CN102137653B

CN102137653B - Powdered hair coloring and bleaching compositions

Info

Publication number: CN102137653B
Application number: CN200980100942.4A
Authority: CN
Inventors: 约翰·M·加德利克; 杰弗里·A·鲍尔斯; 布赖恩·P·墨菲
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 2009-11-24
Filing date: 2009-11-24
Publication date: 2014-09-10
Anticipated expiration: 2029-11-24
Also published as: CN102137653A; JP5540013B2; EP2503985A4; WO2011065934A1; EP2503985A1; MX2012005916A; JP2012503675A

Abstract

The present invention relates to a powder hair coloring or bleaching composition, comprising: a) at least one solid source of carbonate ions, carbamate ions, hydrogencarbonate 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 crosslinked carboxylic acid polymer thickener having a particle size of no more than about 10 microns in an amount which, upon admixture of the powder composition with water to provide a concentration of from about 1% to about 3%, provides the dispersed composition a viscosity of from about 10000 mPas to about 20000 mPas when measured at 0.5 rpm using Brookfield viscometer spindle S52, and a pH of from about 8.5 to about 9.4.

Description

Powdered chromotrichia and bleaching composition

Invention field

The present invention relates to Powdered chromotrichia and bleaching composition, described compositions is formulated for for consumer and adds water.

Background of invention

Two components, three components or four components system of most of oxidizing hair coloring agents products of current retail based on liquid form, described system is comprised of following: the developer that 1) comprises water and hydrogen peroxide, 2) the toning substrate that comprises water, oxidation dye precursors and basifier, with optional 3) with 1) and 2) mix other wrap solvent-laden component, and optional 4) post processing hair conditioner.Due to the material of mobile larger volume, especially water and solvent, therefore packing is complicated, and cost of transportation is considerable.The powdered product forms that preparation adds water use for consumer minimizes the impact of these two problems, therefore with lower cost, provides eco-friendly product.

Powdered chromotrichia and bleaching composition are known in the art, yet with respect to fluid product form, to developing the concern of this product form, are not very high.This cannot compare with liquid form product the performance of powder type product.The not good aspect of common viewed powder type product expression comprises dazzles that degree of dying is low and colouring property is poor, thereby causes the dyeing efficiency of gray hair lower.

In addition, because needs stabilizing dye precursor is to prevent before mixing with water reaction, owing to lacking the method for stabilizing dye precursor, thus the selection of dyestuff former only limit to can sulfate or hydrochloride form obtain those, thereby limited the multiformity of tone.Although proposed the suggestion of one or more components in stable and/or coated product, yet this type of processing will increase cost, so for conventionally orientating this product form of eco-friendly low-cost product as, this is unfavorable.

In addition,, for this product form, when product being mixed with water and alkali reacts with ammonia source, the generation of ammonia will inevitably be there is.This ammonia taste makes the process for preparation of this product form make us very much unhappy.

Described in above, Powdered chromotrichia and bleaching composition need to be provided, what described compositions can provide satisfactory degree dazzles metachromia and colouring property so that they can be used for gray hair, there is the possibility that more extensive diversified tone is provided, and reduce the damage that hair is caused, be easy to preparation simultaneously and there is pleasant abnormal smells from the patient when mixing use with water, and there is sufficient frame Tibetan stability.

Without any prior art, can provide all advantages of the present invention and beneficial effect.

Summary of the invention

The present invention relates to Powdered chromotrichia or bleaching composition, described compositions comprises:

A) solid source of at least one carbanion, carbamic acid radical ion, bicarbonate ion or their mixture;

B) at least one oxidant with solid source;

C) at least one ammonium ion solid source; With

D) crosslinked carboxylic acid polymer thickeners useful, described thickening agent has the granularity that is no more than approximately 10 microns.When powdered composition mixes with water, the amount of described thickening agent can provide approximately 1% to approximately 3% concentration.When using Brookfield viscometer spindle S52 when 0.5rpm measures, described thickening agent can provide the viscosity of about 10000mPas to about 20000mPas and approximately 8.5 to approximately 9.4 pH to the compositions of disperseing.

The invention still further relates to the method for chromotrichia or bleaching, said method comprising the steps of:

A) provide above-mentioned composition;

B) described compositions is mixed with the water of specified amount;

C) compositions of described dispersion is administered on hair;

D) make the compositions of described dispersion on hair, retain approximately 2 to approximately 60 minutes; And

E) compositions of described dispersion is rinsed from hair.

After being administered on hair, what the invention provides satisfactory degree dazzles metachromia and colouring property so that they can be used for gray hair, there is the possibility that more extensive diversified tone is provided, and reduce the damage that hair is caused, be easy to preparation simultaneously and there is pleasant abnormal smells from the patient when mixing use with water, and there is sufficient frame Tibetan stability.

Detailed Description Of The Invention

Although this description by particularly point out and clearly claimed claim of the present invention draw a conclusion, should believe by following explanation and can understand better the present invention.

Pending " hair " of term used herein can be " lived ", on life entity, or " not having lived ", i.e. and wig, artificial brow or other is without life cutin fiber aggregation.Mammiferous hair, the preferred mankind's hair is preferred.Yet Pilus Caprae seu Ovis, fur and other fiber that comprises cutin are also suitable for use as the substrate of the present composition.

All percentage ratio is all by the weighing scale of described total composition, unless stated otherwise.While using more than one compositions during processing, gross weight is considered to be applied in the gross weight (weight that is present in " on head ") of all compositionss on hair simultaneously, except as otherwise noted.All ratios is weight rate, unless stated otherwise.All molar concentrations are all by the stereometer of described total composition and be expressed as molal quantity or " mol/L " of component in one liter of compositions.While using more than one compositions during processing, cumulative volume is considered to be administered to the cumulative volume (volume that is present in " on head ") of all compositionss on hair simultaneously, except as otherwise noted.

As used herein, " compositions " or " powder composition " relates to the present composition of powder type, with this form, to consumer, provide described product, and " compositions of dispersion " relates to by powder composition is mixed to the fluid composition providing with the water of specified amount.

carbanion source

According to the present invention, described compositions comprises carbanion or carbamic acid radical ion or the solid source of bicarbonate ion or peroxide one carbanion or their any mixture.In described compositions, provide the solid source of described ion herein so that at least concentration of 0.2mol/l to be provided when described powder composition mixes with water.When powder composition mixes with water, the present composition aims to provide preferred about 0.4mol/l to about 2.0mol/l, and more preferably from about 0.5mol/l is to the described ion source of about 1.5mol/l.

Can use any solid source of these ions.Be applicable to sodium salt, potassium salt, lithium salts, calcium salt, magnesium salt, barium salt, ammonium salt and their mixture that source herein comprises carbonate, carbamic acid root and bicarbonate ion, as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, calcium carbonate, magnesium carbonate, brium carbonate, ammonium carbonate, ammonium bicarbonate and their mixture.Also can provide carbanion source and oxidizer source with percarbonate.The preferred solid source of carbanion, carbamic acid radical ion and bicarbonate ion is SODIUM PERCARBONATE, potassium percarbonate, percarbonic acid calcium and their mixture.

oxidant

Thus, according to compositions of the present invention, can form peroxide one carbanion.These ions typical case is formed on the spot by the reaction between hydrogen peroxide and carbanion source.Therefore, compositions can comprise at least one oxidizer source as described in the present invention.The oxidant being preferred for is herein that water-soluble solid is crossed peroxygen oxidising agent." water solublity " defined herein refers under usual conditions at least solvable 0.1g in every liter of deionized water, preferably 1g, the more preferably described oxidant of 10g.Oxidant can be used for melanic initial dissolution and decolouring (bleaching), and can promote the oxidation (oxidising dyeing) of oxidative dyestuff precursor in hair shaft.

Any solid oxidizer known in the art all can be used in the present invention.Preferred water-soluble oxidizers is the inorganic peroxy material that can produce hydrogen peroxide in aqueous solution.It is well known in the art that water solublity is crossed peroxygen oxidising agent, and comprises hydrogen peroxide, inorganic base metal peroxide (as sodium metaperiodate and sodium peroxide) and organic peroxide (as urea peroxide, peroxidating tripolycyanamide) and inorganic perhydrate salts bleaching compounds (as the alkali metal salt of perboric acid, percarbonic acid, peroxophosphoric acid, mistake silicic acid, persulfuric acid etc.).These inorganic perhydrate salts can be used as monohydrate, tetrahydrate etc. and mix.Also can use alkyl and aryl peroxides and/or peroxidase.If needed, can use the mixture of two or more above-mentioned oxidants.Be preferred in the present composition is percarbonate (it can be used for providing oxidizer source and carbanion source), persulfate and their combination.

According to the present invention, when powder composition mixes with water, described compositions aims to provide preferably approximately 0.1 % by weight to approximately 10 % by weight, and preferably approximately 1 % by weight is to approximately 7 % by weight, and most preferably from about 2 % by weight to the oxidant of approximately 5 % by weight.

ammonium ion source

According to the present invention, described compositions comprises at least one ammonium ion solid source.Any ammonium ion solid source is all suitable for herein.Preferred source comprises ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium carbonate, ammonium bicarbonate, aminoquinoxaline, ammonium hydroxide, percarbonate, ammonia and their mixture.Especially preferably sulfuric acid ammonium, ammonium carbonate, aminoquinoxaline, ammonia and their mixture.Ammonium ion and carbanion are preferably with 3: 1 to 1: 10, and preferably the weight rate of 2: 1 to 1: 5 is present in described compositions.

When powder composition mixes with water, compositions of the present invention aims to provide preferred approximately 0.1 % by weight to approximately 10 % by weight, and preferably approximately 0.5 % by weight is to approximately 5 % by weight, and most preferably from about 1 % by weight is to the ammonium ion of approximately 3 % by weight.

crosslinked carboxylic acid polymer thickeners useful

In the time of in described compositions is scattered in to water, aforementioned component of the present invention provides percarbonic acid foundation group, and this percarbonic acid foundation group contributes to effectively to bleach with painted in the short period of time.This make to dazzle metachromia and colouring property improvement to they can be used for the degree of gray hair.In addition,, by making the compositions of disperseing have approximately 8.5 to approximately 9.4, preferably approximately 9.0 to approximately 9.4 pH, can reduce the concentration of peroxide to alleviate the damage to hair fiber, also can reduce the release of ammonia simultaneously, and alleviate the abnormal smells from the patient sending from it.After mixing with water, the gained viscosity of described compositions must be controlled and to be suitable for user, is administered on hair within the specific limits.At powder composition, mix to provide with water after approximately 1% to approximately 3% concentration, the target viscosities that use Brookfield viscometer spindle S52 records at 0.5rpm is for about 10000mPas is to about 20000mPas, and preferred about 12000mPas is to about 18000mPas.Those skilled in the art will recognize that, the type of thickening agent and content are not unique factors of the final resulting composition viscosity of impact, and other component and component interaction are also influence factors such as adding the formation etc. of salt and layer structure.Therefore,, for required viscosity is provided, must consider remaining component.According to the present invention, described compositions comprises the buffering thickening agent that meets all following conditions:

(1) with compositions in all the other solid constituents compatible so that stability to be provided during storage life;

(2) when mixing with water, be easy to disperse;

(3), when mixing with water, short time gentle agitation can provide suitable viscosity; And

(4) compositions of described dispersion can be buffered to suitable pH.

Surprisingly, have now found that granularity is no more than approximately 10 microns, preferably the crosslinked carboxylic acid polyalcohol of approximately 0.1 micron to approximately 7 microns can provide fast and effectively thickening power when mixing with water, and suitable viscosity and target pH is provided simultaneously in percarbonate system of the present invention.Be not bound by theory, in the available multiple high molecular in this area and networking polymer, thickening power is only provided to provide fast and effectively and can not be produced unacceptable agglomerate, and can provide required viscosity and without the polymer for the unacceptable long-time stirring of this product form.In addition, crosslinked carboxylic acid polymer thickeners useful of the present invention can be buffered to target pH by the compositions of described dispersion, and this pH is lower than the pH of known other percarbonate system of using with powder type.

Can be used for crosslinked carboxylic acid polyalcohol herein for example can be selected from:

(i) cross-linked acrylic acid homopolymer;

(ii) copolymer of acrylic acid or (methyl) acrylic acid copolymer and acrylic acid or (methyl) acrylic acid C1-C30 Arrcostab.

Preferred polymer is acrylic acid C10-C30 alkyl ester cross-linked polymer.Can be highly for the crosslinked carboxylic acid polyalcohol of commercially available acquisition herein, comprise the product of being sold by Noveon company with trade name Carbopol ETD 2020,10,980,981,954,2984,5984.

Can be furnished with the Mettler Toledo MP220 of standard laboratory pH electrode or the pH that MP225pH equipment is measured described compositions by use.Before each use, use standard calibration buffer agent, and use standard calibration program to calibrate equipment.

free radical scavenger

According to the present invention, described compositions also can comprise free radical scavenger.When powder composition mixes with water, the amount of described free radical scavenger preferably can provide approximately 0.1 % by weight to approximately 10 % by weight, and more preferably from about 1 % by weight is to approximately 7 % by weight.

Can be used for free radical scavenger herein and be defined as and can react with carbonate group, carbonate group is transformed into by a series of fast reactions to the material of low activity material, i.e. carbonate scavenger.

Be not bound by theory, it is believed that the ability of free radical scavenger conversion carbonate group depends on charge transfer reaction energy as follows:

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

Wherein reaction can be by give a definition:

Δ H _r=Δ H _f(product)-Δ H _f(reactant)

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

According to the present invention, described compositions does not comprise its reaction can be for about 0kcal/mol be to about 14kcal/mol, and preferred about 1.5kcal/mol is to the free radical scavenger of about 9kcal/mol.

Can be used for free radical scavenger herein and comprise those with lower molecular weight, it has the combination of hydroxyl and amido, or the combination of carboxyl and amido, as alkanolamine and aminoacid.Highly preferred free radical scavenger choosing is herein the group of following composition freely: glycosamine, glycine, glutamic acid, arginine, lysine, glutamine, histidine, serine and their mixture.

annexing ingredient

Compositions of the present invention also can comprise supplementary element, and described supplementary element includes but not limited to hair dye (such as oxidation dye precursors, non-oxidizable dyestuff), enzyme, surfactant, antioxidant, stabilizing agent (such as arabo-ascorbic acid), chelating agen, hair-waving active substance, spice, reducing agent (thiolactic acid), hair extender and/or polymer.Below describe some in these annexing ingredients in detail.

hair dyes

Hair composition of the present invention is preferably the hair coloring compositions that comprises oxidation dyeing composition.Such composition comprises oxidative hair dyestuff former (being also referred to as main intermediate or developer) from multiple hair color to hair that send.The activation of oxidized dose of these micromolecule and with other molecular reaction to form larger colored complex in hair shaft.

Described precursor can be used alone or be used in combination with other precursor, and one or more precursors can be combined use with one or more coupling agents.The normally colourless molecule of coupling agent (being also referred to as color adaptation agent or less important intermediate).They can produce color under the existence of activation precursor, and can be together with other precursor or coupling agent for generation of specific color effects or make colour stable.The selection of precursor and coupling agent will be depended on desired color, color harmony tinctorial strength.Can be used alone or in combination precursor and coupling agent herein so that the dyestuff with multiple color tones to be provided, described tone is changed to black from light gray golden yellow.

The precursor being applicable in compositions described herein includes but not limited to p-phenylene diamine derivative, for example benzene-Isosorbide-5-Nitrae-diamidogen (being commonly referred to p-phenylenediamine (PPD)); 2-chlorobenzene-Isosorbide-5-Nitrae-diamidogen; N-phenyl benzene-Isosorbide-5-Nitrae-diamidogen; N-(2-ethoxyethyl group) benzene-Isosorbide-5-Nitrae-diamidogen; 2-[(4-aminophenyl)-(2-hydroxyethyl)-amino]-ethanol (being commonly referred to N, N-bis-(2-hydroxyethyl) p-phenylenediamine (PPD)); (2,5-diamino-phenyl)-methanol; 1-(2 '-hydroxyethyl)-2,5-diaminobenzene; 2-(2,5-diamino-phenyl)-ethanol; N-(4-aminophenyl) benzene-Isosorbide-5-Nitrae-diamidogen; 2,6-dimethyl benzene-Isosorbide-5-Nitrae-diamidogen; 2-cumene-Isosorbide-5-Nitrae-diamidogen; 1-[(4-aminophenyl) amino]-propyl-2-alcohol; 2-propylbenzene-Isosorbide-5-Nitrae-diamidogen; 1,3-bis-[(4-aminophenyl) (2-hydroxyethyl) amino] propan-2-ol; N4, N4,2-trimethylbenzene-Isosorbide-5-Nitrae-diamidogen; 2-methoxybenzene-Isosorbide-5-Nitrae-diamidogen; 1-(2,5-diamino-phenyl) ethanol; 1-(2,5-diamino-phenyl) second-1,2-glycol; 2,3-dimethyl benzene-Isosorbide-5-Nitrae-diamidogen; N-(4-amino-3-hydroxy base)-acetamide; 2,6-, bis-base benzene-Isosorbide-5-Nitrae-diamidogen; 2,5-dimethyl benzene-Isosorbide-5-Nitrae-diamidogen; 2-thiophene-2-base benzene-Isosorbide-5-Nitrae-diamidogen; 2-thiene-3-yl-benzene-Isosorbide-5-Nitrae-diamidogen; 2-pyridin-3-yl benzene-Isosorbide-5-Nitrae-diamidogen; 1,1 '-biphenyl-2,5-diamidogen; 2-(methoxy) benzene-Isosorbide-5-Nitrae-diamidogen; 2-(amino methyl) benzene-Isosorbide-5-Nitrae-diamidogen; 2-(2,5-diamino phenoxy) ethanol; N-[2-(2,5-diamino phenoxy) ethyl]-acetamide; N ', N-dimethyl benzene-Isosorbide-5-Nitrae-diamidogen; N, N-diethylbenzene-Isosorbide-5-Nitrae-diamidogen; N, N-dipropyl benzene-Isosorbide-5-Nitrae-diamidogen; 2-[(4-aminophenyl) (ethyl) amino] ethanol; 2-[(4-amino-3-aminomethyl phenyl)-(2-hydroxyethyl)-amino]-ethanol; N-(2-methoxy ethyl)-benzene-Isosorbide-5-Nitrae-diamidogen; 3-[(4-aminophenyl) amino] third-1-alcohol; 3-[(4-aminophenyl)-amino] the third-1,2-glycol; N-{4-[(4-aminophenyl) amino] butyl } benzene-Isosorbide-5-Nitrae-diamidogen; 2-[2-(2-{2-[(2,5-diamino-phenyl)-oxygen base] ethyoxyl } ethyoxyl) ethyoxyl] benzene-Isosorbide-5-Nitrae-diamidogen; 1,3-bis-(N (2-hydroxyethyl)-N-(4-aminophenyl) amino)-2-propanol; 2,2 '-[1,2-second, two base-bis--(oxygen base-2,1-ethylenedioxy)]-bis-benzene-Isosorbide-5-Nitrae-diamidogen; P-aminophenol derivatives, for example: PAP (being commonly referred to para-aminophenol); 4-methylamino phenol; 4-amino-3-methylphenol; 4-amino-2-hydroxymethyl phenol; 4-amino-2-methyl phenol; 4-amino-1-hydroxyl-2-(2 '-hydroxyethyl amino methyl) benzene; 4-amino-2-methoxy phenol; Asacol; 1-(5-amino-2-hydroxy phenyl)-ethyl-1,2-glycol; 4-amino-2-(2-hydroxyethyl) phenol; 4-amino-3-(hydroxymethyl) phenol; 4-amino-3-fluorophenol; 4-amino-2-(amino methyl) phenol; The fluoro-phenol of 4-amino-2-; 1-hydroxyl-2,4-diaminobenzene; O-phenylene diamine derivatives, as: 3,4-diaminobenzoic acid and its salt; O-aminophenol derivatives, for example: Ortho-Aminophenol (being commonly referred to o-aminophenol); 2,4-diaminophenol; 2-amino-5-methylphenol; 2-amino-5-ethyl-phenol; 2-amino-6-methylphenol; N-(4-amino-3-hydroxy base)-acetamide; With 2-amino-4-methylphenol; And Hete rocyclic derivatives, for example: pyrimidine-2,4,5,6-tetramine (being commonly referred to 2,4,5,6-tetraminopyrimidine); 1-methyl isophthalic acid H-pyrazoles-4,5-diamidogen; 2-(4,5-diaminostilbene H-pyrazol-1-yl) ethanol; N2, N2-lutidines-2,5-diamidogen; 2-[(3-amino-6-methoxypyridine-2-yl) amino] ethanol; 6-methoxyl group-N2-picoline-2,3-diamidogen; 2,5,6-Triaminopyrimidine-4 (1H)-one; Pyridine-2,5-diamidogen; 1-isopropyl-1H-pyrazoles-4,5-diamidogen; 1-(4-methyl-benzyl)-1H-pyrazoles-4,5-diamidogen; 1-(benzyl)-1H-pyrazoles-4,5-diamidogen; 1-(4-chlorobenzyl)-1H-pyrazoles-4,5-diamidogen; Pyrazolo [1,5-a]-pyrimidine-3,7-diamidogen; 5,6,7-trimethyl pyrazolo [1,5-a] pyrimidin-3-yl amine hydrochlorate; 7-methylpyrazole is [1,5-a] pyrimidin-3-yl amine hydrochlorate also; 2,5,6,7-tetramethyl pyrazolo [1,5-a] pyrimidin-3-yl amine hydrochlorate; 5,7-, bis--tert-butyl group pyrazolo [1,5-a] pyrimidin-3-yl amine hydrochlorate; 5,7-di-trifluoromethyl-pyrazolo [1,5-a] pyrimidin-3-yl amine hydrochlorate; 2-methylpyrazole is [1,5-a] pyrimidine-3 also, 7-diamine hydrochloride; 4-hydroxyl-2,5,6-Triaminopyrimidine; 2,3-diaminourea-6,7-dihydro-pyrazolo [1,2-a] pyrazoles-1 (5H)-one dimethanesulfonate; 1-hydroxyethyl-4,5-diamino-pyrazole; 2,5-diamino-phenyl ethanol; And their salt.

Other precursor choosing is the group of following composition freely: N-(3-furyl methyl) benzene-Isosorbide-5-Nitrae-diamidogen; N-thiene-3-yl-methylbenzene-Isosorbide-5-Nitrae-diamidogen; N-(2-furyl methyl) benzene-Isosorbide-5-Nitrae-diamidogen; N-thiophene-2-ylmethyl benzene-Isosorbide-5-Nitrae-diamidogen; 3-(2,5-diamino-phenyl)-N-ethyl acrylamide; 2-[3-(3-aminophenyl is amino)-acrylic]-benzene-Isosorbide-5-Nitrae-diamidogen; 2-[3-(4-aminophenyl is amino)-acrylic]-benzene-Isosorbide-5-Nitrae-diamidogen; 2-(6-methyl-pyridine-2-yl)-benzene-Isosorbide-5-Nitrae-diamidogen; 2-pyridine-2-base benzene-Isosorbide-5-Nitrae-diamidogen; 2-[3-(4-aminophenyl is amino)-acrylic]-benzene-Isosorbide-5-Nitrae-diamidogen; 2-[3-(3-aminophenyl is amino)-acrylic]-benzene-Isosorbide-5-Nitrae-diamidogen; 3-(2,5-diamino-phenyl)-N-ethyl acrylamide; 2-thiazol-2-yl benzene-Isosorbide-5-Nitrae-diamidogen; 4-HBA (2,5-diaminourea benzal)-hydrazides; 3 '-fluorine biphenyl-2,5-diamidogen; 2-acrylic-benzene-Isosorbide-5-Nitrae-diamidogen; 2 '-chlordiphenyl-2,5-diamidogen; N-thiene-3-yl-methylbenzene-Isosorbide-5-Nitrae-diamidogen; N-(3-furyl methyl) benzene-Isosorbide-5-Nitrae-diamidogen; 4 '-methoxyl group-biphenyl-2,5-diamidogen; N-(4-amino-benzyl)-benzene-Isosorbide-5-Nitrae-diamidogen; N-[4-amino-2-(2-hydroxyethyl)-2H-pyrazole-3-yl]-3-(5-amino-2-hydroxy phenyl) acrylamide hydrochlorate; 4-amino-2-propyl group amino methyl phenol; 4-amino-2-(isopropylamino methyl)-phenolate hydrochlorate; 4-amino-2-[(2-hydroxyl-5-nitrobenzophenone is amino)-methyl]-phenolate hydrochlorate; 4-amino-2-(pyridin-3-yl amino methyl)-phenol; 5-cyclobutyl amino-2-methyl phenol; 4,5-diaminostilbene-methyl isophthalic acid H-pyrazoles-3-formonitrile HCN; 3-methoxyl group-1-propyl group-1H-pyrazoles-4,5-diamidogen; 3-methoxyl group-1-(2-methoxy ethyl)-1H-pyrazoles-4,5-diamidogen; 1-(2-amino-ethyl)-3-methoxyl group-1H-pyrazoles-4,5-diamidogen; 8-methoxyl group-1,2,4,5-tetrahydro-pyrazole is [5,1-d] [1,3,5] oxygen phenodiazine Zhuo-9-amine also; 1-(2-hydroxyethyl)-3-methoxyl group-1H-pyrazoles-4,5-diamidogen; 1-cyclohexyl-3-methoxyl group-1H-pyrazoles-4,5-diamidogen; 6-methoxyl group-1-methyl-2,3-dihydro-1H-imidazo [1,2-b] pyrazoles-7-amine; 2-methoxyl group-4,5,6,7-tetrahydro-pyrazole is [1,5-a] pyrimidine-3-amine also; 3-methoxyl group-1-octyl group-1H-pyrazoles-4,5-diamidogen; 3-methoxyl group-1-amyl group-1H-pyrazoles-4,5-diamidogen; 6-methoxyl group-2,3-dihydro-1H-imidazo [1,2-b] pyrazoles-7-amine; 3-methoxyl group-N5, N5-dimethyl-1-propyl group-1H-pyrazoles-4,5-diamidogen; 1-hexyl-3-methoxyl group-1H-pyrazoles-4,5-diamidogen; 1-butyl-3-methoxyl group-1H-pyrazoles-4,5-diamidogen; 1-isopropyl-3-methoxyl group-1H-pyrazoles-4,5-diamidogen; 1-ethyl-3-methoxyl group-1H-pyrazoles-4,5-diamidogen; 3-methoxyl group-1-(4-methoxy-benzyl)-1H-pyrazoles-4,5-diamidogen; 3-methoxyl group-1-(pyridine-2-yl)-1H-pyrazoles-4,5-diamidogen; 1-(4-ethylphenyl)-3-methoxyl group-1H-pyrazoles-4,5-diamidogen; 3-methoxyl group-1-p-methylphenyl-1H-pyrazoles-4,5-diamidogen; 3-cyano group-1-(2-hydroxyethyl)-1H-pyrazoles-4,5-diamidogen; 1-butyl-3-cyano group-1H-pyrazoles-4,5-diamidogen; 3-cyano group-1-phenyl-1H-pyrazoles-4,5-diamidogen; 3-cyano group-1-hexyl-1H-pyrazoles-4,5-diamidogen; 1-butyl-3-cyano group-1H-pyrazoles-4,5-diamidogen; 3-cyano group-1-(4-methoxy-benzyl)-1H-pyrazoles-4,5-diamidogen; 3-cyano group-1-isopropyl-1H-pyrazoles-4,5-diamidogen; The fluoro-N5-isopropyl-1H-of 1-cyclohexyl-3-pyrazoles-4,5-diamidogen; 1-methyl-3-(trifluoromethoxy)-1H-pyrazoles-4,5-diamidogen; The fluoro-1-octyl group-1H-of 3-pyrazoles-4,5-diamidogen; The chloro-1-hexyl-1H-of 3-pyrazoles-4,5-diamidogen; The fluoro-1-of 3-(2-hydroxyethyl)-1H-pyrazoles-4,5-diamidogen; The chloro-1-of 3-(2-hydroxyethyl)-1H-pyrazoles-4,5-diamidogen; The chloro-1-of 3-(4-hydroxybutyl)-1H-pyrazoles-4,5-diamidogen; The chloro-1-of 3-(pyridine-2-yl)-1H-pyrazoles-4,5-diamidogen; 3-chloro-1-phenyl-1H-pyrazoles-4,5-diamidogen; The chloro-1-ethyl-1H-of 3-pyrazoles-4,5-diamidogen; 1-(3-methoxy-propyl)-3-(methylsulfinyl)-1H-pyrazoles-4,5-diamidogen; 1-(3-hydroxypropyl)-3-(methylsulfinyl)-1H-pyrazoles-4,5-diamidogen; 1-(4-methoxy-benzyl)-3-(methyl sulphonyl)-1H-pyrazoles-4,5-diamidogen; 1-methyl-3-(methyl sulphonyl)-1H-pyrazoles-4,5-diamidogen; And their salt.

In some embodiments, precursor includes but not limited to: p-phenylene diamine derivative, for example: 2-methylbenzene-Isosorbide-5-Nitrae-diamidogen; Benzene-Isosorbide-5-Nitrae-diamidogen; 1-(2,5-diamino-phenyl)-ethanol; 2-(2,5-diamino-phenyl)-ethanol; 2-(methoxy) benzene-Isosorbide-5-Nitrae-diamidogen; N-(2-methoxy ethyl) benzene-Isosorbide-5-Nitrae-diamidogen; 2-[(4-aminophenyl)-(2-hydroxyethyl)-amino]-ethanol; 1-(2,5-diamino-phenyl) second-1,2-glycol; 1-(2 '-hydroxyethyl)-2,5-diaminobenzene; 1,3-bis-(N-(2-hydroxyethyl)-N-(4-aminophenyl) amino)-2-propanol; 2,2 '-[1,2-second, two base-bis--(oxygen base-2,1-ethylenedioxy)]-bis-benzene-Isosorbide-5-Nitrae-diamidogen; N, N-bis-(2-hydroxyethyl) p-phenylenediamine (PPD); And their mixture; P-aminophenol derivatives, for example: PAP; 4-methylamino phenol; 4-amino-3-methylphenol; 4-amino-2-methoxy phenol; 1-(5-amino-2-hydroxy phenyl)-ethyl-1,2-glycol; 4-amino-2-amino methyl phenol; 4-amino-1-hydroxyl-2-(2 '-hydroxyethyl amino methyl) benzene; 5-aminosalicylic acid and salt thereof; And their mixture; O-phenylene diamine derivatives, as: 3,4-diaminobenzoic acid and its salt; O-aminophenol derivatives, for example: Ortho-Aminophenol; 2-amino-5-methylphenol; 2-amino-6-methylphenol; N-(4-amino-3-hydroxy base)-acetamide; 2-amino-4-methylphenol; 2-amino-5-ethyl-phenol; And their mixture; And Hete rocyclic derivatives, for example: pyrimidine-2,4,5,6-tetramine; 1-methyl isophthalic acid H-pyrazoles-4,5-diamidogen; 2-(4,5-diaminostilbene H-pyrazol-1-yl) ethanol; 1-(4-methyl-benzyl)-1H-pyrazoles-4,5-diamidogen; 1-(benzyl)-1H-pyrazoles-4,5-diamidogen; N2, N2-lutidines-2,5-diamidogen; 4-hydroxyl-2,5,6-Triaminopyrimidine; Their salt; And their mixture.

In certain embodiments, precursor comprises: 2-methylbenzene-Isosorbide-5-Nitrae-diamidogen; 2-(methoxy) benzene-Isosorbide-5-Nitrae-diamidogen; Benzene-Isosorbide-5-Nitrae-diamidogen; N, N-bis-(2-hydroxyethyl) p-phenylenediamine (PPD); PAP; 4-methylamino phenol; 4-amino-3-methylphenol; Ortho-Aminophenol; 2-amino-5-methylphenol; 2-amino-5-ethyl-phenol; 2-amino-6-methylphenol; 1-methyl isophthalic acid H-pyrazoles-4,5-diamidogen; 2-(4,5-diaminostilbene H-pyrazol-1-yl) ethanol; 2,5-diaminotoluene; 2,5-diamino-phenyl ethanol; Their salt; And their mixture.

The coupling agent being applicable in compositions described herein includes but not limited to: phenol, resorcinol, naphthols, m-aminophenol, m-diaminobenzene. and heterocyclic compound and their derivant, such as: 2-amino-5-ethyl-phenol; Naphthalene-1,7-glycol; Benzene-1,3-glycol; 4-chlorobenzene-1,3-glycol; Naphthalene-1-alcohol; 2-methyl-naphthalene-1-alcohol; Naphthalene-1,5-glycol; Naphthalene-2,7-glycol; Benzene-Isosorbide-5-Nitrae-glycol; 2-methylbenzene-1,3-glycol; 7-amino-4-hydroxy-naphthalene-2-sulfonic acid; 2-isopropyl-5-methylphenol; 1,2,3,4-tetrahydrochysene-naphthalene-1,5-glycol; 2-chlorobenzene-1,3-glycol; 4-hydroxyl-naphthalene-1-sulfonic acid; Benzene-1,2,3-triol; Naphthalene-2,3-glycol; 5-chloro-2-methyl benzene-1,3-glycol; 4,6-dichloro-benzenes-1,3-glycol; 2,3-dihydroxy-[Isosorbide-5-Nitrae] naphthoquinone; With 1-acetoxyl group-2-methyl naphthalene; M-diaminobenzene. class, for example: 2,4-diaminophenol; Benzene-1,3-diamidogen; 2-(2,4-diamino phenoxy)-ethanol; 2-[(3-aminophenyl)-(2-hydroxyethyl)-amino]-ethanol; 2-methylbenzene-1,3-diamidogen; 2-[[2-(2,4-diamino phenoxy)-ethyl]-(2-hydroxyethyl)-amino]-ethanol; 4-{3-[(2,4-diamino-phenyl) oxygen base] propoxyl group } benzene-1,3-diamidogen; 2-(2,4-diamino-phenyl)-ethanol; 2-(3-amino-4-methoxyl phenyl amino)-ethanol; 4-(2-amino ethoxy)-benzene-1,3-diamidogen; (2,4-diamino phenoxy)-acetic acid; 2-[2,4-diaminourea-5-(2-hydroxyl-ethyoxyl)-phenoxy group]-ethanol; 4-ethyoxyl-6-methylbenzene-1,3-diamidogen; 2-(2,4-diaminourea-5-methylphenoxy)-ethanol; 4,6-dimethoxy benzene-1,3-diamidogen; 2-[3-(2-hydroxyethyl is amino)-2-aminomethyl phenyl is amino]-ethanol; 3-(2,4-diamino phenoxy)-propyl-1-alcohol; N-[3-(dimethylamino) phenyl] urea; 4-methoxyl group-6-methylbenzene-1,3-diamidogen; The fluoro-6-of 4-methylbenzene-1,3-diamidogen; 2-(3-[(2-hydroxyethyl) and amino]-4,6-Dimethoxyphenyl }-amino) ethanol; 3-(2,4-diamino phenoxy)-propyl-1,2-glycol; 2-[2-amino-4-(methylamino)-phenoxy group] ethanol; 2-[(5-amino-2-ethoxyl phenenyl)-(2-hydroxyethyl)-amino]-ethanol; 2-[(3-aminophenyl) amino] ethanol; 2,4-diaminourea-5-(2 '-hydroxyl-oxethyl) toluene; N, N-dimethyl-3-urea groups aniline; N-(2-amino-ethyl) benzene-1,3-diamidogen; 4-{[(2,4-diamino-phenyl) oxygen base] methoxyl group }-benzene-1,3-diamidogen; 1-methyl-2,6-bis-(2-hydroxyethyl is amino) benzene; With 2,4-dimethoxy benzene-1,3-diamidogen; 1,3-bis--(2,4-diamino phenoxy) propane; 2-methyl-5-[(1-H-pyrroles-2-ylmethyl)-amino]-phenol; 5-[(furan-2-ylmethyl)-amino]-2-methylphenol; 5-isopropylamino-2-methylphenol; Biphenyl-2,4,4 '-tri-amine hydrochlorates; 5-(4-aminophenyl) amino methyl benzene-1,3-diamine hydrochloride 5-phenyl amino methylbenzene-1,3-diamine hydrochloride; 2-[4-amino-2-(3,5-diaminourea-benzylamino)-phenoxy group]-ethylate hydrochlorate; 5-(3-aminophenyl) amino methyl benzene-1,3-diamine hydrochloride; N-(2-aminobenzyl)-benzene-1,3-diamine hydrochloride; N-furan-2-ylmethyl benzene-1,3-diamine hydrochloride; 2-[(3-aminophenyl is amino)-methyl]-phenolate hydrochlorate; 4-amino-2-propyl group amino methyl phenol; N-benzo [1,3] dioxolanes-5-ylmethyl benzene-1,3-diamine hydrochloride; N-[4-amino-2-(2-hydroxyethyl)-2H-pyrazole-3-yl]-3-(5-amino-2-hydroxy phenyl)-acrylamide; 4-amino-2-(isopropylamino-methyl)-phenol; 4-thiene-3-yl-benzene-1,3-diamidogen; 5-phenyl amino methylbenzene-1,3-diamine hydrochloride; 5-(3-aminophenyl) amino methyl benzene-1,3-diamine hydrochloride; 4-thiene-3-yl-benzene-1,3-diamidogen; 2 ', 4 '-benzidine-4-alcohol; 5-cyclobutyl amino-2-methyl phenol; 5-cyclobutyl amino-2-methyl phenol; 4-amino-2-(pyridin-3-yl amino methyl)-phenol; 5-(3-aminophenyl) amino methyl benzene-1,3-diamine hydrochloride; 5-allyl amino methylbenzene-1,3-diamine hydrochloride; N-(4-aminobenzyl)-benzene-1,3-diamine hydrochloride; N-benzyl-benzene-1,3-diamine hydrochloride; 3-[(3-aminophenyl is amino)-methyl]-phenolate hydrochlorate; N-(4-methoxy-benzyl)-benzene-1,3-diamine hydrochloride; N-thiophene-2-ylmethyl benzene-1,3-diamine hydrochloride; 4-amino-2-[(2-hydroxyl-5-nitro-phenyl amino)-methyl]-phenol; 2 ', 4 '-benzidine-4-alcohol hydrochloride; Biphenyl-2,4,4 '-triamine; 5-(4-aminophenyl) amino methyl benzene-1,3-diamine hydrochloride; 2-[4-amino-2-(3,5-diaminourea-benzylamino)-phenoxy group]-ethylate hydrochlorate; 5-allyl amino methylbenzene-1,3-diamine hydrochloride; 5-(3-aminophenyl) amino methyl benzene-1,3-diamine hydrochloride; N-(4-aminobenzyl)-benzene-1,3-diamine hydrochloride; N-benzyl-benzene-1,3-diamine hydrochloride; 3-[(3-aminophenyl is amino)-methyl]-phenolate hydrochlorate; N-(2-aminobenzyl)-benzene-1,3-diamine hydrochloride; N-(4-methoxy-benzyl)-benzene-1,3-diamine hydrochloride; N-furan-2-ylmethyl benzene-1,3-diamine hydrochloride; 2-[(3-aminophenyl is amino)-methyl]-phenolate hydrochlorate; N-thiophene-2-ylmethyl benzene-1,3-diamine hydrochloride; N-benzo [1,3] dioxole-5-ylmethyl benzene-1,3-diamine hydrochloride; M-aminophenyl phenols, for example: 3-amino-phenol; 2-(3-hydroxy-4-methyl phenyl amino)-acetamide; 2-(3-hydroxy phenyl is amino)-acetamide; 5-amino-2-methyl phenol; 3-amino-2,6-xylenol; 5-(2-hydroxyethyl is amino)-2-methylphenol; 5-amino-2, the chloro-phenol of 4-bis-; 3-amino-2-methyl phenol; 3-amino-2,6-xylenol; The chloro-6-methylphenol of 3-amino-2-; 5-amino-2-(2-hydroxyl-ethyoxyl)-phenol; The chloro-5-of 2-(the fluoro-ethylamino of 2,2,2-tri-)-phenol; 5-amino-4-chloro-2-methyl phenol; 3-cyclopenta amino-phenol; 5-[(2-hydroxyethyl) amino]-4-methoxyl group-2-methylphenol; 5-amino-4-methoxyl-2-methylphenol; 3-(dimethylamino) phenol; 3-(diethylamino) phenol; 5-amino-4-fluoro-2-methylbenzene phenol; 5-amino-4-ethyoxyl-2-methylphenol; 3-amino-2, the chloro-phenol of 4-bis-; 3-[(2-methoxy ethyl) amino] phenol; 3-[(2-hydroxyethyl) amino] phenol; 5-amino-2-ethyl-phenol; 5-amino-2-methoxyphenol; 5-[(3-hydroxyl-propyl) amino]-2-methylphenol; 3-[(3-hydroxy-2-methyl phenyl)-amino] the third-1,2-glycol; 3-[(2-hydroxyethyl) amino]-2-methylphenol; 2-methyl-5-[(1-H-pyrroles-2-ylmethyl)-amino]-phenol; 5-[(furan-2-ylmethyl)-amino]-2-methylphenol; 5-isopropylamino-2-methylphenol; 5-cyclobutyl amino-2-methyl phenol; 1-methyl-2-hydroxyl-4-(2 '-hydroxyethyl) amino-benzene; And Hete rocyclic derivatives, for example: 3,4-dihydro-2H-1,4-benzoxazinyl-6-alcohol; 6-methoxy quinoline-8-amine; 4-picoline-2,6-glycol; 2,3-dihydro-Isosorbide-5-Nitrae-benzodioxan-5-alcohol; 1,3-benzo dioxolanes-5-alcohol; 2-(1,3-benzo dioxolanes-5-base is amino) ethanol; 3,4-lutidines-2,6-glycol; 5-chloropyridine-2,3-glycol; 2,6-dimethoxy-pyridine-3,5-diamidogen; 1,3-benzo dioxolanes-5-amine; 2-{[3,5-diaminourea-6-(2-hydroxyl-ethyoxyl)-pyridine-2-yl] oxygen base }-ethanol; 1H-indole-4-alcohol; 5-amino-2,6-dimethoxy-pyridine-3-alcohol; 1H-indole-5,6-glycol; 1H-indole-7-alcohol; 1H-indole-5-alcohol; 1H-indole-6-alcohol; 6-is bromo-1,3-benzo dioxolanes-5-alcohol; PA-3-alcohol; Pyridine-2,6-diamines; 3-[(3,5-diamino-pyridine-2-yl) oxygen base] the third-1,2-glycol; 5-[(3,5-diamino-pyridine-2-yl) oxygen base] penta-1,3-glycol; Indoline-5,6-glycol; 3,5-dimethoxy-pyridine-2,6-diamidogen; 6-methoxypyridine-2,3-diamidogen; 3,4-dihydro-2H-1,4-benzoxazinyl-6-amine; 4-hydroxy-n-methylindole; 1H-5-methylpyrazole-5-ketone; 1-phenyl-3-methylpyrazole-5-ketone; 2,6-dimethyl pyrazole [1,5-b]-1,2,4-triazole; 2,6-dimethyl [3,2-c]-1,2,4-triazole; 6-methylpyrazole is benzimidazole also-[1,5-a]; 2,6-dihydroxy-pyridine; 2,6-dihydroxy-3,4-lutidines; 5-methylpyrazole is [5,1-e]-1,2,3-triazoles also; 5-methyl-6-chlorine pyrazolo [5,1-e]-1,2,3-triazoles; 5-Phenylpyrazole is [5,1-e]-1,2,3-triazoles and addition salts thereof also; 1H-2,6-dimethyl pyrazole [1,5-b]-1,2,4-triazole toluene fulfonate; 7,8-dicyano-4-methylimidazole is [3,2-a] imidazoles also; 2,7-dimethyl pyrazole [1,5-a] pyrimidine-5-ketone; 2,5-dimethyl pyrazole [1,5-a] pyrimidin-7-ones; With 2-methyl-5-methoxy pyrazolo [1,5-a] pyrimidin-7-ones; 6-hydroxy benzo morpholine; With 3-amino-2-methyl amino-6-methoxypyridine; Their salt; And their mixture.

In some embodiments, coupling agent includes but not limited to: phenol, resorcinol and naphthol derivative, for example: 2-amino-5-ethyl-phenol; Naphthalene-1,7-glycol; Benzene-1,3-glycol; 4-chlorobenzene-1,3-glycol; Naphthalene-1-alcohol; 2-methyl-naphthalene-1-alcohol; Naphthalene-1,5-glycol; Naphthalene-2,7-glycol; Benzene-Isosorbide-5-Nitrae-glycol; 2-methylbenzene-1,3-glycol; With 2-isopropyl-5-methylphenol; THB; 1-acetoxyl group-2-methyl naphthalene; And their mixture; M-diaminobenzene. derivant, as benzene-1,3-diamidogen; 2-(2,4-diamino phenoxy)-ethanol; 4-{3-[(2,4-diamino-phenyl) oxygen base] propoxyl group } benzene-1,3-diamidogen; 2-(3-amino-4-methoxyl phenyl amino)-ethanol; 2-[2,4-diaminourea-5-(2-hydroxyl-ethyoxyl)-phenoxy group]-ethanol; And 3-(2,4-diamino phenoxy)-propyl-1-alcohol; 2,4-diaminourea-5-(2 '-hydroxyl-oxethyl) toluene; N, N-dimethyl-3-urea groups aniline; 2,4-diaminourea-5-toluene fluoride; 1-methyl-2,6-bis-(2-hydroxyethyl is amino) benzene; And their mixture; M-aminophenol derivatives, as 3-amino-phenol; 5-amino-2-methylphenol; 3-amino-2,6-xylenol; 5-(2-hydroxyethyl is amino)-2-methylphenol; With 3-amino-2-methyl phenol; 1-hydroxyl-3-amino-2,4-dichloro-benzenes; 1,3-bis--(2,4-diamino phenoxy) propane; 1-hydroxy-2-methyl-5-amino-6-chlorobenzene; 5-amino-4-chloro-2-methyl phenol; And their mixture; And Hete rocyclic derivatives, for example: 3,4-dihydro-2H-1,4-benzoxazinyl-6-alcohol; 1,3-benzo dioxolanes-5-alcohol; 1,3-benzo dioxolanes-5-amine; 1H-indole-4-alcohol; 1H-indole-5,6-glycol; 1H-indole-7-alcohol; 1H-indole-5-alcohol; 1H-indole-6-alcohol; Pyridine-2,6-diamines; PA-3-alcohol; 4-hydroxy-n-methylindole; 1H-5-methylpyrazole-5-ketone; 1-phenyl-3-methylpyrazole-5-ketone; 2,6-dimethyl pyrazole [1,5-b]-1,2,4-triazole; 2,6-dimethyl [3,2-c]-1,2,4-triazole; 6-methylpyrazole is benzimidazole also-[1,5-a]; 2,6-dihydroxy-pyridine; 2,6-dihydroxy-3,4-lutidines; 6-hydroxy benzo morpholine; 2,6-dihydroxy-3,4-lutidines; 3,5-diaminourea-2,6-dimethoxy-pyridine; 3-amino-2-methyl amino-6-methoxypyridine; Their salt; And their mixture.

In certain embodiments, coupling agent comprises: 2-amino-5-ethyl-phenol; Benzene-1,3-glycol; 4-chlorobenzene-1,3-glycol; 4,6-dichloro-benzenes-1,3-glycol; 2-methylbenzene-1,3-glycol; 2-amino-4-(2 '-hydroxyethyl) aminoanisole; 2,4-diaminourea benzylalcohol; 2,4-diamino-phenyl ethanol; M-diaminobenzene.; 5-amino-2-methyl phenol; 3-amino-2,6-xylenol; 2,4-diamino phenoxy ethanol; 4-amino-2-hydroxyphenoxy ethanol; 1-naphthols; 2-methyl naphthols; 3-amino-phenol; 3-amino-2-methyl phenol; 4-hydroxyl-1,2-methylenedioxybenzenes; 4-amino-1,2-methylenedioxybenzenes; 4-(2 '-hydroxyethyl) amino-1,2-methylenedioxybenzenes; 1-methyl-2-hydroxyl-4-(2 '-hydroxyethyl) aminobenzene; 2,4-diaminophenetole; 2,4-diaminourea-5-tolyl ethyl ether; 4-oxyindole; 3-amino-5-hydroxyl-2,6-dimethoxy-pyridine; With 3,5-diaminourea-2,6-dimethoxy-pyridine; Benzene-1,3-diamidogen; PA-3-alcohol; 1-phenyl-3-methylpyrazole-5-ketone; Their salt; And their mixture.

In addition, in some embodiments, developer and coupling agent comprise 5-methoxy-Ortho-Aminophenol; 5-ethyl-Ortho-Aminophenol; 5-phenyl-Ortho-Aminophenol; 5-cyano ethyl-Ortho-Aminophenol; Their salt; And their mixture.

Hair dye composition of the present invention also comprises and is suitable for sending tonal correction or chooses non-oxidizable dyestuff or the direct dyes that dyes effect.Suitable direct dyes includes but not limited to: No. 1, Indian yellow; No. 3, acid orange; No. 7, Red-1 200; Brown No. 17 of alkalescence; No. 52, acid black; Acid black 1 number; No. 4, disperse violet; NPD; 2-nitro p-phenylenediamine; 4,6-dinitro-2-aminophenol.; Red No. 13 of HC; Isosorbide-5-Nitrae-bis--(2 '-hydroxyethyl)-amino-2-Nitrobenzol; Yellow No. 5 of HC, red No. 7 of HC; Blue No. 2 of HC; Yellow No. 4 of HC; Yellow No. 2 of HC; No. 1, HC orange; Red No. 1 of HC; The chloro-5-nitro-N-of 2-hydroxyethyl p-phenylenediamine (PPD); Red No. 3 of HC; 4-amino-3-nitro phenol; 2-hydroxyethyl amino-5-Nitroanisole; 3-nitro is to hydroxyethyl amino-phenol; 2-amino-3-nitro phenol; 6-nitro-o-toluidine; 3-methylamino-4-nitrophenoxy ethanol; 2-nitro-5-glyceryl monomethylaniline.; Yellow No. 11 of HC; Purple No. 1 of HC; No. 2, HC orange; No. 3, HC orange; Yellow No. 9 of HC; 4-nitrobenzophenone amino-ethyl urea; Red No. 10 of HC; Red No. 11 of HC; 2-hydroxyethyl 4,6-dinitro-2-aminophenol.; Blue No. 12 of HC; Yellow No. 6 of HC; Hydroxyethyl-2-nitro-p-toluidine; Yellow No. 12 of HC; Blue No. 10 of HC; Yellow No. 7 of HC; Yellow No. 10 of HC; Blue No. 9 of HC; N-ethyl-3-nitro PABA; Amino-2 '-formic acid of 4-amino-2-nitrobenzophenone; The chloro-6-ethylamino-4-of 2-nitrophenol; 6-nitro-2,5-pyridine diamidogen; Purple No. 2 of HC; The chloro-4-nitrophenol of 2-amino-6-; 4-hydroxypropyl amino-3-nitro phenol; Yellow No. 13 of HC; 1,2,3,4-tetrahydrochysene-6-nitro quinoxaline; Red No. 14 of HC; Yellow No. 15 of HC; Yellow No. 14 of HC; 3-amino-6-methylamino-2-nitropyridine; 2,6-diaminourea-3-((pyridin-3-yl) azo) pyridine; No. 18, alkali red 1:1; No. 69, Basic Orange; N-(2-nitro-4-aminophenyl)-allyl amine; 4-[(4-amino-3-aminomethyl phenyl) (4-imino group-3-methyl-2,5-cyclohexadiene-1-subunit) methyl]-2-aminotoluene hydrochlorate; 2-[[4-(dimethyl-amino) phenyl] azo]-1,3-dimethyl-1H-imidazolitm chloride; 1-methyl-4-[(aminomethyl phenyl hydrazono-) methyl]-pyridine methyl ester sulfate; 2-[(4-aminophenyl) azo]-1,3-dimethyl-1H-imidazolitm chloride; Red No. 22 of alkalescence; Red No. 76 of alkalescence; Brown No. 16 of alkalescence; No. 57, basic yellow; 7-(2 ', 4 '-dimethyl-5 '-sulfophenyl azo base)-5-sulfo group-8-hydroxyl naphthalene; Acid orange 7 number; No. 33, Xylene Red; 1-(3 '-nitro-5 '-sulfo group-6 '-oxygen base phenylazo)-oxygen base naphthalene chromic compound; Acid yellow 23 number; Acid blue 9 number; Basic violet 14 number; Blue 7 number; Alkali blue 26; The sodium salt of the monosulfonic acid of quinophthalone or 2-quinolyl indenes diketone and disulfonic acid (being mainly the latter) mixture; Red No. 2 of alkalescence; No. 99, alkali blue; No. 5, Red-1 200; No. 43, acid violet; No. 1, disperse violet; Acid blue 62 number; Pigment blue 15 number; No. 32, acid black 1; No. 29, basic yellow; Disperse black No. 9; 1-(N-methylmorpholine propyl group is amino)-4-hydroxyanthraquinone methyl ester sulfate; N, N-dimethyl-3-((4-(methylamino)-9,10-dioxy base-9,10-dihydroanthracene-1-yl) amino)-N-propyl group bromination third-1-ammonium; Blue No. 8 of HC; Red No. 8 of HC; Green No. 1 of HC; Red No. 9 of HC; HNQ; No. 99, Blue VRS; No. 25, acid blue; No. 4, Xylene Red; Fingernail premium; Indigo; Alkermes; Blue No. 14 of HC; No. 23, disperse blue; No. 3, disperse blue; No. 377, disperse blue; Red No. 51 of alkalescence; No. 31, Basic Orange; No. 87, basic yellow; And their mixture.Preferred direct dyes includes but not limited to: disperse black No. 9; Yellow No. 2 of HC; Yellow No. 4 of HC; Yellow No. 15 of HC; NPD; The chloro-4-nitrophenol of 2-amino-6-; Red No. 3 of HC; No. 1, disperse violet; Blue No. 2 of HC; No. 3, disperse blue; No. 377, disperse blue; Red No. 51 of alkalescence; No. 31, Basic Orange; No. 87, basic yellow; And their mixture.

When powder composition mixes with water, hair dye composition of the present invention generally comprises approximately 0.001% to approximately 10% dyestuff.For example, after mixing with water, can provide low-intensity dyeing generally to comprise approximately 0.001 % by weight to approximately 5 % by weight such as the naturally golden compositions to light brown hair tone, preferably approximately 0.1 % by weight is to approximately 2 % by weight, and more preferably from about 0.2 % by weight is to precursor and the coupling agent of approximately 1 % by weight.Darker tone comprises by weight 0.001% to approximately 10% conventionally as brown and black, and preferably approximately 0.05% to approximately 7%, more preferably from about 1% to approximately 5% precursor and coupling agent.

surfactant

Compositions of the present invention also can comprise one or more surfactants so that sensation beneficial effect to be provided, such as slickness.Be applicable to surfactant herein and conventionally there is the lipophilic chain that is about 8 to approximately 30 carbon atoms, and can be selected from anion surfactant, non-ionic surface active agent, amphoteric surfactant and cationic surfactant and their mixture.Preferred surfactant comprises non-ionic surface active agent, and described ionic surfactant pack for example, containing one or more polyethylene oxide chains, polyoxyethylene alkyl ether or cithrol.Another kind of preferred surfactant is alkyl ether sulfate or alkyl ether phosphate, and wherein especially preferred is to have 1 to 20, preferably 1 to 10, and the alkyl ether phosphate of 1 to 5 ethylene oxide unit most preferably.

Can use any combination of surfactant.The content that this surfactant is used is conventionally by weight of the composition for approximately 0.05% to approximately 30%, and preferably approximately 0.1% to approximately 15%, more preferably from about 0.2% to approximately 10%.

chelating agen

According to the present invention, described compositions can comprise chelating agen.Chelating agen is well known in the art, and refers to all and can form the molecule of chelate or the mixture of different molecular with metal ion.Chelating agen is well known in the art, and its non-completeness list is found in AE Martell and RM Smith's " Critical Stability Constants " the 1st volume (Plenum Press, New York & London, 1974) and " Metal Complexes in AqueousSolution " (Plenum Press of AE Martell and RD Hancock, New York & London, 1996), in, the two is incorporated herein by reference.

The example that is applicable to chelating agen herein comprises EDDS (EDDS), carboxylic acid (being amino carboxylic acid specifically), phosphonic acids (being aminophosphonic acid specifically) and polyphosphoric acid (being straight chain polyphosphoric acid specifically), their salt and derivant.

Chelating agen can be used as stabilizing agent and/or antiseptic is incorporated in compositions of the present invention.In addition it has also been found that, chelating agen can provide the beneficial effect of prevention hair fiber damage, therefore can further improve hair damages characteristic of the present invention with them.To the most effective chelating agen as diamidogen-N, N '-bis-polyprotic acid and monoamine monoamides-N, N '-bis-polyprotic acid chelating agen (for example EDDS), in the present invention, the content of chelating agen can be low to moderate approximately 0.1%, preferably at least about 0.25%, more preferably from about 0.5%.The effect that depends on chelating agen, the consumption of the chelating agen that effect is lower is by weight of the composition more preferably at least about 1%, even more preferably from about more than 2%.

using method

Should be appreciated that the embodiment of using method as herein described and embodiment are only for the object of explanation.In the situation that not deviating from the spirit and scope of the invention, those skilled in the art can carry out various modification or change to it.

Powder composition of the present invention provides to be suitable for the gas-tight seal packaged form of single use amount.During its storage life, described compositions must be stable, component wherein do not react and not with atmosphere in reaction of moisture.Compositions of the present invention have explanation for consumer according to the water of the powdered composition mixing Sq of single using dosage so that the component of aimed concn to be provided.The water of the specified amount that therefore, can will mix according to powder composition regulates the group component in powder composition of the present invention.Described powder composition is intended to mix with the water of approximately 4 to approximately 5 times of weight conventionally.

Owing to conventionally adopting gentle hand mix to implement in man of consumer with mixing of water, so the reaction of dispersive composition and multiviscosisty be intended to adopt gentle mechanical agitation, in approximately 60 seconds, more preferably in approximately 30 seconds, carries out.Consumer is mixed described compositions before being about to use with water, and is administered on hair.

The dispersive composition of acquisition is being acted on to whole hair area with (being applied in equably on all hairs guaranteeing) after dyeing a few minutes, described compositions is retained on hair is enough to make a period of time of dyeing generation (being generally approximately 2 to 60 minutes, approximately 30 to 45 minutes conventionally).Consumer is then with his/her hair of the thorough rinsing of tap water and make it dry.According to observations, hair is from its original change color to desired color.

The present invention also comprises embodiment, wherein method painted or bleaching hair comprises and uses a kind of compositions, the time of using is at least described compositions is applied to approximately 50% of the hair time, described compositions comprises at least one oxidant, at least one carbanion source, carbamic acid radical ion source or bicarbonate ion source and their mixture, not containing the polymer-thickened system of free radical scavenger, described compositions has approximately 9.4 pH at most with defined herein.

According to the present invention, method painted or bleaching hair also comprises following embodiment, wherein described compositions is administered on hair and preferably makes mixture effect a few minutes (being administered to equably on all hairs guaranteeing).Then make described compositions be retained on hair so that color development a period of time, the described time is less than approximately 20 minutes, is preferably less than approximately 15 minutes, and more preferably from about 5 minutes to approximately 10 minutes, most preferably from about 10 minutes.Consumer also makes trichoxerosis or sizing as usual with his/her hair of tap water cleaning down subsequently.The method, by allowing to dye faster or bleach application, provides extra facility to consumer.

According to alternative embodiment of the present invention, method painted and/or bleaching hair is the method for mutually continuous oxidizing hair coloring or bleaching hair, described method comprises the treatment step of at least two mutually continuous oxidizing hair colorings or bleaching hair, wherein the interval between each processing is 1 to 60 day, preferably 1 to 40 day, more preferably 1 to 28 day, even more preferably 1 to 14 day, and most preferably 1 to 7 day.In the above-described embodiment, the overhead retention time of compositions can be less than approximately 20 minutes, and is preferably and is less than approximately 10 minutes, and most preferably is approximately 2 minutes to approximately 5 minutes.The method makes consumer implement painted or bleaching process to be similar to the mode of conventional hair washing or conditioning process.

Can adopt any standard method to prepare economically compositions herein.Described compositions can structuring packing, the form of capsule or sachet provides, as long as they are made by air non-permeate material, and keeps gas-tight seal within required storage life.Before sealing, the air being retained in packing can be evacuated, or with noble gas such as nitrogen replacement.

Can adopt and assist to realize special-effect and as chosen, dye comb, choose to dye and brush and choose dyer's tool, foil paper and choose and dye cap such as choosing the equipment dying, implement dispersive composition to using on hair.

Can come subsidiary products to be penetrated in hair with other device technique.The embodiment of above-mentioned technology comprises heater, UV-device and ultrasonic unit.

Embodiment

Following examples have further described and have proved the embodiment in the scope of the invention.These embodiment that give are only for the object of explanation, unintelligible for being limitation of the present invention, because its many modification are possible in the situation that not departing from the spirit and scope of the invention.Applicable composition is all identified with chemical name or CTFA name herein, unless below limited in addition.

Following examples illustrate according to oxidative dye composition of the present invention.Should be appreciated that embodiment as herein described and embodiment are only illustrative, in the situation that not deviating from scope of the present invention, one of skill in the art can make a plurality of other changes and modification to it.Embodiment 1 to 29 is according to compositions of the present invention, and comparing embodiment 1 to 5 right and wrong according to of the present invention those.

the compositions of embodiment 1 to 28 and painted result

Embodiment 1 to 28 is Powdered hair coloring compositions of the present invention.Component in the compositions of embodiment 1 to 28 and painted the results are shown in following table 1 to 7 are their method of preparation and the method that we use them subsequently.

table 1

table 2

table 3

table 4

table 5

table 6

table 7

* acrylate/C10-30 alkyl acrylate crosspolymer: Carbopol ETD 2020, derives from Noveon

Compositions of the present invention can provide multiple color tones.

preparation method

Component is fully mixed, in blanket of nitrogen, be transferred in the packing that the material by air impermeable makes and sealing.Provide and instruct so that the content in every dose is mixed with the water of 4 times of weight.

using method and chromotrichia result

By the water hand mix of described compositions and 4 times of weight 60 seconds, be then administered on hair, retain 30 minutes, then water washes away compositions from hair.When being administered on hair according to this guidance, every kind of compositions provides the chromotrichia that shows " result ".Compositions of the present invention can provide multiple chromotrichia result, therefore has the possibility that extensive diversified tone is provided.

gray hair covers

Make above-described embodiment 1 and non-ly according to comparing embodiment 1 of the present invention, carry out gray hair and cover validity test.Comparing embodiment 1 is the Bigen Xpressive Caf é Latte that the 2007 Nian Ke U.S. buy, and it has the tone similar with embodiment 1.

According to using method as above, comparing embodiment 1 joins in 100ml water according to the guidance providing in packing, uses respectively embodiment 1 and comparing embodiment 1 by following bunch dyeing.

1) 3/0 dark brown hair

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

After dyeing, washing experiment hair bunch and undyed 50% gray hair-3/0 hair bunch under the following conditions:

The water of-35 ℃ to 40 ℃, flow is 4 ± 0.51/min

-Pantene Clarifying Shampoo the hair washing of buying with the 2007 Nian Ke U.S. once

-rinsing

-electricity consumption dries up.

After dry, adopt Minolta spectrophotometer CM-3700d, obtain 3/0 hair, 50% gray hair blend of dyeing and L, a, the b value of undyed 50% gray hair blend of dyeing.Then adopt formula use L, a, b value to calculate Δ E value.By these values, can calculate as follows gray hair percentage of coverage:

The gray hair that is as follows embodiment 1 and comparing embodiment 1 gained covers.

	Embodiment 1	Comparing embodiment 1
			Gray hair covers (%)	82.5％	31.4％

From result, can recognize, compare with comparing embodiment 1, the present composition with similar tone can provide significantly better gray hair Color.

thickening agent characteristic and pH

Make according to embodiments of the invention 29 and the non-characteristic test as thickening agent according to comparing embodiment 1 to 5 experience of the present invention.Embodiment 29 and comparing embodiment 1 to 5 do not contain hair dyes to be convenient to observe thickening characteristic.Table 9 shows each base composition of embodiment 29 and comparing embodiment 1 to 5.In this base composition, add the concrete thickening agent as indicated in table 10.

table 9

Component	Weight portion
		SODIUM PERCARBONATE	12.00
Ammonium sulfate	7.08
		Glycine sodium salt	2.52

table 10

Embodiment numbering	Thickening agent is described
		Embodiment 29	Acrylate/C10-30 alkyl acrylate crosspolymer: Carbopol ETD 2020, derives from Noveon

Comparing embodiment 1	PEG 15 stearates: Aculyn 60, derive from Rohm & Haas
		Comparing embodiment 2	Carboxymethyl cellulose 700k, 0.9DS ^*1)
Comparing embodiment 3	Carboxymethyl cellulose 250k, 0.7DS
		Comparing embodiment 4	Carboxymethyl cellulose 250k, 0.9DS
Comparing embodiment 5	Carboxymethyl cellulose 250k, 1.2DS

^*1) k represents weight average molecular weight, and DS represents substitution value.

Every kind of compositions is mixed with the water of 4.17 times of weight, the dispersive composition respectively with 2.44% thickening agent is provided.After mixing with water, by stirring rod, stir every kind of compositions, and observe the time that reaches maximum denseness, and further whether observation condenses.After reaching maximum denseness, by the member of panel of expert, test the adhesiveness of dispersive composition on hair and the spreadability on hair.Only for those dispersive compositions with enough adhesivenesses and spreadability, use Brookfield viscometer spindle S52 to measure viscosity at 0.5rpm.Except feeding-up and cannot measure the comparing embodiment 1 of pH, measure the pH of all dispersive compositions.The result of every kind of thickening agent characteristic item is described in table 11.

table 11

Reach the time (second) of maximum denseness

Condense

Adhesiveness to hair

Spreadability on hair

Viscosity (mPas)

PH value

Embodiment 29

30

No

By

13500

9.25

Comparing embodiment 1

Be

By

Defective

Comparing embodiment 2

140

Be

Defective

By

9.57

Comparing embodiment 3

151

Be

Defective

By

9.55

Comparing embodiment 4

137

Be

Defective

By

9.62

Comparing embodiment 5

110

No

Defective

By

9.67

From the above results, can recognize to only have the embodiment of the present invention 29 that gratifying thickening agent characteristic and suitable pH are provided.

Dimension disclosed herein and value should be interpreted as to the strict restriction to quoted exact value.On the contrary, except as otherwise noted, each such dimension is intended to represent the value quote and around the scope being equal in this value function.For example, disclosed size " 40mm " is intended to represent " about 40mm ".

Unless expressly excluded or otherwise limited, every piece of document quoting herein, comprises patent any cross reference or relevant or patent application, all hereby with way of reference, is incorporated in full herein.The quoting of any document is not it as disclosed herein or be subject to the approval of prior art of any invention of claims protection; or to himself; or with any other combination in any of list of references, or with reference to, propose, suggestion or disclose the approval of any this type of invention.In addition, in presents, any implication of same term or while defining contradiction in any implication of term or definition and the file that is incorporated to way of reference, should obey implication or the definition of giving in the present invention this term.

Although illustrated and described specific embodiment of the invention scheme, having it will be apparent to one skilled in the art that and can make a plurality of other changes and modification in the situation that not deviating from essence of the present invention and scope.Therefore, at additional claims, comprise all these changes and the modification belonging in the scope of the invention consciously.

Claims

1. a Powdered hair coloring compositions, described compositions comprises:

A) at least one peroxide one carbanion, carbamic acid radical ion or the solid source of bicarbonate ion or their mixture, the solid source of wherein said ion is to be selected from following percarbonate: SODIUM PERCARBONATE, potassium percarbonate and percarbonic acid calcium, and the described ion source being wherein included in powder composition provides the described ion source of 0.5mol/1 to 1.5mol/1 when powder composition mixes with the water of 4 to 5 times of weight;

B) at least one oxidant with solid source;

C) at least one ammonium ion solid source; With

D) crosslinked carboxylic acid polymer thickeners useful, wherein said crosslinked carboxylic acid polymer thickeners useful is acrylic acid C10 to C30 alkyl ester cross-linked polymer, described thickening agent has the granularity that is no more than approximately 10 microns; When described powder composition mixes with water, the amount of described thickening agent can provide 1% to 3% concentration; When using Brookfield viscometer spindle S52 when 0.5rpm measures, described thickening agent can provide to the compositions of described dispersion the viscosity of 10000mPas to 20000mPas and 8.5 to 9.4 pH.

2. compositions as claimed in claim 1, the solid source of wherein said carbanion, carbamic acid radical ion, bicarbonate ion or their mixture are percarbonate.

3. compositions as claimed in claim 2, wherein said percarbonate choosing is the group of following composition freely: SODIUM PERCARBONATE, potassium percarbonate and percarbonic acid calcium.

4. compositions as claimed in claim 1, the solid source choosing of wherein said ammonium ion is the group of following composition freely: ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium carbonate, ammonium bicarbonate, aminoquinoxaline and ammonium hydroxide.

5. compositions as claimed in claim 4, the solid source of wherein said ammonium ion is ammonium sulfate.

6. compositions as claimed in claim 1, described compositions also comprises free radical scavenger.

7. compositions as claimed in claim 6, wherein said free radical scavenger choosing is the group of following composition freely: reaction can be not more than 250 alkanolamine and aminoacid for 0kcal/mol to 14kcal/mol and molecular weight.

8. compositions as claimed in claim 7, wherein said free radical scavenger choosing is the group of following composition freely: glycosamine, glycine, glutamic acid, arginine, lysine, glutamine, histidine, serine and their mixture.

9. compositions as claimed in claim 1, described compositions also comprises chelating agen.

10. a method for pigmented hair, said method comprising the steps of:

A) provide compositions as claimed in claim 1;

B) described compositions is mixed with the water of specified amount;

C) compositions of described dispersion is administered on hair;

D) make the compositions of described dispersion on hair, retain 2 to 60 minutes; And

E) compositions of described dispersion is rinsed from hair.