CN102137653B - Powdered hair coloring and bleaching compositions - Google Patents

Abstract

The present invention relates to a powdered hair coloring or bleaching composition comprising: a) at least one solid source of carbonate ions, carbamate ions, bicarbonate ions, or mixtures thereof; b) at least one solid source of an oxidizing agent; c) at least one solid source of ammonium ions; and d) a cross-linked carboxylic acid polymer thickener having a particle size of not more than about 10 microns; said thickener being present in an amount to provide a concentration of from about 1% to about 3% when the powdered composition is mixed with water; and said thickener providing the dispersed composition with a viscosity of from about 10,000 mPas to about 20,000 mPas and a pH of from about 8.5 to about 9.4 as measured using a Brookfield viscometer spindle S52 at 0.5 rpm.

Description

Powdered hair coloring and bleaching compositions

field of invention

The present invention relates to powdered hair coloring and bleaching compositions formulated for use by the consumer with water. the

Background of the invention

Most oxidative hair colorant products currently retailed are based on two-, three- or four-component systems in liquid form consisting of 1) a developer comprising water and hydrogen peroxide, 2) A tinting base comprising water, oxidation dye precursors and an alkalizing agent, and optionally 3) other solvent-containing components mixed with 1) and 2), and optionally 4) a post-treatment hair conditioner. Due to the movement of relatively large volumes of substances, especially water and solvents, packaging is complicated and transportation costs are considerable. Powdered product form formulated for consumer use with water minimizes the effects of both of these problems, thus providing an environmentally friendly product at a lower cost. the

Powdered hair coloring and bleaching compositions are known in the art, however less attention has been paid to developing this product form compared to liquid product forms. This makes the performance of products in powder form incomparable to those in liquid form. Commonly observed underperforming aspects of powder form products include low lift and poor color payoff, resulting in less efficient coloring of gray and gray hair. the

In addition, due to the need to stabilize the dye precursors against reaction prior to mixing with water, the choice of dye precursors is limited to those available in the sulfate or hydrochloride form due to the lack of methods for stabilizing the dye precursors, limiting shades diversity. While proposals have been made to stabilize and/or coat one or more components of the product, such treatment would add cost and is therefore not an option for this product form, which is generally positioned as an environmentally friendly, low-cost product. suitable. the

Furthermore, for this product form, ammonia formation will inevitably occur when the product is mixed with water and the base reacts with the ammonia source. This ammonia odor makes the formulation process of this product form very unpleasant. the

Based on the foregoing, there is a need to provide powdered hair coloring and bleaching compositions that provide a satisfactory degree of lift and color build-up such that they can be used on gray hair, with the ability to provide a wider variety of shades. possible and reduces hair damage while being easy to formulate and has a pleasant odor when mixed with water and has sufficient shelf stability. the

None of the prior art offers all of the advantages and benefits of the present invention. the

Summary of the invention

The present invention relates to powdered hair coloring or bleaching compositions comprising:

a) at least one solid source of carbonate ions, carbamate ions, bicarbonate ions, or mixtures thereof;

b) at least one solid source of oxidizing agent;

c) at least one solid source of ammonium ions; and

d) A cross-linked carboxylic acid polymer thickener having a particle size of not more than about 10 microns. The amount of the thickener may provide a concentration of about 1% to about 3% when the powdered composition is mixed with water. The thickener can provide the dispersed composition with a viscosity of from about 10,000 mPas to about 20,000 mPas and a pH of from about 8.5 to about 9.4 when measured using a Brookfield viscometer spindle S52 at 0.5 rpm. the

The invention also relates to a method of coloring or bleaching hair, said method comprising the steps of:

a) providing the above composition;

b) mixing said composition with a specified amount of water;

c) applying the dispersed composition to the hair;

d) leaving the dispersed composition on the hair for about 2 to about 60 minutes; and

e) Rinse the dispersed composition from the hair. the

After application to the hair, the present invention provides a satisfactory degree of lift and color build-up so that they can be used on gray hair, with the potential to provide a wider variety of shades, and with less damage to the hair, while being easy to use. Formulated and has a pleasant odor when mixed with water and has adequate shelf stability. the

Detailed description of the invention

While the specification concludes with claims which particularly point out and distinctly claim the invention, it is believed that the invention will be better understood from the following description. the

The term "hair" to be treated as used herein may be "living", ie, on a living body, or "inanimate", ie, a wig, eyebrow false or other inanimate keratinous fiber aggregates. Mammalian hair, preferably human hair, is preferred. However, wool, fur and other keratin-containing fibers are also suitable as substrates for the compositions of the present invention. the

All percentages are by weight of the total composition unless specifically stated otherwise. When more than one composition is used during a treatment, the total weight is considered to be the total weight of all compositions applied to the hair simultaneously (ie, the weight present "on the head"), unless otherwise indicated. All ratios are by weight unless specifically stated otherwise. All molar concentrations are by volume of the total composition and are expressed as moles of components in one liter of composition or "mol/L". When more than one composition is used during a treatment, the total volume is considered to be the total volume of all compositions applied to the hair simultaneously (ie, the volume present "on the head"), unless otherwise indicated. the

As used herein, "composition" or "powder composition" refers to the composition of the invention in powder form in which the product is provided to the consumer, and "dispersed composition" refers to the composition obtained by mixing the powder composition with the specified amount of water to provide a fluid composition. the

Carbonate ion source

According to the invention, the composition comprises a solid source of carbonate ions or carbamate ions or bicarbonate ions or peroxymonocarbonate ions, or any mixture thereof. The solid source of ions described herein is provided in the composition to provide a concentration of at least 0.2 mol/l when the powder composition is mixed with water. The composition of the present invention is intended to provide preferably from about 0.4 mol/l to about 2.0 mol/l, more preferably from about 0.5 mol/l to about 1.5 mol/l of said ion source when the powder composition is mixed with water. the

Any solid source of these ions can be used. Sources suitable for use herein include sodium, potassium, lithium, calcium, magnesium, barium, ammonium salts of carbonate, carbamate, and bicarbonate ions, and mixtures thereof, such as sodium carbonate, sodium bicarbonate , potassium carbonate, potassium bicarbonate, lithium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, ammonium carbonate, ammonium bicarbonate and mixtures thereof. Percarbonate may also be used to provide a source of carbonate ions and a source of oxidizing agents. Preferred solid sources of carbonate, carbamate, and bicarbonate ions are sodium percarbonate, potassium percarbonate, calcium percarbonate, and mixtures thereof. the

oxidizing agent

Thus, the composition according to the invention can form peroxymonocarbonate ions. These ions are typically formed in situ from the reaction between hydrogen peroxide and a source of carbonate ions. Accordingly, the composition according to the invention may comprise at least one source of oxidizing agent. Preferred oxidizing agents for use herein are water-soluble solid peroxygen oxidizing agents. "Water-soluble" as defined herein means that at least 0.1 g, preferably 1 g, more preferably 10 g of the oxidizing agent can be dissolved per liter of deionized water under normal conditions. Oxidizing agents are useful for the initial solubilization and depigmentation of melanin (bleaching) and can promote the oxidation of oxidative dye precursors in the hair shaft (oxidative dyeing). the

Any solid oxidizing agent known in the art may be used in the present invention. Preferred water-soluble oxidizing agents are inorganic peroxygen species capable of generating hydrogen peroxide in aqueous solution. Water-soluble peroxygen oxidizing agents are well known in the art and include hydrogen peroxide, inorganic alkali metal peroxides (such as sodium periodate and sodium peroxide) and organic peroxides (such as carbamide peroxide, melamine peroxide), and inorganic perhydrate salt bleaching compounds (such as alkali metal salts of perboric acid, percarbonic acid, perphosphoric acid, persilicate, persulfuric acid, and the like). These inorganic perhydrate salts may be incorporated as monohydrates, tetrahydrates, and the like. Alkyl and aryl peroxides and/or peroxidases may also be used. Mixtures of two or more of the above oxidizing agents may be used if desired. Preferred for use in the compositions of the present invention are percarbonates (which can be used to provide both a source of oxidizing agent and a source of carbonate ions), persulfates, and combinations thereof. the

According to the present invention, when the powder composition is mixed with water, the composition is intended to provide preferably about 0.1 wt. % to about 10 wt. %, preferably about 1 wt. % to about 7 wt. %, and most preferably about 2 wt. About 5% by weight of oxidizing agent. the

ammonium ion source

According to the invention, the composition comprises at least one solid source of ammonium ions. Any solid source of ammonium ions is suitable for use herein. Preferred sources include ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium carbonate, ammonium bicarbonate, ammonium carbamate, ammonium hydroxide, percarbonate, ammonia, and mixtures thereof. Ammonium sulfate, ammonium carbonate, ammonium carbamate, ammonia, and mixtures thereof are especially preferred. Ammonium ions and carbonate ions are preferably present in the composition in a weight ratio of 3:1 to 1:10, preferably 2:1 to 1:5. the

When the powder composition is mixed with water, the compositions of the present invention are intended to provide preferably from about 0.1% to about 10% by weight, preferably from about 0.5% to about 5% by weight, most preferably from about 1% to about 3% by weight of ammonium ions. the

Crosslinked Carboxylic Acid Polymer Thickener

When the composition is dispersed in water, the aforementioned components of the present invention provide percarbonate groups which contribute to effective bleaching and coloring in a relatively short period of time. This improves lift and color development to the point where they can be used on gray hair. In addition, by having a dispersed composition having a pH of from about 8.5 to about 9.4, preferably from about 9.0 to about 9.4, the concentration of peroxide can be reduced to reduce damage to the hair fiber, while also reducing the release of ammonia and mitigating the effects of its smell. After mixing with water, the resulting viscosity of the composition must be controlled within a range suitable for application to the hair by the user. After the powder composition is mixed with water to provide a concentration of from about 1% to about 3%, the target viscosity is from about 10000 mPas to about 20000 mPas, preferably from about 12000 mPas to about 18000 mPas, measured using a Brookfield viscometer spindle S52 at 0.5 rpm. Those skilled in the art realize that the type and amount of thickener is not the only factor affecting the viscosity of the final composition, other components and component interactions such as the addition of salt, and the formation of lamellar structures are also influencing factors. Therefore, the remaining components must be considered in order to provide the desired viscosity. According to the invention, the composition comprises a buffer thickener that meets all of the following conditions:

(1) Compatible with the remaining solid components in the composition to provide stability during shelf life;

(2) It is easy to disperse when mixed with water;

(3) When mixed with water, short periods of gentle agitation provide the proper viscosity; and

(4) The dispersed composition may be buffered to a suitable pH. the

Surprisingly, it has now been found that cross-linked carboxylic acid polymers having a particle size of no more than about 10 microns, preferably from about 0.1 microns to about 7 microns, provide rapid and effective thickening when mixed with water, while in the present invention Proper viscosity and target pH are provided in percarbonate systems. Without being bound by theory, of the variety of high molecular weight and networked polymers available in the art, only those selected provide rapid and effective thickening without unacceptable lumps, and provide the desired viscosity without There is no need for prolonged stirring of the polymer which is unacceptable for this product form. In addition, the cross-linked carboxylic acid polymer thickeners of the present invention can buffer the dispersed composition to a target pH which is lower than that of other percarbonate systems known to be used in powder form. the

The cross-linked carboxylic acid polymers useful herein can be selected from, for example:

(i) cross-linked acrylic acid homopolymer;

(ii) Copolymers of acrylic acid or (meth)acrylic acid and copolymers of acrylic acid or C1-C30 alkyl (meth)acrylates. the

A preferred polymer is a C10-C30 alkyl acrylate crosspolymer. Commercially available crosslinked carboxylic acid polymers that are highly useful herein include those sold by Noveon Corporation under the tradenames Carbopol ETD 2020, 10, 980, 981, 954, 2984, 5984. the

The pH of the composition can be measured by using a Mettler Toledo MP220 or MP225 pH device equipped with a standard laboratory pH electrode. Before each use, use standard calibration buffers and calibrate the device using standard calibration procedures. the

free radical scavengers

According to the invention, the composition may also comprise a radical scavenger. The amount of free radical scavenger preferably provides from about 0.1% to about 10% by weight, more preferably from about 1% to about 7% by weight, when the powder composition is mixed with water. the

Free radical scavengers useful herein are defined as substances capable of reacting with carbonate groups to convert the carbonate groups into less reactive species through a series of rapid reactions, i.e. carbonate scavengers. the

Without being bound by theory, it is believed that the ability of radical scavengers to convert carbonate groups depends on the charge transfer reaction energy as shown below:

Scavenger +CO ₃ ^*- → Scavenger ^*+ +CO ₃ ^2-

where the reaction can be defined by:

ΔH _r = ΔH _f (product) - ΔH _f (reactant)

=ΔH _f (scavenger ^*+ )+ΔH _f (CO ₃ ^2- )-ΔH _f (scavenger)-ΔH _f (CO ₃ ^*- )

According to the invention, the composition does not comprise free radical scavengers whose reactivity is from about 0 kcal/mol to about 14 kcal/mol, preferably from about 1.5 kcal/mol to about 9 kcal/mol. the

Free radical scavengers useful herein include those of lower molecular weight that have a combination of hydroxyl and amine groups, or carboxyl and amine groups, such as alkanolamines and amino acids. Highly preferred free radical scavengers herein are selected from the group consisting of glucosamine, glycine, glutamic acid, arginine, lysine, glutamine, histidine, serine, and mixtures thereof. the

Additional components

The compositions of the present invention may also contain additional ingredients including, but not limited to, hair colorants (such as oxidative dye precursors, non-oxidative dyes), enzymes, surfactants, antioxidants, stabilizers (such as erythorbic acid) , chelating agents, waving actives, fragrances, reducing agents (thiolactic acid), hair bulking agents and/or polymers. Some of these additional components are described in detail below. the

hair dye

The hair composition of the invention is preferably a hair coloring composition comprising an oxidative dyeing composition. Such compositions comprise oxidative hair dye precursors (also known as primary intermediates or developers) that deliver various hair colors to the hair. These small molecules are activated by oxidizing agents and react with other molecules to form larger colored complexes in the hair shaft. the

The precursors may be used alone or in combination with other precursors, and one or more precursors may be used in combination with one or more couplers. Couplers (also known as color modifiers or secondary intermediates) are generally colorless molecules. They produce color in the presence of activated precursors and can be used with other precursors or couplers to produce specific color effects or to stabilize colour. The choice of precursor and coupler will depend on the desired color, shade and tinting strength. Precursors and couplers can be used herein alone or in combination to provide dyes in a variety of shades ranging from ash-gold to black. the

Precursors suitable for use in the compositions described herein include, but are not limited to, p-phenylenediamine derivatives such as benzene-1,4-diamine (commonly known as p-phenylenediamine); 2-chlorobenzene-1,4- Diamine; N-phenylbenzene-1,4-diamine; N-(2-ethoxyethyl)benzene-1,4-diamine; 2-[(4-aminophenyl)-(2- Hydroxyethyl)-amino]-ethanol (commonly known as N,N-bis(2-hydroxyethyl)-p-phenylenediamine); (2,5-diaminophenyl)-methanol; 1-(2′- Hydroxyethyl)-2,5-diaminobenzene; 2-(2,5-diaminophenyl)-ethanol; N-(4-aminophenyl)benzene-1,4-diamine; 2,6- Dimethylbenzene-1,4-diamine; 2-isopropylbenzene-1,4-diamine; 1-[(4-aminophenyl)amino]-propan-2-ol; 2-propylbenzene -1,4-diamine; 1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2-ol; N4,N4,2-trimethylbenzene-1,4 -diamine; 2-methoxybenzene-1,4-diamine; 1-(2,5-diaminophenyl)ethanol; 1-(2,5-diaminophenyl)ethane-1,2- Diol; 2,3-dimethylbenzene-1,4-diamine; N-(4-amino-3-hydroxyphenyl)-acetamide; 2,6-diylbenzene-1,4-diamine ; 2,5-dimethylbenzene-1,4-diamine; 2-thiophen-2-ylbenzene-1,4-diamine; 2-thiophen-3-ylbenzene-1,4-diamine; 2 -pyridin-3-ylbenzene-1,4-diamine; 1,1'-biphenyl-2,5-diamine; 2-(methoxymethyl)benzene-1,4-diamine; 2- (Aminomethyl)benzene-1,4-diamine; 2-(2,5-diaminophenoxy)ethanol; N-[2-(2,5-diaminophenoxy)ethyl]-ethyl Amide; N',N-dimethylbenzene-1,4-diamine; N,N-diethylbenzene-1,4-diamine; N,N-dipropylbenzene-1,4-diamine ; 2-[(4-aminophenyl)(ethyl)amino]ethanol; 2-[(4-amino-3-methylphenyl)-(2-hydroxyethyl)-amino]-ethanol; N- (2-Methoxyethyl)-benzene-1,4-diamine; 3-[(4-aminophenyl)amino]propan-1-ol; 3-[(4-aminophenyl)-amino] Propan-1,2-diol; N-{4-[(4-aminophenyl)amino]butyl}benzene-1,4-diamine; 2-[2-(2-{2-[(2 , 5-diaminophenyl)-oxy]ethoxy}ethoxy)ethoxy]benzene-1,4-diamine; 1,3-bis(N(2-hydroxyethyl)-N- (4-aminophenyl)amino)-2-propanol; 2,2'-[1,2-ethanediyl-bis-(oxyl-2,1-ethanedioxy)]-bisphenyl-1 , 4-diamine; p-aminophenol derivatives, for example: 4-aminophenol (commonly known as p-aminophenol); 4-methylaminophenol; 4-amino-3-methylphenol; 4-amino-2- Hydroxymethylphenol; 4-amino-2-methylphenol; 4-amino-1- Hydroxy-2-(2'-hydroxyethylaminomethyl)benzene; 4-amino-2-methoxymethylphenol; 5-amino-2-hydroxybenzoic acid; 1-(5-amino-2-hydroxy phenyl)-ethane-1,2-diol; 4-amino-2-(2-hydroxyethyl)phenol; 4-amino-3-(hydroxymethyl)phenol; 4-amino-3-fluorophenol; 4-amino-2-(aminomethyl)phenol; 4-amino-2-fluoro-phenol; 1-hydroxy-2,4-diaminobenzene; o-phenylenediamine derivatives, such as: 3,4-diamino Benzoic acid and its salts; o-aminophenol derivatives, for example: 2-aminophenol (commonly known as o-aminophenol); 2,4-diaminophenol; 2-amino-5-methylphenol; 2-amino- 5-ethylphenol; 2-amino-6-methylphenol; N-(4-amino-3-hydroxyphenyl)-acetamide; and 2-amino-4-methylphenol; and heterocyclic derivatives, For example: pyrimidine-2,4,5,6-tetramine (commonly known as 2,4,5,6-tetraaminopyrimidine); 1-methyl-1H-pyrazole-4,5-diamine; 2- (4,5-diamino-1H-pyrazol-1-yl)ethanol; N2,N2-lutidine-2,5-diamine; 2-[(3-amino-6-methoxypyridine- 2-yl)amino]ethanol; 6-methoxy-N2-methylpyridine-2,3-diamine; 2,5,6-triaminopyrimidin-4(1H)-one; pyridine-2,5- Diamine; 1-isopropyl-1H-pyrazole-4,5-diamine; 1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine; 1-(benzyl) -1H-pyrazole-4,5-diamine; 1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine; pyrazolo[1,5-a]-pyrimidine-3, 7-diamine; 5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride; 7-methylpyrazolo[1,5-a]pyrimidine- 3-ylamine hydrochloride; 2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride; 5,7-di-tert-butylpyrazole [1,5-a]pyrimidin-3-ylamine hydrochloride; 5,7-bis-trifluoromethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride; 2 -Methylpyrazolo[1,5-a]pyrimidine-3,7-diamine hydrochloride; 4-hydroxy-2,5,6-triaminopyrimidine; 2,3-diamino-6,7- Dihydropyrazolo[1,2-a]pyrazol-1(5H)-one dimesylate; 1-hydroxyethyl-4,5-diaminopyrazole; 2,5-diaminophenyl Alcohols; and their salts. the

Other precursors are selected from the group consisting of: N-(3-furylmethyl)benzene-1,4-diamine; N-thiophen-3-ylmethylbenzene-1,4-diamine; N-( 2-furylmethyl)benzene-1,4-diamine; N-thiophen-2-ylmethylbenzene-1,4-diamine; 3-(2,5-diaminophenyl)-N-ethane 2-[3-(3-aminophenylamino)-propenyl]-benzene-1,4-diamine; 2-[3-(4-aminophenylamino)-propenyl]-benzene -1,4-diamine; 2-(6-methyl-pyridin-2-yl)-benzene-1,4-diamine; 2-pyridin-2-ylbenzene-1,4-diamine; 2- [3-(4-aminophenylamino)-propenyl]-benzene-1,4-diamine; 2-[3-(3-aminophenylamino)-propenyl]-benzene-1,4-diamine Amine; 3-(2,5-diaminophenyl)-N-ethylacrylamide; 2-thiazol-2-ylbenzene-1,4-diamine; 4-hydroxybenzoic acid (2,5-diamino Benzylidene)-hydrazide; 3'-fluorobiphenyl-2,5-diamine; 2-propenyl-benzene-1,4-diamine; 2'-chlorobiphenyl-2,5-diamine; N-thiophen-3-ylmethylbenzene-1,4-diamine; N-(3-furylmethyl)benzene-1,4-diamine; 4'-methoxy-biphenyl-2,5 -diamine; N-(4-amino-benzyl)-benzene-1,4-diamine; N-[4-amino-2-(2-hydroxyethyl)-2H-pyrazol-3-yl] -3-(5-amino-2-hydroxyphenyl)acrylamide hydrochloride; 4-amino-2-propylaminomethylphenol; 4-amino-2-(isopropylaminomethyl)-phenol 4-amino-2-[(2-hydroxy-5-nitrophenylamino)-methyl]-phenol hydrochloride; 4-amino-2-(pyridin-3-ylaminomethyl)- Phenol; 5-cyclobutylamino-2-methylphenol; 4,5-diamino-1-methyl-1H-pyrazole-3-carbonitrile; 3-methoxy-1-propyl-1H- Pyrazole-4,5-diamine; 3-methoxy-1-(2-methoxyethyl)-1H-pyrazole-4,5-diamine; 1-(2-aminoethyl)- 3-methoxy-1H-pyrazole-4,5-diamine; 8-methoxy-1,2,4,5-tetrahydropyrazolo[5,1-d][1,3,5 ]Oxadiazepine-9-amine; 1-(2-hydroxyethyl)-3-methoxy-1H-pyrazole-4,5-diamine; 1-cyclohexyl-3-methoxy-1H -pyrazole-4,5-diamine; 6-methoxy-1-methyl-2,3-dihydro-1H-imidazo[1,2-b]pyrazol-7-amine; 2-form Oxy-4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidin-3-amine; 3-methoxy-1-octyl-1H-pyrazole-4,5-di Amine; 3-methoxy-1-pentyl-1H-pyrazole-4,5-diamine; 6-methoxy-2,3-dihydro-1H-imidazo[1,2-b]pyridine Azol-7-amine; 3-methoxy-N5, N5-dimethyl-1- Propyl-1H-pyrazole-4,5-diamine; 1-hexyl-3-methoxy-1H-pyrazole-4,5-diamine; 1-butyl-3-methoxy-1H- Pyrazole-4,5-diamine; 1-isopropyl-3-methoxy-1H-pyrazole-4,5-diamine; 1-ethyl-3-methoxy-1H-pyrazole- 4,5-diamine; 3-methoxy-1-(4-methoxybenzyl)-1H-pyrazole-4,5-diamine; 3-methoxy-1-(pyridine-2- Base)-1H-pyrazole-4,5-diamine; 1-(4-ethylphenyl)-3-methoxy-1H-pyrazole-4,5-diamine; 3-methoxy- 1-p-tolyl-1H-pyrazole-4,5-diamine; 3-cyano-1-(2-hydroxyethyl)-1H-pyrazole-4,5-diamine; 1-butyl- 3-cyano-1H-pyrazole-4,5-diamine; 3-cyano-1-phenyl-1H-pyrazole-4,5-diamine; 3-cyano-1-hexyl-1H- Pyrazole-4,5-diamine; 1-butyl-3-cyano-1H-pyrazole-4,5-diamine; 3-cyano-1-(4-methoxybenzyl)-1H -pyrazole-4,5-diamine; 3-cyano-1-isopropyl-1H-pyrazole-4,5-diamine; 1-cyclohexyl-3-fluoro-N5-isopropyl-1H -pyrazole-4,5-diamine; 1-methyl-3-(trifluoromethoxy)-1H-pyrazole-4,5-diamine; 3-fluoro-1-octyl-1H-pyridine Azole-4,5-diamine; 3-chloro-1-hexyl-1H-pyrazole-4,5-diamine; 3-fluoro-1-(2-hydroxyethyl)-1H-pyrazole-4, 5-diamine; 3-chloro-1-(2-hydroxyethyl)-1H-pyrazole-4,5-diamine; 3-chloro-1-(4-hydroxybutyl)-1H-pyrazole- 4,5-diamine; 3-chloro-1-(pyridin-2-yl)-1H-pyrazole-4,5-diamine; 3-chloro-1-phenyl-1H-pyrazole-4,5 -diamine; 3-chloro-1-ethyl-1H-pyrazole-4,5-diamine; 1-(3-methoxypropyl)-3-(methylsulfinyl)-1H-pyridine Azole-4,5-diamine; 1-(3-hydroxypropyl)-3-(methylsulfinyl)-1H-pyrazole-4,5-diamine; 1-(4-methoxybenzyl Base)-3-(methylsulfonyl)-1H-pyrazole-4,5-diamine; 1-methyl-3-(methylsulfonyl)-1H-pyrazole-4,5-diamine; and their salt. the

In some embodiments, precursors include, but are not limited to: p-phenylenediamine derivatives such as: 2-methylbenzene-1,4-diamine; benzene-1,4-diamine; 1-(2,5 -diaminophenyl)-ethanol; 2-(2,5-diaminophenyl)-ethanol; 2-(methoxymethyl)benzene-1,4-diamine; N-(2-methoxy Ethyl) benzene-1,4-diamine; 2-[(4-aminophenyl)-(2-hydroxyethyl)-amino]-ethanol; 1-(2,5-diaminophenyl) ethyl- 1,2-diol; 1-(2'-hydroxyethyl)-2,5-diaminobenzene; 1,3-bis(N-(2-hydroxyethyl)-N-(4-aminophenyl )amino)-2-propanol; 2,2'-[1,2-ethanediyl-bis-(oxyl-2,1-ethanedioxy)]-bisphenyl-1,4-diamine; N,N-bis(2-hydroxyethyl)-p-phenylenediamine; and mixtures thereof; p-aminophenol derivatives, for example: 4-aminophenol; 4-methylaminophenol; 4-amino-3-methyl Phenol; 4-amino-2-methoxymethylphenol; 1-(5-amino-2-hydroxyphenyl)-ethane-1,2-diol; 4-amino-2-aminomethylphenol; 4 -Amino-1-hydroxy-2-(2'-hydroxyethylaminomethyl)benzene; 5-aminosalicylic acid and its salts; and mixtures thereof; o-phenylenediamine derivatives such as: 3,4- Diaminobenzoic acid and its salts; o-aminophenol derivatives, such as: 2-aminophenol; 2-amino-5-methylphenol; 2-amino-6-methylphenol; N-(4-amino-3 -hydroxyphenyl)-acetamide; 2-amino-4-methylphenol; 2-amino-5-ethylphenol; and mixtures thereof; and heterocyclic derivatives such as: pyrimidine-2,4,5, 6-tetramine; 1-methyl-1H-pyrazole-4,5-diamine; 2-(4,5-diamino-1H-pyrazol-1-yl)ethanol; 1-(4-methyl Benzyl)-1H-pyrazole-4,5-diamine; 1-(benzyl)-1H-pyrazole-4,5-diamine; N2,N2-lutidine-2,5-diamine ; 4-hydroxy-2,5,6-triaminopyrimidine; their salts; and mixtures thereof. the

In certain embodiments, the precursors include: 2-methylbenzene-1,4-diamine; 2-(methoxymethyl)benzene-1,4-diamine; benzene-1,4-diamine ; N, N-di(2-hydroxyethyl)-p-phenylenediamine; 4-aminophenol; 4-methylaminophenol; 4-amino-3-methylphenol; 2-aminophenol; 2-amino-5 -methylphenol; 2-amino-5-ethylphenol; 2-amino-6-methylphenol; 1-methyl-1H-pyrazole-4,5-diamine; 2-(4,5-di amino-1H-pyrazol-1-yl)ethanol; 2,5-diaminotoluene; 2,5-diaminophenylethanol; their salts; and mixtures thereof. the

Couplers suitable for use in the compositions described herein include, but are not limited to: phenol, resorcinol, naphthol, m-aminophenol, m-phenylenediamine, and heterocyclic compounds, and their derivatives, such as: 2-amino -5-Ethylphenol; Naphthalene-1,7-diol; Benzene-1,3-diol; 4-Chlorobenzene-1,3-diol; Naphthalene-1-ol; 2-Methyl-naphthalene- 1-alcohol; naphthalene-1,5-diol; naphthalene-2,7-diol; benzene-1,4-diol; 2-methylbenzene-1,3-diol; 7-amino-4- Hydroxy-naphthalene-2-sulfonic acid; 2-isopropyl-5-methylphenol; 1,2,3,4-tetrahydro-naphthalene-1,5-diol; 2-chlorobenzene-1,3- Diol; 4-Hydroxy-naphthalene-1-sulfonic acid; Benzene-1,2,3-triol; Naphthalene-2,3-diol; 5-chloro-2-methylbenzene-1,3-diol ; 4,6-dichlorobenzene-1,3-diol; 2,3-dihydroxy-[1,4]naphthoquinone; and 1-acetoxy-2-methylnaphthalene; m-phenylenediamines, For example: 2,4-diaminophenol; benzene-1,3-diamine; 2-(2,4-diaminophenoxy)-ethanol; 2-[(3-aminophenyl)-(2-hydroxy Ethyl)-amino]-ethanol; 2-methylbenzene-1,3-diamine; 2-[[2-(2,4-diaminophenoxy)-ethyl]-(2-hydroxyethyl )-amino]-ethanol; 4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine; 2-(2,4-diaminophenyl )-ethanol; 2-(3-amino-4-methoxyphenylamino)-ethanol; 4-(2-aminoethoxy)-benzene-1,3-diamine; (2,4-diamino phenoxy)-acetic acid; 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol; 4-ethoxy-6-methylbenzene-1, 3-diamine; 2-(2,4-diamino-5-methylphenoxy)-ethanol; 4,6-dimethoxybenzene-1,3-diamine; 2-[3-(2 -Hydroxyethylamino)-2-methylphenylamino]-ethanol; 3-(2,4-diaminophenoxy)-propan-1-ol; N-[3-(dimethylamino)benzene base] urea; 4-methoxy-6-methylbenzene-1,3-diamine; 4-fluoro-6-methylbenzene-1,3-diamine; 2-({3-[(2- hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol; 3-(2,4-diaminophenoxy)-propane-1,2-diol; 2-[2 -amino-4-(methylamino)-phenoxy]ethanol; 2-[(5-amino-2-ethoxyphenyl)-(2-hydroxyethyl)-amino]-ethanol; 2-[ (3-aminophenyl)amino]ethanol; 2,4-diamino-5-(2'-hydroxyethoxy)toluene; N,N-dimethyl-3-ureidoaniline; N-(2- Aminoethyl) benzene-1,3-diamine; 4-{[(2,4-diaminophenyl)oxy]methoxy}-benzene-1,3-diamine; 1-methyl-2 , 6-bis(2-hydroxyethylamino)benzene; and 2,4-dimethyl Oxybenzene-1,3-diamine; 1,3-bis-(2,4-diaminophenoxy)propane; 2-methyl-5-[(1-H-pyrrol-2-ylmethyl )-amino]-phenol; 5-[(furan-2-ylmethyl)-amino]-2-methylphenol; 5-isopropylamino-2-methylphenol; biphenyl-2,4,4 '-Triamine hydrochloride; 5-(4-aminophenyl)aminomethylbenzene-1,3-diamine hydrochloride 5-phenylaminomethylbenzene-1,3-diamine hydrochloride; 2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride; 5-(3-aminophenyl)aminomethylbenzene-1,3- Diamine hydrochloride; N-(2-aminobenzyl)-benzene-1,3-diamine hydrochloride; N-furan-2-ylmethylbenzene-1,3-diamine hydrochloride; 2 -[(3-Aminophenylamino)-methyl]-phenol hydrochloride; 4-amino-2-propylaminomethylphenol; N-benzo[1,3]dioxolan-5-yl Methylbenzene-1,3-diamine hydrochloride; N-[4-amino-2-(2-hydroxyethyl)-2H-pyrazol-3-yl]-3-(5-amino-2- hydroxyphenyl)-acrylamide; 4-amino-2-(isopropylamino-methyl)-phenol; 4-thiophen-3-ylbenzene-1,3-diamine; 5-phenylaminomethylbenzene -1,3-diamine hydrochloride; 5-(3-aminophenyl)aminomethylbenzene-1,3-diamine hydrochloride; 4-thiophen-3-ylbenzene-1,3-diamine ; 2′,4′-diaminobiphenyl-4-ol; 5-cyclobutylamino-2-methylphenol; 5-cyclobutylamino-2-methylphenol; 4-amino-2-(pyridine -3-ylaminomethyl)-phenol; 5-(3-aminophenyl)aminomethylbenzene-1,3-diamine hydrochloride; 5-allylaminomethylbenzene-1,3-diamine Amine hydrochloride; N-(4-aminobenzyl)-benzene-1,3-diamine hydrochloride; N-benzyl-benzene-1,3-diamine hydrochloride; 3-[(3- Aminophenylamino)-methyl]-phenol hydrochloride; N-(4-methoxybenzyl)-benzene-1,3-diamine hydrochloride; N-thiophen-2-ylmethylbenzene- 1,3-diamine hydrochloride; 4-amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol; 2′,4′-diaminobiphenyl-4 -alcohol hydrochloride; biphenyl-2,4,4'-triamine; 5-(4-aminophenyl)aminomethylbenzene-1,3-diamine hydrochloride; 2-[4-amino- 2-(3,5-Diamino-benzylamino)-phenoxy]-ethanol hydrochloride; 5-allylaminomethylbenzene-1,3-diamine hydrochloride; 5-(3- Aminophenyl)aminomethylbenzene-1,3-diamine hydrochloride; N-(4-aminobenzyl)-benzene-1,3-diamine hydrochloride; N-benzyl-benzene-1, 3-diamine hydrochloride; 3-[(3-aminophenylamino)-methyl]-phenol hydrochloride; N-(2-aminobenzyl)-benzene-1,3-diamine hydrochloride ; N-(4-methoxybenzyl)-benzene-1,3-diamine Hydrochloride; N-furan-2-ylmethylbenzene-1,3-diamine hydrochloride; 2-[(3-aminophenylamino)-methyl]-phenol hydrochloride; N-thiophene- 2-ylmethylbenzene-1,3-diamine hydrochloride; N-benzo[1,3]dioxol-5-ylmethylbenzene-1,3-diamine hydrochloride; m-aminophenols, for example: 3-aminophenol; 2-(3-hydroxy-4-methylphenylamino)-acetamide; 2-(3-hydroxyphenylamino)-acetamide; 5-amino-2 -methylphenol; 3-amino-2,6-dimethylphenol; 5-(2-hydroxyethylamino)-2-methylphenol; 5-amino-2,4-dichloro-phenol; 3- Amino-2-methylphenol; 3-amino-2,6-dimethylphenol; 3-amino-2-chloro-6-methylphenol; 5-amino-2-(2-hydroxy-ethoxy) -phenol; 2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol; 5-amino-4-chloro-2-methylphenol; 3-cyclopentylaminophenol; 5- [(2-Hydroxyethyl)amino]-4-methoxy-2-methylphenol; 5-amino-4-methoxy-2-methylphenol; 3-(dimethylamino)phenol; 3 -(diethylamino)phenol; 5-amino-4-fluoro-2-methylphenol; 5-amino-4-ethoxy-2-methylphenol; 3-amino-2,4-dichloro- Phenol; 3-[(2-methoxyethyl)amino]phenol; 3-[(2-hydroxyethyl)amino]phenol; 5-amino-2-ethylphenol; 5-amino-2-methoxy 5-[(3-hydroxy-propyl)amino]-2-methylphenol; 3-[(3-hydroxy-2-methylphenyl)-amino]propan-1,2-diol; 3-[(2-Hydroxyethyl)amino]-2-methylphenol; 2-methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol; 5-[( Furan-2-ylmethyl)-amino]-2-methylphenol; 5-isopropylamino-2-methylphenol; 5-cyclobutylamino-2-methylphenol; 1-methyl-2 -Hydroxy-4-(2'-hydroxyethyl)amino-benzene; and heterocyclic derivatives such as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol; 6-form Oxyquinolin-8-amine; 4-methylpyridine-2,6-diol; 2,3-dihydro-1,4-benzodioxan-5-ol; 1,3-benzobis Oxolane-5-ol; 2-(1,3-benzodioxolan-5-ylamino)ethanol; 3,4-lutidine-2,6-diol; 5-chloropyridine- 2,3-diol; 2,6-dimethoxypyridine-3,5-diamine; 1,3-benzodioxolane-5-amine; 2-{[3,5-diamino- 6-(2-Hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol; 1H-indol-4-ol; 5-amino-2,6-dimethoxypyridin-3-ol ; 1H-indole-5,6-diol; 1H-indole-7-ol; 1H-indole-5-ol; 1H-indole-6-ol; 6-bromo- 1,3-benzodioxolane-5-ol; 2-aminopyridin-3-ol; pyridine-2,6-diamine; 3-[(3,5-diaminopyridin-2-yl)oxy Base] propane-1,2-diol; 5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1,3-diol; indoline-5,6-diol ; 3,5-dimethoxypyridine-2,6-diamine; 6-methoxypyridine-2,3-diamine; 3,4-dihydro-2H-1,4-benzoxazine- 6-amine; 4-hydroxy-N-methylindole; 1H-5-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; 6-methylpyridine Azolo-[1,5-a]benzimidazole; 2,6-dihydroxypyridine; 2,6-dihydroxy-3,4-lutidine; 5-methylpyrazolo[5,1- e]-1,2,3-triazole; 5-methyl-6-chloropyrazolo[5,1-e]-1,2,3-triazole; 5-phenylpyrazolo[5, 1-e]-1,2,3-triazole and its addition salts; 1H-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole toluenesulfonic acid salt; 7,8-dicyano-4-methylimidazo[3,2-a]imidazole; 2,7-dimethylpyrazolo[1,5-a]pyrimidin-5-one; 2, 5-dimethylpyrazolo[1,5-a]pyrimidin-7-one; and 2-methyl-5-methoxymethylpyrazolo[1,5-a]pyrimidin-7-one; 6-hydroxybenzomorpholine; and 3-amino-2-methylamino-6-methoxypyridine; their salts; and mixtures thereof. the

In some embodiments, coupling agents include, but are not limited to: phenol, resorcinol, and naphthol derivatives, such as: 2-amino-5-ethylphenol; naphthalene-1,7-diol; benzene-1, 3-diol; 4-chlorobenzene-1,3-diol; naphthalene-1-ol; 2-methyl-naphthalene-1-ol; naphthalene-1,5-diol; naphthalene-2,7-diol alcohols; benzene-1,4-diol; 2-methylbenzene-1,3-diol; and 2-isopropyl-5-methylphenol; 1,2,4-trihydroxybenzene; 1-acetyl Oxy-2-methylnaphthalene; and their mixtures; m-phenylenediamine derivatives, such as: benzene-1,3-diamine; 2-(2,4-diaminophenoxy)-ethanol; 4- {3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine; 2-(3-amino-4-methoxyphenylamino)-ethanol; 2 -[2,4-Diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol; and 3-(2,4-diaminophenoxy)-propan-1-ol; 2 , 4-diamino-5-(2′-hydroxyethoxy)toluene; N,N-dimethyl-3-ureidoaniline; 2,4-diamino-5-fluorotoluene; 1-methyl- 2,6-Bis(2-hydroxyethylamino)benzene; and mixtures thereof; m-aminophenol derivatives, such as 3-aminophenol; 5-amino-2-methylphenol; 3-amino-2,6- Dimethylphenol; 5-(2-hydroxyethylamino)-2-methylphenol; and 3-amino-2-methylphenol; 1-hydroxy-3-amino-2,4-dichlorobenzene; 1 , 3-bis-(2,4-diaminophenoxy)propane; 1-hydroxy-2-methyl-5-amino-6-chlorobenzene; 5-amino-4-chloro-2-methylphenol; and mixtures thereof; and heterocyclic derivatives such as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol; 1,3-benzodioxolan-5-ol; 1,3-Benzodioxolane-5-amine; 1H-indole-4-ol; 1H-indole-5,6-diol; 1H-indole-7-ol; 1H-indole- 5-alcohol; 1H-indole-6-ol; pyridine-2,6-diamine; 2-aminopyridin-3-ol; 4-hydroxy-N-methylindole; 1H-5-methylpyrazole -5-one; 1-phenyl-3-methylpyrazol-5-one; 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole; 2, 6-Dimethyl[3,2-c]-1,2,4-triazole; 6-methylpyrazolo-[1,5-a]benzimidazole; 2,6-dihydroxypyridine; 2 , 6-dihydroxy-3,4-lutidine; 6-hydroxybenzomorpholine; 2,6-dihydroxy-3,4-lutidine; 3,5-diamino-2,6- Dimethoxypyridine; 3-amino-2-methylamino-6-methoxypyridine; their salts; and mixtures thereof. the

In certain embodiments, coupling agents include: 2-amino-5-ethylphenol; benzene-1,3-diol; 4-chlorobenzene-1,3-diol; 4,6-dichlorobenzene- 1,3-diol; 2-methylbenzene-1,3-diol; 2-amino-4-(2'-hydroxyethyl)aminoanisole; 2,4-diaminobenzyl alcohol; 2, 4-diaminophenylethanol; m-phenylenediamine; 5-amino-2-methylphenol; 3-amino-2,6-dimethylphenol; 2,4-diaminophenoxyethanol; 4-amino -2-Hydroxyphenoxyethanol; 1-naphthol; 2-methylnaphthol; 3-aminophenol; 3-amino-2-methylphenol; 4-hydroxy-1,2-methylenedioxybenzene ; 4-amino-1,2-methylenedioxybenzene; 4-(2′-hydroxyethyl)amino-1,2-methylenedioxybenzene; 1-methyl-2-hydroxy-4- (2'-Hydroxyethyl)aminobenzene; 2,4-diaminophenetole; 2,4-diamino-5-methylphenetole; 4-oxindole; 3-amino-5-hydroxy-2, 6-dimethoxypyridine; and 3,5-diamino-2,6-dimethoxypyridine; benzene-1,3-diamine; 2-aminopyridin-3-ol; 1-phenyl-3 -Methylpyrazol-5-ones; their salts; and mixtures thereof. the

Additionally, in some embodiments, the developer and coupler include 5-methoxymethyl-2-aminophenol; 5-ethyl-2-aminophenol; 5-phenyl-2-aminophenol; 5- Cyanoethyl-2-aminophenol; their salts; and mixtures thereof. the

The hair dye compositions of the present invention also comprise non-oxidative or direct dyes suitable for delivering shade correction or highlighting effects. Suitable direct dyes include, but are not limited to: Acid Yellow No. 1; Acid Orange No. 3; Disperse Red No. 17; Basic Brown No. 17; Acid Black No. 52; Acid Black No. 1; Disperse Violet No. 4; Phenylenediamine; 2-nitro-p-phenylenediamine; picric acid; HC red No. 13; 1,4-bis-(2′-hydroxyethyl)-amino-2-nitrobenzene; HC yellow No. 5, HC Red No. 7; HC Blue No. 2; HC Yellow No. 4; HC Yellow No. 2; HC Orange No. 1; HC Red No. 1; 2-chloro-5-nitro-N-hydroxyethyl p-phenylenediamine; HC Red No. 3; 4-amino-3-nitrophenol; 2-hydroxyethylamino-5-nitroanisole; 3-nitro p-hydroxyethylaminophenol; 2-amino-3-nitrophenol; 6-nitro-o-toluidine; 3-methylamino-4-nitrophenoxyethanol; 2-nitro-5-glycerylmethylaniline; HC yellow No. 11; HC purple No. 1; HC orange No. 2 ; HC Orange No. 3; HC Yellow No. 9; 4-Nitrophenylaminoethylurea; HC Red No. 10; HC Red No. 11; 2-Hydroxyethylpicric acid; HC Blue No. 12; HC Yellow No. 6 ; Hydroxyethyl-2-nitro-p-toluidine; HC Yellow No. 12; HC Blue No. 10; HC Yellow No. 7; HC Yellow No. 10; HC Blue No. 9; N-ethyl-3-nitroPABA; 4 -Amino-2-nitrophenylamino-2'-carboxylic acid; 2-chloro-6-ethylamino-4-nitrophenol; 6-nitro-2,5-pyridinediamine; HC Violet No. 2; 2-amino-6-chloro-4-nitrophenol; 4-hydroxypropylamino-3-nitrophenol; HC Huang No. 13; 1,2,3,4-tetrahydro-6-nitroquinoxaline ; HC Red No. 14; HC Yellow No. 15; HC Yellow No. 14; 3-amino-6-methylamino-2-nitropyridine; 2,6-diamino-3-((pyridin-3-yl) even Nitro)pyridine; Basic Red No. 118; Basic Orange No. 69; N-(2-nitro-4-aminophenyl)-allylamine; 4-[(4-amino-3-methylphenyl )(4-imino-3-methyl-2,5-cyclohexadien-1-ylidene)methyl]-2-methylaniline hydrochloride; 2-[[4-(dimethyl- Amino)phenyl]azo]-1,3-dimethyl-1H-imidazole chloride; 1-methyl-4-[(methylphenylhydrazino)methyl]-pyridine methyl sulfate; 2-[(4-aminophenyl)azo]-1,3-dimethyl-1H-imidazole chloride; Basic Red No. 22; Basic Red No. 76; Basic Brown No. 16; Basic Yellow 57 No.; 7-(2′,4′-dimethyl-5′-sulfophenylazo)-5-sulfo-8-hydroxynaphthalene; Acid Orange No. 7; Acid Red No. 33; 1-(3 '-Nitro-5'-sulfo-6'-oxyphenylazo)-oxynaphthalene chromium complex; Acid Yellow No. 23; Acid Blue No. 9; Basic Violet No. 14; Basic Blue No. 7 ; Basic Blue 26; Sodium salt of a mixture of monosulfonic and disulfonic acids (mainly the latter) of quinophthalone or 2-quinolindanedione; Basic Red No. 2; Basic Blue No. 99; disperse Red No. 15; Acid Violet No. 43; Disperse Violet No. 1; Acid Nature Blue No. 62; Pigment Blue No. 15; Acid Black No. 132; Basic Yellow No. 29; Disperse Black No. 9; 1-(N-methylmorpholinium propylamino)-4-hydroxyanthraquinone methyl ester sulfate ; N, N-dimethyl-3-((4-(methylamino)-9,10-dioxy-9,10-dihydroanthracen-1-yl)amino)-N-propyl bromide Propan-1-ammonium; HC Blue No. 8; HC Red No. 8; HC Green No. 1; HC Red No. 9; 2-hydroxy-1,4-naphthoquinone; Acid Blue No. 199; Acid Blue No. 25; Acid Red 4 Henna; Indigo; Carmine; HC Blue No. 14; Disperse Blue No. 23; Disperse Blue No. 3; Disperse Blue No. 377; Basic Red No. 51; Basic Orange No. 31; Basic Yellow No. 87; and their mixture. Preferred direct dyes include, but are not limited to: Disperse Black No. 9; HC Yellow No. 2; HC Yellow No. 4; HC Yellow No. 15; 4-nitro-o-phenylenediamine; Phenol; HC Red No. 3; Disperse Violet No. 1; HC Blue No. 2; Disperse Blue No. 3; Disperse Blue No. 377; Basic Red No. 51; Basic Orange No. 31; Basic Yellow No. 87; and mixtures thereof. the

The hair dye compositions of the present invention generally comprise from about 0.001% to about 10% dye when the powder composition is mixed with water. For example, compositions capable of providing low intensity coloring such as natural blonde to light brown hair shades, when mixed with water, generally comprise from about 0.001% to about 5%, preferably from about 0.1% to about 2%, more preferably from about 0.2% to about 1% by weight of precursors and couplers. Darker shades such as brown and black typically contain from 0.001% to about 10%, preferably from about 0.05% to about 7%, more preferably from about 1% to about 5%, by weight of precursors and couplers. the

Surfactant

The compositions of the present invention may also contain one or more surfactants to provide sensory benefits, such as slip. Surfactants suitable for use herein typically have a lipophilic chain length of from about 8 to about 30 carbon atoms, and can be selected from anionic, nonionic, amphoteric, and cationic surfactants and combinations thereof. mixture. Preferred surfactants include nonionic surfactants comprising one or more polyethylene oxide chains, such as polyoxyethylene alkyl ethers or polyethylene glycol fatty acid esters. Another preferred surfactant is an alkyl ether sulfate or alkyl ether phosphate, wherein especially preferred are alkyl groups having 1 to 20, preferably 1 to 10, most preferably 1 to 5 ethylene oxide units ether phosphate. the

Any combination of surfactants can be used. Such surfactants are generally employed at levels of from about 0.05% to about 30%, preferably from about 0.1% to about 15%, more preferably from about 0.2% to about 10%, by weight of the composition. the

Chelating agent

According to the invention, the composition may comprise a chelating agent. Chelating agents are well known in the art and refer to molecules or mixtures of different molecules each capable of forming a chelate with a metal ion. Chelating agents are well known in the art and a non-exhaustive list thereof can be found in AE Martell and RM Smith, "Critical Stability Constants", Vol. 1 (Plenum Press, New York & London, 1974) and AE Martell and RD Hancock, "Metal Complexes in Aqueous Solution" (Plenum Press, New York & London, 1996), both of which are incorporated herein by reference. the

Examples of chelating agents suitable for use herein include EDDS (ethylenediamine disuccinic acid), carboxylic acids (specifically aminocarboxylic acids), phosphonic acids (specifically aminophosphonic acids), and polyphosphoric acids (specifically straight-chain polyphosphoric acid), their salts and derivatives. the

Chelating agents may be incorporated into the compositions of the present invention as stabilizers and/or preservatives. It has also been found that chelating agents can provide hair fiber damage prevention benefits and thus they can be used to further improve the hair damage profile of the present invention. For the most effective chelating agent such as diamine-N, N'-dibasic acid and monoamine monoamide-N, N'-dibasic acid chelating agent (such as EDDS), the content of chelating agent in the present invention It can be as low as about 0.1%, preferably at least about 0.25%, more preferably about 0.5%. Depending on the efficacy of the chelating agent, less effective chelating agents are more preferably present at levels of at least about 1%, even more preferably greater than about 2%, by weight of the composition. the

Instructions

It should be understood that the examples and embodiments of methods of use described herein are for illustrative purposes only. Various modifications and changes can be made by those skilled in the art without departing from the spirit and scope of the present invention. the

The powder composition of the present invention is provided in a hermetically sealed package in an amount suitable for single use. During its shelf life, the composition must be stable, with the components therein unreactive and unreactive with atmospheric moisture. The compositions of the present invention have instructions for the consumer to mix the appropriate amount of water to provide the target concentrations of the components for a single use dose of the powdered composition. Accordingly, the amounts of components in the powder compositions of the present invention can be adjusted according to the specified amount of water with which the powder compositions are to be mixed. The powder composition is generally intended to be mixed with about 4 to about 5 times the weight of water. the

Since mixing with water is typically carried out in the consumer's home with gentle hand mixing, the reaction and thickening of the dispersed composition is intended to take place within about 60 seconds, more preferably within about 30 seconds, with gentle mechanical agitation. The consumer mixes the composition with water and applies it to the hair just before use. the

After applying the resulting dispersion composition to the entire hair area for coloring for a few minutes (to ensure even application to all the hair), the composition is left on the hair for a period of time sufficient for coloring to occur (generally about 2 to 60 minutes, usually about 30 to 45 minutes). The consumer then rinses his/her hair thoroughly with tap water and allows it to dry. It was observed that the hair had changed from its original color to the desired color. the

The present invention also includes embodiments wherein the method of coloring or bleaching hair comprises applying a composition comprising at least one oxidizing agent for at least about 50% of the time that said composition is applied to the hair , at least one source of carbonate ions, carbamate ions, or bicarbonate ions, and mixtures thereof, and a free radical scavenger-free polymer thickening system as defined herein, said composition having at most about pH of 9.4. the

The method of coloring or bleaching hair according to the invention also includes embodiments wherein the composition is applied to the hair and the mixture is preferably allowed to act for a few minutes (to ensure even application to all the hair). The composition is then left on the hair to develop the color for a period of less than about 20 minutes, preferably less than about 15 minutes, more preferably from about 5 minutes to about 10 minutes, most preferably about 10 minutes. The consumer then rinses his/her hair thoroughly with tap water and dries or styles the hair as usual. This method provides additional convenience to the consumer by allowing faster dye or bleach application. the

According to an alternative embodiment of the present invention, the method of coloring and/or bleaching of hair is a sequential oxidative hair coloring or hair bleaching method comprising at least two consecutive oxidative hair coloring or hair bleaching methods wherein the time interval between each treatment is 1 to 60 days, preferably 1 to 40 days, more preferably 1 to 28 days, even more preferably 1 to 14 days, and most preferably 1 to 7 days. In the above embodiments, the composition may remain on the head for less than about 20 minutes, and preferably less than about 10 minutes, and most preferably from about 2 minutes to about 5 minutes. This method enables the consumer to perform a coloring or bleaching process in a manner similar to conventional hair washing or conditioning processes. the

The compositions herein may be prepared economically by any of a variety of standard methods. The compositions may be provided in structured packs, cartridges or sachets, provided they are made of air-impermeable material and remain hermetically sealed for the desired shelf life. The air remaining within the package may be evacuated, or replaced with an inert gas such as nitrogen, prior to sealing. the

Application of the dispersion composition to the hair can be carried out using equipment that assists in achieving special effects such as highlights, such as highlighting combs, highlighting brushes and tools, foils, and highlighting caps. the

Other device technologies can be used to assist product penetration into the hair. Examples of the aforementioned technologies include heating devices, ultraviolet light devices, and ultrasonic devices. the

Example

The following examples further describe and demonstrate embodiments within the scope of the present invention. These examples are given for the purpose of illustration only and are not to be construed as limitations of the invention, since many variations thereof are possible without departing from the spirit and scope of the invention. Where applicable, ingredients are identified by chemical or CTFA name unless otherwise defined below. the

The following examples illustrate oxidative dye compositions according to the invention. It should be understood that the examples and embodiments described herein are illustrative only and that numerous other changes and modifications may be made thereto by those skilled in the art without departing from the scope of the invention. Examples 1 to 29 are compositions according to the invention, while comparative examples 1 to 5 are those not according to the invention. the

Compositions and Coloring Results of Examples 1 to 28

Examples 1 to 28 are powdery hair coloring compositions of the present invention. The components and coloration results in the compositions of Examples 1 to 28 are listed in Tables 1 to 7 below, followed by the method by which they were made and how we used them. the

Table 1

Table 2

table 3

Table 4

table 5

Table 6

Table 7

*Acrylates/C10-30 Alkyl Acrylate Crosspolymer: Carbopol ETD 2020 from Noveon

The compositions of the present invention are capable of providing a wide variety of shades. the

Preparation

The components were mixed well, transferred into packages made of air-impermeable material and sealed under nitrogen atmosphere. Instructions are provided to mix the contents of each dose with 4 times its weight in water. the

How to use and hair coloring results

The composition was hand mixed with 4 times the weight of water for 60 seconds, then applied to the hair, left on for 30 minutes, and then the composition was rinsed from the hair with water. When applied to hair in accordance with this direction, each composition provides hair coloration indicative of a "result". The compositions of the present invention are capable of providing a variety of hair coloring results and thus have the potential to provide a wide variety of shades. the

gray hair covering

Example 1 above and Comparative Example 1 not in accordance with the present invention were subjected to a gray hair coverage effectiveness test. Comparative Example 1 is Bigen Xpressive Café Latte available in the United States in 2007, which has a similar hue to Example 1. the

The following hair switches were dyed with Example 1 and Comparative Example 1, respectively, according to the method of use as described above, while Comparative Example 1 was added to 100 ml of water according to the instructions provided on the package. the

1) 3/0 dark brown hair

2) 50/50 blend of gray hair and 3/0 hair

After dyeing, test hair switches as well as undyed 50% gray hair-3/0 hair switches were washed under the following conditions:

For water from -35°C to 40°C, the flow rate is 4±0.51/min

-One wash with Pantene Clarifying Shampoo available in the US in 2007

- rinse

- Blow dry with a hair dryer. the

After drying, L, a, b values were obtained for the dyed 3/0 hair, dyed 50% gray hair blend, and undyed 50% gray hair blend using a Minolta spectrophotometer CM-3700d. Then take the formula ΔE values were calculated using the L, a, b values. From these values, the percent gray hair coverage can be calculated as follows:

The gray hair coverage obtained in Example 1 and Comparative Example 1 is as follows. the

the Example 1 Comparative Example 1 Gray hair coverage (%) 82.5% 31.4%

From the results, it can be seen that the composition of the present invention having a similar shade provides significantly better gray hair coloring than Comparative Example 1. the

Thickener properties and pH

Example 29 according to the invention and comparative examples 1 to 5 not according to the invention were subjected to a test of their properties as thickeners. Example 29 and Comparative Examples 1 to 5 did not contain hair dye to allow easy observation of thickening properties. Table 9 shows the base composition of each of Example 29 and Comparative Examples 1 to 5. To this base composition were added specific thickeners as indicated in Table 10. the

Table 9

components parts by weight Sodium percarbonate 12.00 ammonium sulfate 7.08 Glycine sodium salt 2.52

Table 10

Example number Thickener Description Example 29 Acrylates/C10-30 Alkyl Acrylate Crosspolymer: Carbopol ETD 2020 from Noveon

the Comparative Example 1 PEG 15 Stearate: Aculyn 60 from Rohm & Haas Comparative Example 2 Carboxymethylcellulose 700k, 0.9DS ^* 1) Comparative Example 3 Carboxymethyl cellulose 250k, 0.7DS Comparative Example 4 Carboxymethyl cellulose 250k, 0.9DS Comparative Example 5 Carboxymethyl cellulose 250k, 1.2DS

^* 1)k stands for weight average molecular weight, DS stands for degree of substitution.

Each composition was mixed with 4.17 times the weight of water to provide dispersed compositions each having 2.44% thickener. After mixing with water, each composition was stirred with a stir bar and observed for the time to maximum consistency and further observed for coagulation. After reaching the maximum consistency, the dispersion composition was tested for adhesion on the hair and spreadability on the hair by an expert panelist. Viscosity was measured only for those dispersed compositions with sufficient adhesion and spreadability using a Brookfield viscometer spindle S52 at 0.5 rpm. The pH was measured for all dispersion compositions except Comparative Example 1 which was too thick to measure the pH. The results for each thickener property item are described in Table 11. the

Table 11

the Time to reach maximum consistency (seconds) condensation Adhesion to hair Spreadability on hair Viscosity (mPas) PH value Example 29 30 no pass pass 13500 9.25 Comparative Example 1 the yes pass unqualified the the Comparative Example 2 140 yes unqualified pass the 9.57 Comparative Example 3 151 yes unqualified pass the 9.55 Comparative Example 4 137 yes unqualified pass the 9.62 Comparative Example 5 110 no unqualified pass the 9.67

From the above results, it can be understood that only Example 29 of the present invention provided satisfactory thickener properties as well as a suitable pH. the

The dimensions and values disclosed herein are not to be construed as strict limitations to the precise values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a disclosed dimension of "40mm" is intended to mean "about 40mm". the

Every document cited herein, including any cross-referenced or related patent or application, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein, either by itself or in any combination with any other reference, or to refer to, suggest, suggest or Discloses any acknowledgment of such inventions. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern. the

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention. the

Claims (10)

1. A powdered hair coloring composition comprising: a) at least one solid source of peroxymonocarbonate ions, carbamate ions or bicarbonate ions or mixtures thereof, wherein the solid source of ions is a percarbonate selected from the group consisting of sodium percarbonate, Potassium percarbonate and calcium percarbonate, wherein said ion source contained in a powder composition provides 0.5 mol/1 to 1.5 mol/1 of said ion source when the powder composition is mixed with 4 to 5 times the weight of water; b) at least one solid source of oxidizing agent; c) at least one solid source of ammonium ions; and d) a cross-linked carboxylic acid polymer thickener, wherein the cross-linked carboxylic acid polymer thickener is a C10 to C30 alkyl acrylate crosspolymer, the thickener having a particle size of not more than about 10 microns ; when the powder composition is mixed with water, the amount of the thickener can provide a concentration of 1% to 3%; when measured at 0.5 rpm using a Brookfield viscometer spindle S52, the thickener can contribute to The dispersed composition provides a viscosity of 10000 mPas to 20000 mPas and a pH of 8.5 to 9.4. 2. The composition of claim 1, wherein the solid source of carbonate ions, carbamate ions, bicarbonate ions, or mixtures thereof is percarbonate. 3. The composition of claim 2, wherein the percarbonate is selected from the group consisting of sodium percarbonate, potassium percarbonate and calcium percarbonate. 4. The composition of claim 1, wherein the solid source of ammonium ions is selected from the group consisting of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium carbonate, ammonium bicarbonate, Ammonium Carbamate and Ammonium Hydroxide. 5. The composition of claim 4, wherein the solid source of ammonium ions is ammonium sulfate. 6. The composition of claim 1 further comprising a free radical scavenger. 7. The composition of claim 6, wherein the free radical scavenger is selected from the group consisting of alkanolamines and amino acids having a reaction energy of 0 kcal/mol to 14 kcal/mol and a molecular weight of no greater than 250. 8. The composition of claim 7, wherein the free radical scavenger is selected from the group consisting of glucosamine, glycine, glutamic acid, arginine, lysine, glutamine, histamine acid, serine, and their mixtures. 9. The composition of claim 1 further comprising a chelating agent. 10. A method of coloring hair, said method comprising the steps of: a) providing a composition as claimed in claim 1; b) mixing said composition with a specified amount of water; c) applying said dispersed composition to the hair; d) leaving the dispersed composition on the hair for 2 to 60 minutes; and e) Rinse the dispersed composition from the hair.