 90 seconds until a visually uniform mixture was obtained (SpeedMixer from Inc., Landrum, SC). The amount of color contained in each sample was adjusted so that each sample exhibited the same color intensity. The maximum absorbance of the colored cream was 0.67 when measured at a concentration of 10 g / L in methanol with a 1 cm optical path length. After mixing, the samples were first stored at room temperature for 7 days and then moved to a 40°C oven. Color stability was evaluated by room temperature equivalent days, which is based on the number of days it takes for the color initially measured in the cream to reach 50% color loss at time zero as measured by UV-VIS. Color loss is due to discoloration caused by chemical changes in the colorant from oxidative cream ingredients including peroxides.

[0198] Calculate the room temperature equivalent days using the following equation:

[0199] Room temperature equivalent days

[0200] = Room temperature storage days + 40℃ storage days * 3.48

[0201] Using the room temperature equivalent number of days for the color to degrade to 50%, a rating was generated according to Table 1. A rating of "1" indicates the most stable, while a rating of "5" indicates the least stable.

[0202] Table 1: Rating scale for stability of oxidative hair creams containing colorants

[0203] Rating To 50% of the room temperature equivalent days 1 More than 300 days 2 From 150 to 300 days 3 From 50 to 150 days 4 From 20 to 50 days 5 Less than 20 days

[0204] The colorants of the present invention and the stability test results are shown in Table 2A. The comparative colorants and the stability test results are shown in Table 2B.

[0205] Table 2A: Colorants of the Invention

[0206]

[0207] Table 2B: Comparative Colorants

[0208]

[0209]

[0210] The test results demonstrate that all polymeric triarylmethane dyes are unstable (Comparative Examples 1-5). Other polymeric dye species such as cyanine (Comparative Example 6), methine (Comparative Example 7) and anthraquinone (Comparative Examples 8 and 9) are also unstable. Monomeric anthraquinone dyes such as External D&C Violet 2 (Comparative Example 10) and Solvent Violet 13 (Comparative Example 11) were found to be difficult to blend into creams, but had better stability than their polymeric counterparts (Comparative Examples 8 and 9).

[0211] Coloring performance evaluation

[0212] Material:

[0213] Blonde (lightly bleached black hair) cut into 3cm wide and 20cm long

[0214] Fanola Purple Bleaching Powder

[0215] Fanola 40 Volume (12% Peroxide) Oxidizing Cream

[0216] program:

[0217] First weigh the hair to calculate the amount of cream required (4 grams of cream per gram of hair). Mix the color and oxidative cream developer as described above. Check the mixture and remix if necessary to ensure that the color is completely uniform. Weigh Fanola purple bleaching powder (available from Fanola in Italy) into a small weighing boat (two parts cream to one part bleaching powder). Add the appropriate amount of oxidative cream to the bleaching powder. Use the wooden end of a cotton-tipped applicator to stir the bleach / cream until it is completely mixed. Transfer the bleach / cream mixture to a large weighing boat with the hair sample. Spread the mixture over the entire hair and work it into the hair with your fingertips until the mixture is completely and evenly incorporated into the entire hair. Allow the bleach to stand on the hair for 15 minutes, then rinse the hair sample thoroughly with warm water, comb it, and dry it in an oven at 60°C for 45 minutes. Use an X-Rite Color-i with a 6mm hole to measure the color of the hair with a D-65 light source. When taking the measurement, twist the hair tightly and press it against the hole. Use the average of 6-8 measurements.

[0218] CIE WI is a good indicator of the degree of hair lightening. Initial hair has a whiteness index (WI) of -76.6 due to its yellow color. After treatment, the WI value increases, indicating that the hair is lighter. The difference in WI, ΔWI, between the treated hair and the initial hair is recorded. A larger ΔWI indicates better hair lightening.

[0219] The WI and ΔWI values ​​for initial hair, bleach control (no dye), and bleach compositions comprising Example 1, Example 2, and Comparative Example 10 (External D&C Violet 2) are shown in Table 3. The bleach compositions of Example 1 and Example 2 provide better lightening than the bleach control and Comparative Example 10 bleach.

[0220] Table 3: Color evaluation

[0221] sample WI value ΔWI value The initial hair -76.6 n / a Oxidative hair cream comparison -60.0 16.6 Oxidative hair cream of Example 1 -46.1 30.5 Oxidative hair cream of Example 2 -47.1 29.5 Oxidative hair cream of Comparative Example 12 -55.7 20.9

[0222] When black hair is bleached, melanin is destroyed, which results in a visual enhancement of red pigment and an undesirable warm orange-red or "brassy" tint projected onto the bleached hair. This brassy tint is typically corrected by a post-bleach application of a violet or blue dye. Blue or violet complements orange and tan tones and effectively neutralizes such tints. The dye can be delivered in a shampoo, conditioner, hair mask, hair cream or the like. Preferably, the violet or blue colorant is added to the bleaching cream so that the brassy tint is neutralized directly during the bleaching process, so no additional color treatment is required. The challenge is that oxidative creams are typically aggressive conditions that discolor many colorants. The present invention is directed to a specific subset of dyes that are stable in oxidative creams upon storage and also have the correct color for neutralizing the brassy tint.

[0223] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0224] In the context of describing the subject matter of the present application (especially in the context of the following claims), the use of the terms "a" and "an" and "the" and similar indicators should be interpreted as covering the singular and plural, unless otherwise specified herein or clearly contradicted by the context. The terms "comprising", "having", "including" and "containing" should be interpreted as open terms (i.e., meaning "including but not limited to"), unless otherwise specified. Unless otherwise specified herein, the description of the numerical range herein is intended only to be used as a shorthand method of individually referring to each individual value falling within the range, and each individual value is incorporated into the specification as if it were individually described herein. All methods described herein can be performed in any suitable order, unless otherwise specified herein or clearly contradicted by the context. The use of any and all examples or exemplary language (e.g., "for example") provided herein is intended only to better illustrate the subject matter of the present application, and does not limit the scope of the subject matter, unless otherwise stated. Any language in the specification should not be interpreted as indicating that any unclaimed element is essential to the practice of the subject matter described herein.

[0225] Preferred embodiments of the subject matter of the present application are described herein, including the best mode known to the inventor for implementing the claimed subject matter. After reading the foregoing description, variations of those preferred embodiments will be apparent to those of ordinary skill in the art. The inventor expects that such variations will be appropriately adopted by those skilled in the art, and the inventor intends to practice the subject matter described herein in a manner different from that specifically described herein. Therefore, the present disclosure includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. In addition, unless otherwise specified herein or clearly contradictory to the context, the present disclosure covers any combination of the above-mentioned elements in all possible variations thereof.

Claims

1. An oxidative hair cream composition, wherein the composition comprises at least one thiophene azo colorant and at least one oxidative hair cream ingredient, wherein the at least one thiophene azo colorant is a dye according to the following structure: wherein each x and y is independently an integer from 0 to 20, The at least one oxidative hair cream ingredient is a source of hydrogen peroxide.

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

3. The oxidative hair cream composition of claim 1, wherein the at least one oxidative hair cream ingredient is hydrogen peroxide.

4. An oxidative hair cream composition according to claim 3, wherein the composition comprises from 0.01% to 33% hydrogen peroxide.

5. An oxidative hair cream composition according to claim 3, wherein the composition comprises from 0.1% to 15% hydrogen peroxide.

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

7. A method for treating hair, the method comprising the steps of: (a) providing the oxidative hair cream composition according to claim 1, and (b) contacting the oxidative hair cream composition with human hair.

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