CN1209052A - Hair coloring compositions - Google Patents

Hair coloring compositions Download PDF

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Publication number
CN1209052A
CN1209052A CN 96180116 CN96180116A CN1209052A CN 1209052 A CN1209052 A CN 1209052A CN 96180116 CN96180116 CN 96180116 CN 96180116 A CN96180116 A CN 96180116A CN 1209052 A CN1209052 A CN 1209052A
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hair
acid
composition
compositions
dyestuff
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路易斯·C·迪亚斯
罗伊纳·J·F·普兰
艾莉森·J·桑格
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Procter and Gamble Co
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Procter and Gamble Co
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/38—Percompounds, e.g. peracids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
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Abstract

A hair coloring composition comprising: (a) an organic peroxyacid oxidising agent; and (b) one or more oxididative hair coloring agents. The products can provide excellent hair coloring and in-use efficacy benefits including excellent initial color and good wash fastness in combination with reduced hair damage at lower pH.

Description

Composition for hair dying
Technical field
The present invention relates to the composition for hair dying and the method thereof that are used to have hair dyed, more specifically to the composition for hair dying that comprises at least a preformed organic peroxy acid oxidant and one or more oxide hair dyes.
Background of invention
Because in Rome Empire Age, people have often changed the color of hair so that adapting to fashoined changes, and therefore, the color that people wish to change hair is not a modern aspect.Yet the initial color that hair is definite keeps one section desired time to become more unintelligible target.Difficulty when exploitation can obtain the composition for hair dying of accurate long-time color is that part is the corresponding construction owing to hair itself, and part is the reason owing to the required condition of the process of effectively having hair dyed.
Usually, the situation of people's hair and structure are irregular along sending out shaft length.People's hair will stand various chemistry and mechanical treatment, as combing, brush, wash, heat, perm and being exposed under the sunlight.Therefore, with respect to the hair that newly grows near the scalp place, present the vestige of damage usually at the hair of sending out place, axle two ends.Because absorb hair dye brokenly along sending out on the shaft length, therefore, when hair is dyeed, this damage will cause inconsistent dyeing.Therefore, need a kind of composition for hair dying, said composition can obtain the hair dyeing result of basically identical on whole hair.
After in case hair dyeed, wish the decolourization of the anti-sun of this color and other external factor, and this color can keep one section preset time in the mode of unanimity.Therefore, wish a kind of composition for hair dying of exploitation, during normal the cleaning, said composition demonstrates fading of minimizing and the washability of improvement is provided.Usually another difficulty relevant with people's hair-dyeing is, the dye system that need not have side effects to user hair and skin.
For many years, people are devoted to eliminate the relevant many problems of dyeing with people's hair always.Particularly, developed micromolecular, and can diffuse into oxidative dyestuff in the hair.As what hereinafter will describe in detail, these micromolecule can be activated by peroxide material, and with other molecular reaction, in sending out axle, form bigger colored complex.
In order to utilize the oxidative dyestuff technology that human or animal's hair is dyeed, need handle hair with the mixture of suitable oxidative coloration agent and at least a dyestuff oxidant usually.Hydrogen peroxide is a dyestuff oxidant the most commonly used.Yet, except that the Oxidation of dyestuff, hair is carried out hydrogen peroxide treatment also can dissolve coloured melanocyte composition in the hair, and can cause undesirable hair quality, as because fragility that increases and the very poor state due to the hair damage.These undesirable quality, part is because conventional peroxidating is handled due to (part of hair dyeing process) required condition, the high pH of these processing needs (＞pH9), processing time (10-60 minute) that prolongs and quite high oxidation liquid concentration (up to the oxygen of 20% volume) are so that obtain effective dyestuff oxidation.Therefore, the composition for hair dying of color and the desirable hair conditioning characteristic that needs to provide good.
The composition for hair dying that contains oxidative dyestuff except that dyestuff and peroxide source, comprises peroxide activator usually, many auxilliary cosmetics and peroxide stabilisers that add.Peroxide dyestuff oxidant can make the oxidative dyestuff oxidation at certain pH range (pH2-12).Yet, be known that the hair care agent (HSA) that can regulate oxidation liquid pH by using, can obtain enhanced dyestuff Oxidation.By the swelling to hair fiber, described HSA ' s has further strengthened this oxidation and dyeing course, thus help peroxide and hair dye to diffuse in the hair and make dyestuff oxidation and the hair dyeing faster, more thorough.The preferred HSA that is used to regulate peroxide hair oxidising composition pH is the aqueous solution (alkalescence) that comprises ammonia (ammonium hydroxide).Yet when using with about 1% weight combinations thing or higher consumption, ammonia can make skin cause inflammation.
Can use oxidative dyestuff and peroxide dyestuff oxidant to provide multiple color to hair.Yet the described composition for hair dying that comprises oxidative dyestuff and peroxide dyestuff oxidant can not provide consumer main needs, as color saturation, color clear, accurate initial color precordainment, the washability of improvement, the hair condition of improvement and the safety of improvement.
The applicant has found that, in composition for hair dying, the mixture that comprises preformed peroxy acid oxidant and one or more oxide hair dyes can obtain excellent initial hair color, the fastness to washing of good hair dye within official hour, the color saturation and the distinctiveness of wishing, the hair damage that reduces is effectively under low pH value, and can has hair dyed more quickly.
Therefore, the composition for hair dying that the objective of the invention is a kind of fast-acting.
Another object of the present invention provides a kind of composition for hair dying of the hair dyeing effect that can be improved.
A further object of the present invention provide a kind of when low pH value effective composition for hair dying.
Another purpose of the present invention provides a kind of composition for hair dying that reduces damage that hair fiber is had.
Except as otherwise noted, all percentage ratios of compositions all by weight.
Brief summary of the invention
Theme of the present invention is a kind of composition for hair dying, and said composition is suitable for human body or animal hair.
According to an aspect of the present invention, provide a kind of composition for hair dying, said composition comprises:
(a) preformed organic peroxy acid oxidant; With
(b) one or more oxide hair dyes.
Detailed Description Of The Invention
Processed " hair " of the term of Shi Yonging can be " lived " in the present invention, promptly be grown on the life entity, and maybe can be " abiotic ", i.e. wig is sent out the aggregation of sheet (hairpiece) or other no life fiber.Preferred mammal, preferably people's hair.Yet Pilus Caprae seu Ovis, fur and other melaniferous fiber all are base materials that the present composition is fit to.
The term of Shi Yonging " composition for hair dying " uses in a broad sense in the present invention, and it will comprise the mixture of preformed organic peroxy acid dye oxidant and one or more oxide hair dyes and other batching.In addition, this composition for hair dying also will comprise: contain the complex composition of other component, described other component can the yes or no active batching.Therefore, term " composition for hair dying " is applicable to and also comprises other material such as sequestering agent, thickening agent except that comprising active oxidizer and oxide hair dye, buffer agent, carrier, surfactant, solvent, antioxidant, polymer, the compositions of non-oxidizable dyestuff and conditioner.
In preferred compositions of the present invention, the consumption of preformed peroxy acid component can be represented with weight and/or with available oxygen (AO).
Term " available oxygen " (will further define in the embodiment part) is the theoretical amount that can be delivered to the oxygen in the system from preformed organic peroxy acid oxidant.In preferred compositions, the total amount of available oxygen that derives from preformed organic peroxide acid is from about 0.5 to about 60, preferably from about 2 to about 55, and especially from about 3 to about 50.
Dyestuff oxidation and hair dyeing process
Those skilled in the art know, in order successfully to dye with the hair of oxidative dyestuff to the human or animal, need handle hair with dyestuff oxidant and oxidative dyestuff usually.As previously mentioned, the dyestuff oxidant in the present composition is preformed organic peroxide acid.
The mechanism that makes the reaction of oxidant of the present invention and oxidative dyestuff produce the oxidative dyestuff that is used to have hair dyed still imperfectly understands.Described mechanism is discussed under the title oxidative dyestuff, and according to this mechanism, oxidant of the present invention can interact with main oxidative dyestuff intermediate, and reacts with coupling agent, produces colored substance.
Preformed organic peroxide acid
The main organic peroxy acid oxidant of thing combined according to the invention is that this organic peroxide acid can be expressed from the next at this defined preformed organic peroxide acid:
Figure A9618011600071
The preferred average carbon chain length degree of X=is from C in the formula 1-C 12Replacement or unsubstituted alkyl or aromatic yl group.What be preferred for this is that carbon chain lengths is respectively C 1And C 12Preformed organic peroxide acid be peracetic acid and cross lactic acid (pemanoic acid).Preformed organic peroxide acid, in composition for hair dying weight, its consumption is usually from about 0.01% to about 5% weight, more preferably from about 0.1% to about 4% weight, especially from about 0.2% to about 3% weight.
Preferred organic peroxy acid compound is the chemical compound that following general formula, amide replace: R in the formula 1Be the alkyl of 1-14 carbon atom, aryl or alkaryl, R 2For comprising the alkylidene of 1-14 carbon atom, arlydene and alkarylene group, R 5For H or comprise the alkyl of 1-10 carbon atom, aryl, or alkylaryl group.The organic peroxy acid compound that this class amide replaces is disclosed among the EP-A-0170386.
Other organic peroxide acid comprises: amino oxy hexanoic acid (NAPCA), diacyl and four acyl peroxides, especially diperoxy dodecandioic acid, diperoxy dodecane dicarboxylic acid and the diperoxy tetradecane dicarboxylic acid crossed of nonanoyl.In addition, in the present invention, one-and two-cross Azelaic Acid, one-and two-crossing tridecane bisgallic acid and N-phenyl-diformyl, amino to cross oxy hexanoic acid also be suitable.
Except that above-mentioned main preformed peroxy acid, compositions of the present invention can be chosen wantonly and contain the peroxy acid of being derived and being obtained by the peroxyacid precursor of following formula:
Figure A9618011600073
L is a leaving group in the formula, and X mainly is to promote the functional group of hydrolysis and is the leaving group that is weaker than L that therefore, when crossing hydrolysis, the structure of the peroxy acid that is produced is:
Figure A9618011600081
In the mechanism that is proposed, peroxy acid is produced by peroxyacid precursor, it is believed that by perhydroxyl radical anion (I), and peroxyacid precursor carries out nucleophyllic chemical adsorption and corrodes, thereby forms peroxycarboxylic acid (II); Described perhydroxyl radical anion is produced by the proton abstraction of hydrogen peroxide.Described nucleophyllic chemical adsorption etching reaction was commonly referred to hydrolysis.The general expression formula of crossing hydrolysis is expressed as follows:
In above-mentioned example, R can be an alkyl or aryl, and R ' is any suitable leaving group.The example that R and R ' are suitable is at those groups described in the peroxyacid precursor of title of the present invention.When thinking the initial step of above-mentioned hydrolytic process excessively by hydrogen peroxide generation perhydroxyl radical anion (I), for promoting this conversion, it will be vital keeping The optimum reaction conditions.The scope of the pKa value of hydrogen peroxide is from about 11.2 to about 11.6, therefore, when the pH value of oxidant about 9 to about 12 the time, normally effective.On the contrary, the pKa value of the peroxyacid precursor of hereinafter describing in detail is about 7 to about 9.5.
Suitable peroxy acid bleach precursor compound comprises one or more N-or O-carboxyl groups usually in the L position, described precursor can be selected from a lot of class materials.Suitable kind comprises: the acid anhydride of imidazoles and oxime, ester, acid imide, lactams, enol ether, sulphonic acid ester amide and acyl derivative.The example of useful materials is disclosed among the GB-A-1586789 in these class materials.Suitable ester is disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in.
Leaving group
Leaving group (hereinafter being referred to as the L group) is crossed hydrolysis and must be had enough activity for what in the desirable time (for example from 0-20 minute, preferably from 0-10 minute, more preferably from response time of 1-5 minute) took place.
Preferred L group is selected from following group:
Figure A9618011600091
And the mixture of these groups, R in the formula 1For comprising the alkyl of 1-14 carbon atom, aryl, or alkaryl, R 3For comprising the alkyl chain of 1-8 carbon atom, R 4Be H or R 3, Y is H or solubilizing group, wherein solubilizing group is to increase the water miscible any suitable hydrophilic radical of L group.R 1, R 3And R 4Any can be replaced by any basically functional group, and described functional group for example comprises: alkyl, hydroxyl, alkoxyl, halogen, amine, nitrosyl radical, amide and ammonium or alkyl ammonium group.
Preferred solubilizing group is :-SO 3 2-M +,-CO 3 2-M +,-SO 4 2-M +,-N +(R 3) 4X -And O＜--N (R 3) 3, most preferably-SO 3 2-M +With-CO 3 2-M +, R wherein 3Be the alkyl chain that comprises 1-4 carbon atom, M provides deliquescent cation for giving the precursor auxiliary agent, and X is for providing deliquescent anion to precursor.Preferably, M is an alkali metal, the ammonium cation of ammonium or replacement, and most preferably sodium and potassium, X is halogenide, hydroxide, methylsulfate or acetic acid anion.
In addition, many peroxyacid precursors can be included in the composition for hair dying of the present invention.These materials comprise: alkyl peroxycarboxylic acid precursors, alkyl peroxy acids precursor, peroxybenzoic acid precursors, cation peroxyacid precursor and benzoxazinyl organic peroxy acid precursors that amide replaces.
The alkyl peroxycarboxylic acid precursors
The alkyl peroxycarboxylic acid precursors forms percarboxylic acids when crossing hydrolysis.Preferred this class precursor provides peracetic acid when hydrolysis.Usually, any have the about 1 alkyl peroxycarboxylic acid precursors to the alkyl carbon chain length of about 20 carbon atoms and all be applicable to the present invention.Alkyl chain can be that replace or unsubstituted.
The preferred alkyl peroxycarboxylic acid precursors chemical compound of acid imide comprises: N-, N, N 1N 1-tetra-acetylatedization Alkylenediamine, wherein alkylidene group comprises 1-6 carbon atom, and particularly wherein alkylidene comprises those chemical compounds of 1,2 and 6 carbon atom.Particularly preferably be tetra acetyl ethylene diamine (TAED).
Other preferred alkyl peroxycarboxylic acid precursors comprises: 3,5,5-trimethyl six pelargonyl group sodium sulfocarbolate .s (different-NOBS), pelargonyl group sodium sulfocarbolate. (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and penta-acetyl glucose.The pelargonyl group sodium sulfocarbolate. is expressed as follows:
Figure A9618011600101
In above-mentioned example, R=C 8H 17, X=C wherein 8H 17, L=O-C 6H 4-SO 3 -
The alkyl peroxy acids precursor that amide replaces
The alkyl peroxy acids precursor compound that amide replaces is applicable to the present invention, and they comprise the chemical compound of following general formula:
Figure A9618011600102
Or R in the formula 1Be the alkyl of 1-14 carbon atom, R 2For comprising the alkylidene group of 1-14 carbon atom, R 5For H or comprise the alkyl group of 1-10 carbon atom, L can be any leaving group basically.The precursor compound that this class amide replaces is disclosed among the EP-A-0170386.
Peroxybenzoic acid precursors
The peroxybenzoic acid precursors chemical compound provides benzylhydroperoxide when crossing hydrolysis.Suitable O-acetyl group peroxybenzoic acid precursors chemical compound comprises: replace and unsubstituted benzoyl sulfophenylate; and sorbitol; the benzoylation product of glucose and other polysaccharide and benzoylating agent; and comprising N-benzoyl succimide, four benzoyl ethylenediamines and N-benzoyl replace the acid imide material of urea.Suitable imidazoles peroxybenzoic acid precursors comprises: N-benzoyl imidazoles, N-benzoyl caprolactam and N-benzoyl benzimidazole.The peroxybenzoic acid precursors that comprises the N-acyl group that other is useful comprises: N-benzoyl pyrrole alkane ketone, dibenzoyl taurine and benzoyl pyroglutamic acid.Following Example has illustrated the N-benzoyl caprolactam:
Figure A9618011600111
The cation peroxyacid precursor
Cation peroxyacid precursor chemical compound produces the cation peroxy acid when crossing hydrolysis.
Usually, by with positively charged functional group such as ammonium or alkylammonium, preferred ethyl or ammonium methyl group replace the peroxy acid part of suitable peroxyacid precursor chemical compound and form the cation peroxyacid precursor.The cation peroxyacid precursor is present in the composition for hair dying of the present invention with the form with the salt of suitable anion such as halide ion usually.
So the peroxyacid precursor chemical compound of cationization replacement can be a benzylhydroperoxide, or the derivant of its replacement, and aforesaid precursor compound.In addition, this peroxyacid precursor chemical compound can also be the alkyl peroxycarboxylic acid precursors chemical compound as described below or the alkyl peroxy acids precursor of amide replacement.
The cation peroxyacid precursor is described in US4, and 904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; GB-A-1,382,594; EP-A-0,475,512; EP-A-0,458,396 and EP-A-0,284,292; And JP-A-87-318, in 332.
The example of preferred cation peroxyacid precursor is described in GB-A-9407944.9 and US-A-08/298903; 08/298650; In 08/298904 and 08/298906.
Suitable cation peroxyacid precursor comprises: alkyl or benzoyl sulfophenylate that ammonium or alkylammonium replace, the tetra-acetylated glucose benzoyl peroxide of a N-acyl group caprolactam and a benzoyl.N-acyl group caprolactam class preferred cation peroxyacid precursor comprises: trialkyl ammonium methylene benzoyl caprolactam and trialkyl ammonium methylene alkyl caprolactam.What list below is the benzoyl sulfophenylate of alkylammonium replacement and the example of trialkyl ammonium methylene benzoyl caprolactam:
Figure A9618011600112
Figure A9618011600121
Or
Benzoxazinyl organic peroxy acid precursors
What also be suitable in addition is the benzo oxazinyl precursor compound, as EP-A-332, and 294 and EP-A-482, disclosed in 807, the chemical compound of following structure particularly:
Figure A9618011600123
R in the formula 1Be H, alkyl, alkaryl, aryl or aralkyl.
Hair dye
In addition, compositions of the present invention comprises one or more oxide hair dyes as basic feature.Described oxide hair dye can use with oxidation system of the present invention, thereby makes forever, and part is permanent, semipermanent or temporary transient composition for hair dying.
The permanent composition for hair dying of Xian Dinging is such compositions in the present invention, in case be applied on the hair, it will be wash-resistant basically.The permanent composition for hair dying of the part of Xian Dinging is such compositions in the present invention, is washing at the most after 24 times, and it will be washed off from hair basically.The semipermanent composition for hair dying of Xian Dinging is such compositions in the present invention, in case be applied on the hair, after washing for 10 times at the most, it will be washed off from hair basically.The temporary transient composition for hair dying of Xian Dinging is such compositions in the present invention, in case be applied on the hair, after washing for 2 times at the most, it will be washed off basically.Defined in the present invention washing off refers to such process, and by this process, hair dye is removed from hair during normal hair cleans.
The concentration of various oxide hair dyes is from about 0.001% to about 6% weight in composition for hair dying of the present invention, preferably from about 0.01% to about 2.0% weight.
The total amount of oxide hair dye is from about 0.01% to about 15% weight in the present composition, preferably from about 0.1% to about 10% weight, more preferably from about 0.5% to about 5% weight.(I) oxidative dyestuff
It mainly is aromatic diamine class, amino-phenol and derivant thereof that the dyestuff that uses in oxidative dyestuff forms intermediate.The intermediate that these can be formed dyestuff is categorized into: main intermediate (primaryintermediates), inferior intermediate (secondaryintermediates) and nitro dye.Main intermediate is the chemical compound that itself will form dyestuff when oxidation.Inferior intermediate also is referred to as color modifier or coupling agent, and uses with other intermediate for specific color effects or in order to stablize color.Nitro dye is unique, and they are to need not oxidation and the direct dyes of having hair dyed.
The oxidative dyestuff intermediate that is applicable to the present composition and method comprises: aromatic diamines, polyhydroxy phenol, the derivant of amino-phenol and these aromatics (for example derivant of the N-of amine replacement and the ethers of phenol).Before Oxidation, the normally colourless molecule of the main intermediate of oxidative dyestuff.When main intermediate is " activated ", produce the color of oxidative dyestuff, use time intermediate (coupling agent, by also be colourless) catalysis to form coloured conjugated molecule subsequently.
Do not wish to be bound by a particular theory, the representative that is used to activate with coupling reaction that is proposed is described as follows: wherein, that knows usually is the active matter (OX) " activation " (oxidation) that organic peroxy acid oxidant that main dyestuff intermediate (A) is pre-formed and/or auxiliary selective oxidation agent (if present) are discharged during decomposing.The dyestuff intermediate of this " activation "-can have structural formula (B)-subsequently and suitable bigger " coloured " dye composition of coupling agent reaction formation, as dimer and trimer.
Figure A9618011600131
The oxidative dyestuff intermediate diffuses into to be sent out in the axle, activates then and coupling, thereby form dye ligand compound that be not easy to wash off, bigger in sending out axle; Described axle is by the effect of HSA (if present) and pre-swelling.
In general, oxidation hair-dye precursor or intermediate comprise: form those monomer materials of oligomer or polymer when oxidation, described oligomer or polymer have the electron conjugated system of extension in its molecular structure.Because this new electronic structure, final oligomer and polymer have a displacement with respect to visible-range in its electronic spectrum, and are colored.For example, the oxidative dyestuff precursor that can form colored polymeric comprises: the material as aniline, this material have simple function group and form when oxidation and drop on green a series of conjugated imines and quinoid dimer, trimer etc. to the black scope.Have chemical compound two functional groups, as p-phenylenediamine and can carry out oxidation polymerization, form high molecular more, have the colored materials of the conjugated electrons system of extension.Color modifier (coupling agent) as hereinafter describing in detail, preferably uses with oxidative dyestuff precursor of the present invention, and think and during it forms, itself get involved in the colored polymeric, and in its electronic spectrum, will produce displacement, thus, make color produce slight change.Be applicable to that representational oxidative dyestuff precursor of the present invention can be referring to " cosmetic science and the technology " of Sagarin, Interscience, Special Edn. the 2nd volume, the 308th to 310 page.What should understand is, oxidation promoter of the present invention is suitable for using with all oxidative dyestuff precursors and color the modifier peroxide source of this detailed description (and), and precursor described in detail below is illustrative, do not constitute the qualification to the compositions and methods of the invention.
Aforesaid as the typical aromatic diamines of main dyestuff former, polyhydroxy phenol, amino-phenol, and derivant, the substituent group on aromatic rings also can be arranged in addition, for example, halogen, aldehyde, carboxylic acid, nitro, sulfonic acid, replace and unsubstituted alkyl, and amino nitrogen and on phenol oxygen base other substituent group, for example replacement and unsubstituted alkyl and aromatic yl group.
Suitable aromatic diamines, amino-phenol, the corresponding example of polyhydroxy phenol and derivant thereof are to have following logical formula VI, the chemical compound of (VII) and (VIII): Or
Figure A9618011600142
Y is a hydrogen in the formula, halogen (for example fluorine, chlorine, bromine or iodine), and nitro, amino, hydroxyl,
Figure A9618011600151
-COOM or-SO 3M (wherein M is hydrogen or alkali or alkaline-earth metal, ammonium, or the replacement ammonium that replaced by the alkyl of 1-3 carbon atom or hydroxyalkyl group of the one or more hydrogen on the ammonium ion wherein), R in the formula 1, R 2, R 3And R 4Be same to each other or different to each other, and be selected from: hydrogen, C 1-C 4Alkyl or alkenyl, and C 6-C 9Aryl, alkaryl or aralkyl, R 5Be hydrogen, wherein substituent group is selected from the C of above-mentioned Y 1-C 4The alkyl or alkenyl that does not replace or replace, or wherein substituent group is selected from the C of above-mentioned Y 6-C 9The aryl, alkaryl or the aralkyl that do not replace or replace.Because the precursor of structure formula VI is an amine, therefore, the form of the salt that they can described peroxide compatible is used, and wherein X is illustrated in the anion of the sort of peroxide compatible of detailed earlier herein.The general formula that it should be understood that the salt of expression comprises having one, two and the anionic salt of trivalent.
The object lesson of structural formula (VII) chemical compound is: ortho-phenylene diamine, between-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, 2-iodo-p-phenylenediamine, 4-nitro-ortho-phenylene diamine, 2-nitro-p-phenylenediamine, 1,3, the 5-triaminobenzene, 2-hydroxyl-p-phenylenediamine, 2, the 4-diaminobenzoic acid, 2,4-diaminobenzoic acid sodium, two (2, the 4-diaminobenzoic acid) calcium, 2,4-amino benzoic Acid ammonium, 2,4-diaminobenzoic acid trimethylammonium, 2,4-diaminobenzoic acid three (2-ethoxy) ammonium, 2,4-diaminobenzene formaldehyde carbonic ester, 2, the 4-diamino benzene sulfonic acid, 2,4-diamino benzene sulfonic acid potassium, N, N-diisopropyl-p-phenylenediamine two carbonic esters, N, N-dimethyl-p-phenylenediamine, N-ethyl-N '-(2-acrylic)-p-phenylenediamine, N-phenyl-p-phenylenediamine, N-phenyl-N-benzyl-p-phenylenediamine, N-ethyl-N '-(3-ethylbenzene base)-p-phenylenediamine, 2,4-toluenediamine, 2-ethyl-p-phenylenediamine, 2-(2-bromoethyl)-p-phenylenediamine, 2-phenyl-p-phenylenediamine laurate, 4-(2, the 5-diamino-phenyl) benzaldehyde, 2-benzyl-p-phenylenediamine acetas, 2-(4-nitrobenzyl)-p-phenylenediamine, 2-(4-tolyl)-p-phenylenediamine, 2-(2, the 5-diamino-phenyl)-the 5-ar-Toluic acid, the methoxyl group p-phenylenediamine (PPD), dimethyl-p-phenylenediamine, 2, the 5-dimethyl-p-phenylenediamine, 2-methyl-5-methoxyl group-p-phenylenediamine, 2,6-methyl-5-methoxyl group-p-phenylenediamine, 3-methyl-4-amino-N, the N-diethylaniline, N, N-two (beta-hydroxyethyl)-p-phenylenediamine, 3-methyl-4-amino-N, N-two (beta-hydroxyethyl) aniline, 3-chloro-4-amino-N, N-two (beta-hydroxyethyl) aniline, 4-amino-N-ethyl-N-(carbonyl methyl) aniline, 3-methyl-4-amino-N-ethyl-N-(carbonyl methyl) aniline, 4-amino-N-ethyl-(β-piperidones and ethyl) aniline, 3-methyl-4-amino-N-ethyl-(β-piperidones and ethyl) aniline, 4-amino-N-ethyl-N-(β-morpholino ethyl) aniline, 3-methyl-4-amino-N-ethyl-N-(β-morpholino ethyl) aniline, 4-amino-N-ethyl-N-(β-acetylamino ethyl) aniline, 4-amino-N-('beta '-methoxy ethyl) aniline, 3-methyl-4-amino-N-ethyl-N-(β-acetylamino ethyl) aniline, 4-amino-N-ethyl-N-(β-methanesulfonamido ethyl) aniline, 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamido ethyl) aniline, 4-amino-N-ethyl-N-(β-thio-ethyl) aniline, 3-methyl-4-amino-N-ethyl-N-(β-thio-ethyl) aniline, N-(4-aminophenyl) morpholine, N-(4-aminophenyl) piperidines, 2,3-dimethyl-p-phenylenediamine, isopropyl-p-phenylenediamine, N, N-two (2-ethoxy)-p-phenylenediamine sulfuric ester. Or
Figure A9618011600162
Identical in the formula in X and Y and the structure formula VI, R 1And R 2Each other can be identical or different and with the structure formula VI in identical, R 5Identical with in the structure formula VI, R 6For hydrogen or wherein substituent group be selected from the C of Y in the structure formula VI 1-C 4Replacement or unsubstituted alkyl or thiazolinyl.
The object lesson of structural formula (VII) chemical compound is: O-aminophenol, between-amino-phenol, para-aminophenol, 2-iodo-para-aminophenol, 2-nitro-para-aminophenol, 3,4-dihydroxy aniline, 3, the 4-diaminophenol, the chloracetic acid ester, 2-hydroxyl-4-amino benzoic Acid, 2-hydroxyl-4-aminobenzaldehyde, 3-amino-4-hydroxy benzenesulfonic acid, N, N-diisopropyl-para-aminophenol, N-methyl-N-(1-acrylic)-para-aminophenol, N-phenyl-N-benzyl-para-aminophenol sulfuric ester, N-methyl-N-(3-ethylbenzene base)-right-amino phenols, 2-nitro-5-ethyl-para-aminophenol, 2-nitro-5-(2-bromoethyl)-para-aminophenol, (2-hydroxyl-5-aminophenyl) acetaldehyde, 2-methyl-para-aminophenol, (2-hydroxyl-5-amino-phenol) acetic acid, 3-(2-hydroxyl-5-aminophenyl)-1-propylene, 3-(2-hydroxyl-5-aminophenyl)-2-chloro-1-propylene, 2-phenyl-para-aminophenol cetylate, 2-(4-nitrobenzophenone)-para-aminophenol, 2-benzyl-para-aminophenol, 2-(4-benzyl chloride base)-para-aminophenol perchlorate, 2-(4-tolyl)-para-aminophenol, 2-(2-amino-4-tolyl)-para-aminophenol, right-aminoanisole, 2-bromoethyl-4-aminophenyl ether phosphate, 2-nitro-ethyl-4-aminophenyl ether bromide, 2-amino-ethyl-4-aminophenyl ether, 2-ethoxy-4-aminophenyl ether, (4-amino-benzene oxygen) acetaldehyde, (4-amino-benzene oxygen) acetic acid, (4-amino-benzene oxygen) methanesulfonic acid, 1-acrylic-4-aminophenyl ether isobutyrate, (2-chlorine)-1-acrylic-4-aminophenyl ether, (2-nitro)-1-acrylic-4-aminophenyl ether, (2-amino)-acrylic-4-aminophenyl ether, (2-hydroxyl)-1-acrylic-4-aminophenyl ether, N-methyl-para-aminophenol, 3-methyl-4-amino-phenol, 2-chloro-4-amino-phenol, 3-chloro-4-amino-phenol, 2,6-dimethyl-4-amino-phenol, 3,5-dimethyl-4-amino-phenol, 2,3-dimethyl-4-amino-phenol, 2,5-dimethyl-4-amino-phenol, 2-methylol-4-amino-phenol, 3-methylol-4-amino-phenol. Y in the formula, R 5And R 6As the definition in the top structural formula (VII).
The object lesson of structural formula (VIII) chemical compound is: neighbour-hydroxyl phenol (catechol), between hydroxyl phenol (resorcinol), para hydroxybenzene phenol (hydroquinone), the 4-methoxyphenol, the 2-methoxyphenol, 4-(2-chloroethoxy) phenol, 4-(2-propylene oxygen) phenol, 4-(3-chloro-2-propylene oxygen) phenol, 2-chloro-4-hydroxyl phenol (2-chlorohydroquinone), 2-nitro-4-hydroxyl phenol (2-p-hydroquinone), 2-amino-4-hydroxy phenol, 1,2,3-trihydroxy benzene (1,2, the 3-benzenetriol), 2, the 4-4-dihydroxy benzaldehyde, 3,4-hydroxy benzoic acid, 2, the 4-dihydroxy benzenes sulfonic acid, 3-ethyl-4-hydroxyl phenol, 3-(2-nitro-ethyl)-4-hydroxyl phenol, 3-(2-acrylic)-4-hydroxyl phenol, 3-(3-chloro-2-acrylic)-4-hydroxyl phenol, 2-phenyl-4-hydroxyl phenol, 2-(4-chlorphenyl)-4-hydroxyl phenol, 2-benzyl-4-hydroxyl phenol, 2-(2-nitrobenzophenone)-4-hydroxyl phenol, 2-(2-aminomethyl phenyl)-4-hydroxyl phenol, 2-(2-methyl-4-chlorphenyl)-4-hydroxyl phenol, 3-methoxyl group-4-hydroxy benzaldehyde, 2-methoxyl group-4-(1-acrylic) phenol, 4-hydroxyl-3-methoxy cinnamic acid, 2, the 5-dimethoxyaniline, 2-methylresorcinol, alpha-Naphthol and salt thereof.
As previously mentioned, the color modifier that is applicable to composition for hair dying of the present invention and method comprises: some aromatic amine and phenol with and derivant, described modifier can not produce color separately, but it can change color, tone or the color intensity that is produced by the oxidative dyestuff precursor.Some aromatic amine and oxybenzene compound, and derivant comprises the said structure formula VI, (VII) and (VIII) described some aromatic diamines and polyhydroxy phenol, but these are materials that are not suitable for the oxidative dyestuff precursor well known in the art, are suitable for color modifier of the present invention.In addition, polyhydroxy phenol also is suitable as color modifier.
Aromatic amine and phenol derivmives blend biology as color modifier also can have the other substituent group on aromatic rings as previously mentioned; halogen for example; aldehyde; carboxylic acid; nitro, sulfonyl, and by alkyl replacement and replacement; and the other substituent group on amino nitrogen or phenol oxygen base, for example replacement and unsubstituted alkyl and aryl.In addition, its peroxide-compatible salt also is applicable to this.
The example of aromatic amine, phenol and derivant thereof is the chemical compound of following structural formula (IX) and (X): Or Z is a hydrogen in the formula, C 1And C 3Alkyl, halogen (for example fluorine, chlorine, bromine or iodine), nitro,
Figure A9618011600183
-COOM or-SO 3M (wherein M is hydrogen or alkali or alkaline-earth metal, ammonium, or the replacement ammonium that replaced by the alkyl of 1-3 carbon atom or hydroxyalkyl group of the one or more hydrogen on the ammonium ion wherein), R in the formula 1And R 2Be same to each other or different to each other, and be selected from: hydrogen, C 1-C 4Alkyl or alkenyl, and C 6-C 9Aryl, alkaryl or aralkyl, R 7Be hydrogen, wherein substituent group is selected from the C of above-mentioned Z 1-C 4The alkyl or alkenyl that does not replace or replace, or wherein substituent group is selected from the C of above-mentioned Z 6-C 9The aryl that does not replace or replace, alkaryl or aralkyl, wherein X represents as the definition in the structure formula VI.
The object lesson of structural formula (IX) chemical compound is: aniline, and right-chloroaniline, para-fluoroaniline, paranitroanilinum, para aminotenzaldehyde, para-amino benzoic acid, para aminobenzoic acid sodium salt, para-amino benzoic acid lithium, two (para-amino benzoic acid) calcium, the para-amino benzoic acid ammonium, para-amino benzoic acid trimethyl ammonium, para-amino benzoic acid three (2-ethoxy) ester, p-anilinesulfonic acid., p-anilinesulfonic acid. potassium, methylphenylamine, N-propyl group-N-phenylaniline, N-methyl-N-2-acrylic aniline, Phenhenzamine, N-(2-ethylbenzene base) aniline, 4-monomethylaniline., 4-(2-bromoethyl) aniline, 2-(2-nitro-ethyl) aniline, (4-aminophenyl) acetaldehyde, (4-aminophenyl) acetic acid, 4-(2-acrylic) phenylglycine ester, 4-(3-bromo-2-acrylic) aniline, 4-phenylaniline chloracetic acid ester, 4-(3-chlorphenyl) aniline, the 4-benzylaniline, 4-(4-benzyl iodide) aniline, 4-(3-ethylbenzene base) aniline, 4-(2-chloro-4-ethylbenzene base) aniline. Z and R in the formula 7Such as in the structural formula (IX) definition, R 8For hydrogen or wherein substituent group be selected from the C of Z in the structural formula (IX) 1-C 4That replace or unsubstituted alkyl or thiazolinyl.
The object lesson of structural formula (X) chemical compound is: phenol, parachlorophenol, paranitrophenol, hydroxy benzaldehyde, P-hydroxybenzoic acid, p-hydroxybenzenyl sulfonate, ethylphenyl ether, 2-chloroethyl phenyl ether, 2-nitro-ethyl phenyl ether, phenoxy acetaldehyde, phenoxyacetic acid, 3-phenoxy group-1-propylene, 3-phenoxy group-2-nitro-1-propylene, 3-phenoxy group-2-bromo-1-propylene, 4-propylphenol, 4-(3-bromopropyl) phenol, 2-(2-nitro-ethyl) phenol, (4-hydroxyphenyl) acetaldehyde, (4-hydroxyphenyl) acetic acid, 4-(2-acrylic) phenol, 4-phenylphenol, the 4-benzylphenol, 4-(3-fluoro-2-acrylic) phenol, 4-(4-benzyl chloride base) phenol, 4-(3-ethylbenzene base) phenol, 4-(2-chloro-3-ethylbenzene base) phenol, 2, the 5-xylenols, 2, the 5-diamino-pyridine, 2-hydroxyl-5-aminopyridine, 2-amino-3-pyridone, tetraminopyrimidine, 1,2, the 4-trihydroxy benzene, 12,4-trihydroxy-5-(C1-C6-alkyl) benzene, 1,2,3-trihydroxy benzene, 4-aminoresorcinol, 1, the 2-dihydroxy benzenes, 2-amino-1,4-dihydroxy benzenes, 2-amino-4-methoxyphenol, 2,4-diaminophenol, 3-methoxyl group-1, the 2-dihydroxy benzenes, 1,4-dihydroxy-2-(N, N-lignocaine) benzene, 2,5-diaminourea-4-methoxyl group-1-hydroxy benzenes, 4,6-dimethoxy-3-amino-1-hydroxy benzenes, 2,6-dimethyl-4-[N-(to hydroxyphenyl) amino]-the 1-hydroxy benzenes, 1,5-diaminourea-2-methyl-4-[N-(to hydroxyphenyl) amino] benzene and salt thereof.
Be applicable to that other oxidative dyestuff precursor of the present invention comprises: catechol, particularly it comprises catechol " DOPA " class of DOPA itself, and the homologue of DOPA, analog and derivant.The example of suitable catechol comprises: half light amine acyl DOPA, 1-4 is arranged in alkyl, and the alpha-alkyl DOPA of preferred 1-2 carbon atom, epinephrine, and 1-6 is arranged, the DOPA Arrcostab of preferred 1-2 carbon atom in alkyl.
Usually, suitable catechol is represented by following structural formula (XI):
Figure A9618011600191
R in the formula 1, R 2And R 3Can be identical or different, and for being selected from H, rudimentary (C 1-C 6) alkyl, OH, OR, COOR, NHCOR, CN, COOH, halogen, NO 2, CF 3, SO 3H or NR 4R 5Electron donor or receptor substituent group, precondition is R 1, R 2And R 3In have only one can be CN, COOH, halogen, NO 2, CF 3Or SO 3H; R 4And R 5Can be identical or different and be H, rudimentary (C 1-C 6) alkyl, or the rudimentary (C that replaces 1-C 6) alkyl, wherein said substituent group can be OH, OR, NHCOR 6, NHCONH 2, NHCO 2R 6, NHCSNH 2, CN, COOH, SO 3H, SO 2NR 6Or CO 2R 6R 6Be rudimentary (C 1-C 6) alkyl, be connected to rudimentary (C on the nitrogen-atoms by alkylidene chain 1-C 6) the hydroxyalkyl phenyl, phenyl or have R 1The phenyl of substituent replacement, R are C 1-C 6Alkyl or C 1-C 6Hydroxyalkyl.
In the present invention, the oxidative dyestuff precursor can use separately or be used in combination with other oxidative dyestuff precursor, one or more dyestuff formers can be used in combination with one or more color modifier.The selection of single dyestuff former and modifier will be by desirable color, and the color harmony color density is determined.In the present invention, having can be separately or 19 kinds of preferred oxidative dyestuff precursors that are used in combination, thereby the oxide hair dye from ash golden yellow (ashblonde) to the various tones of black is provided; These 19 kinds of hair dyes are: 1,2, and 3-benzenetriol, resorcinol, to toluenediamine, p-phenylenediamine (PPD), o-phenylenediamine, m-diaminobenzene., o-aminophenol, para-aminophenol, 4-amino-2-nitrophenol, nitro-p-phenylenediamine (PPD), N-phenyl-p-phenylenediamine (PPD), m-aminophenol, 2-amino-3-pyridone, 1-naphthols, N, N-two (2-ethoxy) p-phenylenediamine (PPD), 4-amino-2-hydroxy-methylbenzene, 1,5-dihydroxy naphthlene and 2,4-diamino anisole.These materials can use with the molecular forms that describes in detail above or with the form of the salt of peroxide compatible.
Described in the present invention main oxidative dyestuff intermediate and coupling material can be in conjunction with so that provide multiple color to hair.Hair dye can change the degree of depth of color and the intensity of color.Described in the present invention color intensity refers to, and forms and be retained in the quantity of colored compound in the hair on hair.Usually, described in the present invention high strength refers to dead color or dark color, as peony, and dark-brown or black etc.Therefore, according to the above description,, can make the hair dye of different colours intensity by regulating the initial consumption of each oxidative dyestuff.
For example, low-intensity such as natural golden yellow to light brown hair comprises usually from the about 0.001% total amount oxide hair dye to about 0.5% weight (in composition for hair dying weight), and can by with main intermediate as 1,4-diaminourea-benzene, 2,5-diaminotoluene, 2, the 5-diamino anisole, the 4-amino-phenol, 2,5-diaminobenzene methanol and 2-(2 ', 5 '-diaminourea) phenethanol and coupling agent such as resorcinol, 2-methylresorcinol or 4-chloro-resorcinol combine and obtain.
By with above-mentioned main intermediate such as 5-amino-2-methyl phenol and 1, the 3-diamino benzene derivant is as 2, and the 4-diamino anisole carries out the redness that similar combination (total amount of hair dye from about 0.5% to about 1%) can obtain moderate strength.High-intensity color such as blueness to indigo plant-purple can by with above-mentioned main intermediate and coupling agent as 1,3-diaminobenzene or derivatives thereof is as 2, the combination of 5-diaminotoluene (total consumption of hair dye be composition weight about 1% to about 6% weight) obtains.Black hair dye can by with above-mentioned main intermediate and coupling agent as 1, the combination of 3-diaminobenzene or derivatives thereof and obtaining.
Yet the problem that needs to consider is to be commonly used to give the physiological compatibility of hair with the para-aminophenol of redness.Similarly, as 1, the physiological compatibility of 4-para diaminobenzene throws doubt upon for some hair dye that is commonly used to produce black.Therefore, needed a kind of oxidative hair dye composition already, said composition has the safety of improvement, and particularly dark color can be provided is high color intensity to this oxidative dye composition, and has the safety of improvement.
As previously mentioned, the applicant has found that the preformed organic peroxy acid oxidant that the present invention is specific combines with oxidative dyestuff for excellent color saturation is provided, and distinctiveness and initial dyeing property are very important.Yet the applicant finds that also the compositions of the present invention that comprises specific preformed organic peroxy acid precursors oxidant and oxidative dyestuff is very important for the dye dosage that provides good high strength color (dark color) and reduce.Particularly, the applicant finds, utilizes dyestuff oxidation system of the present invention and with respect to the composition for hair dying of the routine dyestuff below 50% at the most, can obtain good hair dyeing result.Therefore, except that having more acceptant safety, compositions of the present invention for the hair conditions that improvement is provided and good initial color and the washability at the appointed time be very important.
Therefore, according to a further aspect in the invention, provide a kind of composition for hair dying, said composition comprises:
(a) from about 0.01% to the preformed organic peroxy acid oxidant of about 5% weight;
(b) from about 0.0005% one or more oxide hair dyes to about 3% weight.(ⅱ) non-oxidizable dyestuff and other dyestuff
Except that main oxidative coloration of hair agent, composition for hair dying of the present invention also can be chosen wantonly in addition and comprise non-oxidizable dyestuff and other dyestuff.Optional non-oxidizable dyestuff and other dyestuff of being applicable to composition for hair dying of the present invention and method comprise: semipermanent dyestuff, temporary transient dyestuff and other dyestuff.Ding Yi non-oxidizable dyestuff comprises so-called " directly acting on dyestuff " in the present invention, metal dye, metal-chelator dyestuff, fibre-reactive dye and other synthetic and natural dyestuff.Various non-oxidizable dyestuffs are specified in the following document: " human hair's the Chemical Physics performance " of ClarenceRobbins, the 250th～259 page, the third edition; " The Chemistry and Manufacture of Cosmetics ", IV volume, second edition, Maison G.De Navarre, the 45th chapter (G.S.Kass, 841-920 page or leaf); " cosmetics: science and technology ", second edition, II volume, BalsamSagarin, the 23rd chapter (F.E.Wall, 279-343 page or leaf); By " the hair care science " that C.Zviak edits, " hair dye " of the 7th chapter (235-261 page or leaf) and J.C.Johnson (NoyesDataCorp., ParkRidge, USA, 1973, the 3-91 pages or leaves and 113-139 page or leaf).
The direct effect dyestuff that need not Oxidation for the generation color also is referred to as the hair toner, and is well known in the art.They normally are applied on the hair in comprising the base material of surface active material.Directly the effect dyestuff comprises nitro dye, as the derivant of nitro amino benzene or nitro amino phenol; Disperse dyes, as nitro aromatic amine, amino anthraquinones or azo dye; Anthraquinone dye, naphthoquinone dyestuff; Basic stain is as acridine orange C.I.46005.
Directly other example of effect dyestuff comprises: Arianor dyestuff bismarck brown 17, C.I. (Colour Index)-12,251; Alkalescence is red 76, C.I.-12,245; Bismarck brown 16, C.I.-12,250; Basic yellow 57, C.I.-12,719 and alkali blue 99, C.I.-56,059, and other direct effect dyestuff, as Indian yellow 1, C.I.-10,316 (D﹠amp; Yellow No. 7 of C); Indian yellow 9, C.I.-13,015; Alkalescence is purple, C.I.-45,170; Disperse yellow 3, C.I.-11,855; Basic yellow 57, C.I.-12,719; Disperse yellow 1, C.I.-10,345; Alkaline purple 1, C.I.-42,535, alkaline purple 3, C.I.-42,555; Greenish blue, C.I.-42090 (FD﹠amp; Blue No. 1 of C); Gold-tinted is red, C.I.-14700 (FD﹠amp; Red No. 4 of C); Huang, C.I.19140 (FD﹠amp; Yellow No. 5 of C); The gold-tinted orange, C.I.-15985 (FD﹠amp; Yellow No. 6 of C); Blue light is green, C.I.-42053 (FD﹠amp; Green No. 3 of C); Gold-tinted is red, C.I.-16035 (FD﹠amp; Red No. 40 of C); Blue light is green, C.I.-61570 (D﹠amp; Green No. 3 of C); Orange, C.I.-45370 (D﹠amp; No. 5, C orange); Red, C.I.-15850 (D﹠amp; Red No. 6 of C); Blue light is red, C.I.-15850 (D﹠amp; Red No. 7 of C); Light blue light is red, C.I.-45380 (D﹠amp; Red No. 22 of C); Blue light is red, C.I.-45410 (D﹠amp; Red No. 28 of C); Blue light is red, C.I.-73360 (D﹠amp; Red No. 30 of C); The HONGGUANG purple, C.I.-17200 (D﹠amp; Red No. 33 of C); Turbid bluish red, C.I.-15880 (D﹠amp; Red No. 34 of C); Bright Huang is red, C.I.-12085 (D﹠amp; Red No. 36 of C); Bright orange, C.I.-15510 (D﹠amp; No. 4, C orange); The green glow Huang, C.I.-47005 (D﹠amp; Yellow No. 10 of C); Blue light is green, C.I.-59040 (D﹠amp; Green No. 8 of C); The blue light purple, C.I.-60730 (Ext.D﹠amp; Purple No. 2 of C); The green glow Huang, C.I.-10316 (Ext.D﹠amp; Yellow No. 7 of C);
Fibre-reactive dye comprises: derive from ICI respectively, Sandoz, Ciba-Geigy, the Procion of Bayer and Hoechst (RTM), Drimarene (RTM), Cibacron (RTM), Levafix (RTM) and Remazol (RTM) dyestuff.
Natural dye and vegetable colour in this definition comprise: Flos Impatientis (Lawsoniaalba), and Chamomile (Matricariachamomila or Anthemisnobilis), indigo, the extract of Lignum Sappan and walnut shell.
Temporary hair dyestuff, or the hair dyeing purificant is sent out the interior and dye molecule that only worked in the hair outside of axle and is formed to not diffusing into by big usually.These dyestuffs normally can the exsiccant step (leave-inprocedure) of keeping apply on hair surface by dye liquor wherein.Therefore, these dyestuffs usually not too the durable surface activating agent cleaning of hair and is easy to wash off from hair.Any temporary transient hair dyestuff can suitably be used for compositions of the present invention, and its preferred example is as follows:
Semipermanent hair dyestuff is such dyestuff, and described dyestuff general size is littler and play temporary transient hair rinse agent, but usually greater than permanent (oxidation) dyestuff.Common semipermanent dyestuff and oxidative dyestuff play similar effect, and wherein they have the potential probability of sending out in the axle that diffuses to.Yet the size of the semipermanent dyestuff conjugated oxidation dyestuff size than above-mentioned usually is little, therefore, tends to diffuse out once more from hair gradually.Simply the cleaning action to hair will promote described this process, and therefore, after to about 5-8 time of hair washing, semipermanent dye system will be washed off in large quantities.Semipermanent dye system can suitably be used for compositions of the present invention.The suitable semipermanent dyestuff that is used for the present composition is: the yellow 4.HC of the blue 2.HC of HC is red 3, and disperse violet 4 is disperseed the blue 7.HC Huang 2 of black 9.HC, disperse blue 3, disperse violet 1 and composition thereof.The example of semipermanent dyestuff is as follows:
Figure A9618011600232
Figure A9618011600241
Typical semipermanent dye system comprises the mixture of big or small dye molecule.Because the size of hair is not uniformly from root of hair to sending out the tip, therefore, micromolecule will and be sent out the diffusion of tip place at root of hair, do not send out in the tip but do not stay, and macromole can only diffuse into the two ends of hair usually.Use the combination of this dye molecule, not only at the coloration result that all helps to obtain extremely sending out tip homogeneous during the initial hair dyeing but also during washing subsequently from root of hair.
Buffer agent
The preferred pH value scope of composition for hair dying of the present invention is about 2 to about 12, more preferably from about 5 to about 10.5, and especially from about 4 to about 9.
As previously mentioned, the preferred composition for hair dying of the present invention can comprise one or more buffer agents and/or the sweller (HSAs) of pH regulator to desired value.The pH of the ingredient of final composition or final composition is regulated in available some kinds of different pH regulator agent.
By using at the processing angle azelon, the acidulant of knowing in the field of people's hair particularly, can carry out this pH regulator, described acidulant for example has: inorganic and organic acid example hydrochloric acid, tartaric acid, citric acid, phosphoric acid and carboxylic acid or sulfonic acid such as ascorbic acid, acetolactic acid, sulphuric acid, formic acid, ammonium sulfate and sodium dihydrogen phosphate/phosphoric acid, sodium hydrogen phosphate/phosphoric acid, potassium chloride/hydrochloric acid, phthalic acid potassium dihydrogen/hydrochloric acid, sodium citrate/hydrochloric acid, potassium citrate dihydrogen/hydrochloric acid, potassium citrate dihydrogen/citric acid, sodium citrate/citric acid, sodium tartrate/tartaric acid, sodium lactate/lactic acid, sodium acetate/acetic acid, sodium hydrogen phosphate/citric acid and sodium chloride/glycine/hydrochloric acid and composition thereof.
The further example of suitable buffer agent comprises: ammonium hydroxide, ethamine, di-n-propylamine, triethylamine and alkane diamine are as 1, the 3-diaminopropanes, anhydrous alkaline alkanolamine such as monoethanolamine or diethanolamine, preferred amino those amines such as the dimethylaminoethanol that is replaced fully, polyalkylenepolyamines class such as diethylenetriamines or heterocyclic amine such as morpholine, and alkali-metal hydroxide, as sodium hydroxide and potassium hydroxide, the hydroxide of alkaline-earth metal, as magnesium hydroxide and calcium hydroxide, basic amino acid such as L-alginic acid, lysine, oxidation lysine and histidine, and alkanolamine such as dimethylaminoethanol and aminoalkyl propylene glycol, and composition thereof.Be applicable to also that in addition of the present invention is to form HCO by being dissolved in the water 3 -Chemical compound (hereinafter being referred to as " forming ionic chemical compound ").The example of the ionic chemical compound of suitable formation is Na 2CO 3, NaHCO 3, K 2CO 3, (NH4) 2CO 3, NH 4HCO 3, CaCO 3And Ca (HCO 3) 2, and composition thereof.
As previously mentioned, some ealkaline buffer such as ammonium hydroxide and monoethyl amine (MEA) also can play sweller (HSA ' s).
The buffer agent that is preferably used as composition for hair dying of the present invention is an ammonium hydroxide.
As hereinafter will as described in, composition for hair dying of the present invention is made up of the final solution that comprises preformed peroxy acid oxidant and one or more oxide hair dyes, mixing before wherein each component is in application on the hair.Therefore, compositions of the present invention can comprise the many independent component of complete (kits) of hair dyeing, can comprise optionally oxidant such as hydrogen peroxide in addition.
In the oxidation and painted complete component that comprise auxiliary optional peroxide-based oxidant such as hydrogen peroxide (they can be solid or liquid), need buffer agent solution to come stable peroxide hydrogen.Because hydrogen peroxide is stable, therefore, need to use the buffer agent in this pH scope in the scope of pH2-4.Diluted acid is the buffer agent of suitable hydrogen peroxide.Phosphoric acid is to be used to cushion the hydrogenperoxide steam generator preferred reducing agents.
Bleaching catalyst
Composition for hair dying of the present invention can be chosen wantonly and comprise the transition metal that contains the catalyst that is useful on oxidant.A kind of appropriate catalyst is, comprises the catalyst system of determining the active heavy metal ion of bleach catalyst, as copper, and ferrum or manganese ion; Almost there is not or do not have the active assistant metal ion of bleach catalyst, as zinc or aluminium ion; And sequestering agent, particularly ethylenediaminetetraacetic acid with definite catalysis and assistant metal cationic stabilized constant, ethylenediamine tetraacetic (methylene phosphonic acid) and water soluble salt thereof.At US4, described these catalyst have been disclosed in 430,243.
The suitable catalyst of other class comprises: at US5, and the manganio coordination compound that discloses in 246,621 and US5,244,594.Preferred example comprises Mn in these catalyst IV 2(u-O) 3(1,4,7-trimethyl-1,4,7-7-triazacyclononane) 2-(PF 6) 2, Mn III 2(u-O) 1(u-OAc) 2(1,4,7-trimethyl-1,4,7-7-triazacyclononane) 2-(ClO 4) 2, Mn IV 4(u-O) 6(1,4, the 7-7-triazacyclononane) 4-(ClO 4) 2, Mn IIIMn IV 4(u-O) 1(u-OAc) 2(1,4,7-trimethyl-1,4,7-7-triazacyclononane) 2-(ClO 4) 3And composition thereof.Other catalyst is described in EP-A-0, in 549,272.Other is applicable to that ligand of the present invention comprises: 1,5, and 9-trimethyl-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-7-triazacyclononane and composition thereof.
The example of relevant appropriate catalyst, referring to US4,246,612 and US5,227,084.In addition also can be referring to US5,194,416, this patent has been informed monokaryon manganese (IV) coordination compound, as Mn (1,4,7-trimethyl-1,4,7-7-triazacyclononane) (OCH 3) 3-(PF 6).In addition, at US5, the another kind of catalyst that discloses in 114,606 is, manganese (III), and/or the water-soluble complexes of (IV) and a ligand, and described ligand is for having the non-carboxylate polyol of three adjacent C-OH group at least.Other example comprises: the double-core Mn with four-N-dentate and two-N-dentate ligand cooperates comprises N 4Mn III(u-O) 2Mn IVN 4) +[Bipy2Mn III(u-O) 2Mn IVBipy 2]-(ClO 4) 3
In the patent documentation below other suitable bleaching catalyst for example is described in, described document comprises: EP-A-0,408,131 (cobalt complex catalyst), EP-A-0,384,503 and EP-A-0,306,089 (catalysis of metalloporphyrin agent), US4,728,455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), US4,711,748 and EP-A-0,224,952 (on aluminosilicate, having absorbed the catalyst of manganese), US4,601,845 (being loaded with the aluminosilicate carrier of manganese and zinc or magnesium salt), US4,626,373 (manganese/ligand catalyst), US4,119,557 (iron complex catalyst), DE-A-2,054,019 (cobalt chelating catalyst), CA-A-866,191 (salt that comprise transition metal), US4,430,243 (chelating agen that have manganese cation and on-catalytic metal cation), and US4,728,455 (manganese gluconate catalyst).
The heavy metal ion sequestering agent
Composition for hair dying of the present invention preferably contains the heavy metal ion sequestering agent as the selectivity composition.In the present invention, the heavy metal ion sequestering agent means, and plays the component of sequester (chelating or removing) heavy metal ion effect.These components also can have the ability to calcium and magnesium chelating, but preferably, and they are in conjunction with heavy metal ion such as ferrum, and manganese and copper ion have selectivity.Described sequestering agent is very important for obtaining the Oxidation of controlled bleaching and provide excellent storage stability to hair dyeing product in foregoing composition for hair dying.
The consumption of heavy metal ion sequestering agent is generally about 0.005% to about 20% with composition weight meter, preferably from about 0.01% to about 10%, more preferably from about 0.05% to about 2% weight.
With regard to described purposes, various sequestering agents comprise amino phosphonates do, derive from the Dequest (RTM) of Monsanto, the nitrilo-acetate, and ethoxy ethylidene triamine etc. all is known.Being used for suitable heavy metal ion sequestering agent of the present invention comprises: organic phosphonate, and as amino alkylidenyl many (alkylene phosphonic acids salt), alkali metal ethane 1-hydroxyl diphosphate and nitrilo-trimethylene phosphonic salt.
In above-mentioned these materials, diethylenetriamines five (methylene phosphonic acid salt) preferably, ethylene diamine three (methylene phosphonic acid salt), hexamethylene diamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene-1,1-diphosphate.
Being suitable for preferred biodegradable non-phosphorus heavy metal ion sequestering agent of the present invention comprises: the amino tetraacethyl of nitrilotriacetic acid(NTA) and polyamino carboxylic acid such as ethylene, the ethylidene pentaacetic acid, ethylene diamine two succinic acid, ethylene diamine two 1,3-propanedicarboxylic acids, 2-hydroxy propylidene diamidogen two succinic acid or their salt.Especially preferred is ethylene diamine-N, N '-two succinic acid (EDDS).Referring to US4,704,233, or alkali metal, alkaline-earth metal, ammonium, or their substituted ammonium salt, or their mixture.
Being used for heavy metal ion sequestering agent that other is suitable for of the present invention is, is described in EP-A-317, and the iminodiacetic acid derivatives in 542 and EP-A-399,133 is as 2-ethoxy oxalic acid or glyceryl iminodiacetic acid.At EP-A-516, iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and the aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestering agent described in 102 also are applicable to the present invention.Also being applicable to of the present invention in addition is to be described in EP-A-509, the Beta-alanine-N in 382, N '-oxalic acid, aspartic acid-N, N '-oxalic acid, aspartic acid-N-one acetic acid and imino-diacetic succinic acid sequestering agent.
EP-A-476,257 have described the suitable sequestering agent based on amino.EP-A-510,331 have described by collagen protein, keratin or the casein derived suitable sequestering agent that obtains.EP-A-528,859 have described suitable alkyl imino oxalic acid sequestering agent.In addition, two pyridine carboxylic acids and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acids also is fit to.What also be fit in addition has: Aminoacetamide-N, N '-two succinic acid (GADS), ethylenediamine-N-N '-two 1,3-propanedicarboxylic acid (EDDG) and 2-hydroxy propylidene diamidogen-N-N '-two succinic acid (HPDDS).
Heavy metal ion sequestering agent of the present invention can use with the form of its alkali metal salt or alkali salt.
Thickening agent in addition, composition for hair dying of the present invention also can include thickening agent, its consumption is from about 0.05% to about 20%, preferably from about 0.1% to about 10%, more preferably from about 0.5% to about 5% weight.The thickening agent that is applicable to the present composition is selected from: oleic acid, spermol, oleyl alcohol, sodium chloride, 16/stearyl alcohol, stearyl alcohol, synthetic thickening agent such as Carbopol, Aculyn and Acrosyl and composition thereof.Being preferred for thickening agent of the present invention is Aculyn22 (RTM), the steareth-20 methacrylate copolymer; Aculyn44 (RTM), polyurethane resin and Acuso1830 (RTM) derive from RohmandHaas (Philadelphia, PA, acrylate copolymer USA).Be applicable to that other thickening agent of the present invention comprises: sodium alginate or Radix Acaciae senegalis, or cellulose derivative, as methylcellulose, or the sodium salt of carboxymethyl cellulose, or acrylate copolymer.
Solvent
Being used for the preferred main diluent of the present composition is water.Therefore, compositions of the present invention can comprise that one or more are as the auxilliary solvent that adds diluted material.Usually select and the miscible and harmless solvent of water skin.The solvent that is applicable to this comprises: C 1-C 20Monohydric alcohol or polyhydric alcohol and ether thereof, glycerol, wherein preferred monohydric alcohol and dihydroxylic alcohols and ether thereof.In these chemical compounds, preferably comprise the pure residue of 2-10 carbon atom.Therefore, particularly preferred chemical compound comprises ethanol, isopropyl alcohol, normal propyl alcohol, butanols, propylene glycol, ethylene glycol, single ethylether and composition thereof.
Enzyme
Can be used for the auxilliary material that adds other in the present composition is one or more enzymes.
Suitable enzyme material comprises: commercially available lipase, at, amylase, the protease of neutral and alkalescence, esterase, cellulase, pectase, Lactose enzyme and mix peroxidase in the cleaning compositions usually.Suitable enzyme is disclosed in US3, in 519,570 and 3,533,139, is incorporated herein these two pieces of patents as a reference.
Peroxidase is that peroxide is had specific hemoglobin, but can use many materials as donor.Just have similar structure and performance usually and can bring H 2O 2Some Oxidation, comprise the catalase of the peroxide of degrading at this.H 2O 2Degraded can think the oxidation of a molecule causing by other material.Described enzyme is distributed widely in the aerobic cell and may has some important effect.The coenzyme peroxidase be not hemoglobin and at least a be flavoprotein.In other receptor, other flavoprotein such as xanthine oxidase also will use H 2O 2, and to H 2O 2Be non-specific aspect, described coenzyme peroxidase and these enzymes like rather than similar to the peroxidase of routine.Suitable enzyme comprises to be used for the present composition: Cochlearia Armoracia oil peroxidase, Japanese trailing plants grape peroxidase, milk peroxidase, Mouse Liver peroxidase, linginase and haloperoxidase such as chloro peroxidase and bromoperoxidase.
Enzyme is optional composition, and its consumption is in the compositions of every gram treatment of hair of the present invention, and to be enough to provide up to 50mg, the more typically about 0.01mg extremely organized enzyme of about 10mg is as the criterion.Described other peroxidase also can mix in the compositions of the present invention, its consumption with composition weight meter from about 0.0001% to about 5%, preferably from about 0.001% to about 1%, more preferably from about 0.01% to about 1% organized enzyme.
Commercially available protease comprises: the product that NovoIndustriesA/S (Denmark) sells with following trade name: Alcalase, Savinase, Primase, Durazym and Esperase; Gist-Brocades is with trade name Maxatase, the product that Maxacal and Maxapem sell; The product that GenencorIntemational sells; And SolvayEnzymes is with the product of trade name Opticlear and Optimase sale.Protease can be mixed in the compositions of the present invention, its consumption is in compositions, from 0.0001% to 4% organized enzyme.
Amylase comprises: for example, at GB-1, α-Dian Fenmei that describe in detail, that derive from the special bacterial strain of B licheniformin (lichenifbrmis) among 269,839 (Novo).Preferred commercially available amylase comprises: for example, and the product that Gist-Brocades sells with trade name Rapidase; The product that NovoIndustriesA/S sells with trade name Termamyl and BAN.Amylase can be mixed in the compositions of the present invention, its consumption is in compositions, from 0.0001% to 2% organized enzyme.
Lipolytic enzyme can be present in the compositions of the present invention, and wherein active lipolytic enzyme amount is from 0.0001% to 2% weight of compositions, preferred from 0.001 to 1% weight, best from 0.001% to 0.5% weight.
Lipase can be, for example derives from the Humicola that produces lipase, and Thermomycessp. or Rhodopseudomonas comprise the fungus or the antibacterial of the bacterial strain of pseudomonas pseudoalcaligenes or pseudomonas fluorescens.Also can use the lipase that in the mutant of chemistry or genetic modification, obtains by these bacterial strains in the present invention.Preferred lipase derives from pseudomonas pseudoalcaligenes, and these lipases are disclosed in the European patent of mandate, among the EP-B-0218272.
Described in Europe patent application EP-A-0258068, derive from the gene of Humicola lanuginosa and in the aspergillus oryzae host, express this gene by the clone, obtained preferred in the present invention another kind of lipase, described lipase can derive from NovoIndustriesA/S (Bagsvaerd, Denmark), commodity Lipolase by name.In addition, at US4, also disclosed this lipase in 810,414 (the investing people such as Huge-Jensen in March, 1989).
Surfactant material
Compositions of the present invention also can comprise surfactant system in addition.Being included in surfactant suitable in the present composition has chain to be about the oleophylic chain of 8-22 carbon atom usually, and can be selected from: anion, cation, nonionic, both sexes, zwitterionic surfactant and composition thereof.(ⅰ) anion surfactant
Be applicable to that the anion surfactant in the present composition comprises: alkyl sulfate; the alkyl sulfate of ethoxylation; alkyl glyceryl ether sulfonate; the formoxyl taurate; fat acidyl glycine salt, N-acyl glutamate, acyl-hydroxyethyl sulfonate; alkyl sulfo succinate; the alkyl ethoxy sulfosuccinate, α-alpha-sulfonated fatty acid, their salt and/or ester; alkyl ethoxy carboxylate; alkyl phosphate salt, the alkyl phosphate salt of ethoxylation, alkyl sulfate; acyl sarcosinates and fatty acid/protein condensation substance, and composition thereof.The alkyl and/or the acyl group chain length that are used for these surfactants are C 12-C 22, preferred C 12-C 18, more preferably C 12-C 14(ⅱ) non-ionic surface active agent
Compositions of the present invention also can comprise water soluble nonionic surfactant.This class surfactant comprises: C 12-C 14The fatty acid list-and diglycollic amide, sucrose polyfatty acid esters surfactant and the polyhydroxy fatty acid amide surfactant with following general formula.
Figure A9618011600301
According to the preferred N-alkyl of top structural formula, N-alkoxyl or N-aryloxy group, polyhydroxy fatty acid amide surfactant are following materials: R wherein 8Be C 5-C 13Alkyl, preferred C 6-C 19Alkyl comprises the alkyl and the thiazolinyl of straight chain and side chain or its mixture; R 9Be generally C 1-C 8Alkyl or hydroxyalkyl are preferably methyl, or structural formula-R 1-O-R 2Group, R in the formula 1For comprising straight chain, the C of side chain and ring-type (comprising aryl) 2-C 8Alkyl is preferably C 2-C 4Alkylidene, R 2Be C 1-C 8Straight chain, side chain and cyclic hydrocarbon group comprise aryl and oxyl, are preferably C 1-C 4Alkyl, especially methyl, or phenyl.Z 2For having the polyhydroxy alkyl part of linear hydrocarbyl chain, wherein at least 2 hydroxyls (in the occasion of glyceraldehyde) or at least 3 hydroxyls (in the occasion of other reducing sugar) are connected directly on the described hydrocarbyl chain, and perhaps Z2 is the derivant of the alkoxylate (preferred ethoxylation or propoxylation) of described polyhydroxy part.Preferred Z2 is derived by the reducing sugar in the reductive amination reaction and obtains, and the best is glycosyl (glycityl) part.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, galactose, mannose and xylose, and glyceraldehyde.As raw material, can use high dense (high) glucose corn syrup, high dense fructose corn syrup and high dense maltose corn syrup, and the various sugar of listing above.These corn syrup can obtain being used for Z 2The mixture of saccharic composition.It should be understood that at this without any the meaning of getting rid of other suitable feedstock.Preferred Z 2Be selected from :-CH 2-(CHOH) n-CH 2OH ,-CH (CH 2OH)-(CHOH) N-1-CH 2H, CH 2(CHOH) 2(CHOR ') CHOH-CH 2OH, wherein, n is the integer (comprising 1 and 5) of 1-5, R ' is H or ring-type monosaccharide or polysaccharide and its oxyalkylated derivant.Be to be noted that most preferably n wherein is 4 glycosyl, particularly-CH 2(CHOH) 4-CH 2OH.
The structural formula of most preferred polyhydroxy fatty acid amide is R 8(CO) N (CH 3) CH 2(CHOH) 4CH 2OH, wherein R 8Be C 6-C 19Straight chained alkyl or alkenyl group.In the chemical compound of following formula, R 8-CO-N＜for example can be coconut monoethanolamide, stearmide, oleamide, lauramide, myristamide, decyl amide, palmitamide, Adeps Bovis seu Bubali amide etc.
Being used for suitable oily deutero-ionic surfactant pack of the present invention draws together: soft and moist dose of the deutero-water solublity of plant and animal, as be embedded with the triglyceride of polyglycol chain; The list of ethoxylation and two glyceride; The derivant of polyethoxylated lanoline and ethoxylated tallow.The general formula of the preferred oily deutero-non-ionic surface active agent (being used for of the present invention) of one class is as follows:
Figure A9618011600311
N is about 200 from about 5-in the formula, and is preferably about 100 from about 20-, more preferably about 85 from about 30-, and R comprises and on average contains about 20 carbon atoms of about 5-in the formula, preferably from the aliphatic group of about 7-18 carbon atom.
The oil ﹠ fat of the ethoxylation that described this class is suitable comprises the polyethyleneglycol derivative of following material, and described material is: glyceryl cocoate, caproin, caprylin, tallow acid glyceride, tripalmitin, tristerin, glyceryl laurate ester, olein, castor oil acid glyceride, and by triglyceride such as Petiolus Trachycarpi oil, the glycerin fatty ester that almond oil and Semen Maydis oil are derived and obtained, preferably Adeps Bovis seu Bubali glyceride and glyceryl cocoate.
The glycerin fatty ester surfactant of suitable polyethoxylated comprises the polyethyleneglycol derivative of following material, and described material is: glyceryl cocoate, caproin, caprylin, tallow acid glyceride, tripalmitin, tristerin, glyceryl laurate ester, olein, castor oil acid glyceride, and by triglyceride such as night primrose oil, Petiolus Trachycarpi oil, the glycerin fatty ester that castor oil hydrogenated, almond oil and Semen Maydis oil are derived and obtained.
Be preferred for of the present inventionly be: every mole of surfactant on average contain about 5 to about 50 ethylidene oxygen part, polyethylene glycol groups polyethoxylated C 9-C 15Fatty alcohol nonionic surfactant.
Be applicable to suitable polyethylene glycol groups polyethoxylated C of the present invention 9-C 15Aliphatic alcohol comprises: C 9-C 11Pareth-3, C 9-C 11Pareth-4, C 9-C 11Pareth-5, C 9-C 11Pareth-6, C 9-C 11Pareth-7, C 9-C 11Pareth-8, C 11-C 15Pareth-3, C 11-C 15Pareth-4, C 11-C 15Pareth-5, C 11-C 15Pareth-6, C 11-C 15Pareth-7, C 11-C 15Pareth-8, C 11-C 15Pareth-9, C 11-C 15Pareth-10, C 11-C 15Pareth-11, C 11-C15Pareth-12, C 11-C 15Paceth-13 and C 11-C 15Pareth-14.The hydrogenant Oleum Ricini of PEG40 derives from BASF, and commodity are called Cremophor (RTM).PEG7 glyceryl cocoate and PEG20 glyceryl laurate ester derive from Henkel, and trade name is respectively Cetiol (RTM) HE and Lamacit (RTM) GML20.C 9-C 11Pareth-8 derives from ShellLtd, and commodity are called Dobanol (RTM) 9l-8.Be used for the polyglycol ether that particularly preferably is spermol of the present invention, as Ceteareth25, described material can derive from BASF, and commodity are called CremaphorA25.
Also be applicable in addition and of the present inventionly be: the non-ionic surface active agent and the derivant thereof that obtain by the composite plant fat of the fruit extraction of SheaTree (ButyrospermumKarkiiKotschy).Similarly, Fructus Mangifera Indicae, the ethoxylated derivative of Cortex cocois radicis and illipe also can be used for compositions of the present invention.Although these materials are classified into non-ionic surface active agent, it should be understood that certain proportion wherein can give over to the vegetable oil or the fat of non-ethoxylatedization.
Other suitable oily deutero-ionic surfactant pack is drawn together the ethoxylated derivative of following oil, and described oil comprises: almond oil, Oleum Arachidis hypogaeae semen, Testa oryzae oil, Semen Tritici aestivi germ oil, Semen Lini oil, simmondsia oil, Apricot kernel oil, walnut oil, palm kernel oil, pistachio nut oil, sesame seed oil, Oleum Brassicae campestris, cade oil, Semen Maydis oil, Semen Persicae oil, seed of Papaver somniferum L. powder, Oleum Pini, Oleum Ricini, Oleum Glycines, American Avocado Tree oil, safflower oil, Oleum Cocois, hazelnut oil, olive oil, Oleum Vitis viniferae, and sunflower seed oil.(ⅲ) amphoteric surfactant
Be applicable to that amphoteric surfactant of the present invention comprises:
(a) imidazoline surfactant of structural formula (XII) R in the formula 1Be C 7-C 22Alkyl or alkenyl, R 2Be hydrogen or CH 2Z, each Z represents CO independently 2M or CH 2CO 2M, M are H, alkali metal, alkaline-earth metal, ammonium or alkanol ammonium; And/or the ammonium derivative of structural formula (X III)
Figure A9618011600322
R in the formula 1, R 2As above define with Z;
(b) the aminoalkanol hydrochlorate of structural formula (XI V)
R 1NH(CH 2) nCO 2M
The imino-diacetic alkanol hydrochlorate of structural formula (X V)
R 1N[(CH 2) mCO 2M] 2
The imino group multichain alkyl salt of structural formula (X VI)
R 1[N(CH 2) p] q[CH 2CO 2M] 2
|
CH 2CO 2M
N in the formula, m, p and q are the number of 1-4, R 1Be selected from above-mentioned group respectively with M;
(c) their mixture.
Suitable (a) class amphoteric surfactant is with trade name Miranol and Empigen product sold, and is interpreted as comprising the complex mixture of these materials.Traditionally, Miranol has been described as and has general formula (XII), but CTFA cosmetic ingredients dictionary (CosmeticIngredientDictionary) third edition has disclosed non-ring structure (X III), and the 4th edition has disclosed wherein R 2Be the isomer O-connection rather than the another kind of structure that N-connects.In fact, may there be the complex mixture of ring-type and non-annularity material, and, for the purpose of improving, provided this two kinds of definition.Yet being preferred for of the present invention is non-ring.
The example of suitable (a) class amphoteric surfactant comprises: structural formula (XII) and/or X III chemical compound, wherein R 1Be C 8H 17(especially iso-octyl), C 9H 19And C 11H 23Alkyl.Especially preferred is R wherein 1Be C 9H 19, Z is CO 2M, R 2Chemical compound for H; R wherein 1Be C 11H 23, Z is CO 2M, R 2Be CH 2CO 2The chemical compound of M; R wherein 1Be C 11H 23, Z is CO 2M, R 2Chemical compound for H.
In the CTFA nomenclature, be applicable to that material of the present invention comprises: Cortex cocois radicis both sexes carboxyl (cocoampho-carboxy) propionate, Cortex cocois radicis both sexes carboxyl propanoic acid, especially Cortex cocois radicis both sexes acetate and Cortex cocois radicis both sexes diacetin (also being referred to as Cortex cocois radicis both sexes carboxyl glycinate in addition).Concrete commercially available prod comprises: with trade name Ampholak7TX (the carboxymethyl Adeps Bovis seu Bubali gather propylamine sodium), Empigen CDL60 and CDR60 (Albright﹠amp; Wilson), Miranol H2M Conc.Miranol C2M Conc.N.P., Miranol C2M Conc.O.P., Miranol C2M SF, Miranol CM Special (Rh ne-Poulenc); Alkateric 2CIB (Alkaril Chemicals); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Mona-teric CSH-32 (MonaIndustries); RewotericAM-2C (Rewo Chemical Group); Product with Schercotic MS-2 (Scher Chemicals) sale.The further example that is applicable to amphoteric surfactant of the present invention comprises: Octoxynol-1 (RTM), polyoxyethylene (1) octyl phenyl ether; Nonoxynol-4 (RTM), polyoxyethylene (4) nonylplenyl ether and Nonoxyol-9, polyoxyethylene (9) nonylplenyl ether.
It should be understood that the commercially available amphoteric surfactant of many these classes with electroneutral complex form production and selling, for example, has the surfactant of hydroxide counter ion counterionsl gegenions or anion sulfate acid root or sulfonate radical, especially Sulfated C 8-C 18Alcohol, C 8-C 18The alcohol of ethoxylation, or C 8-C 18The acylglycerol esters.Be pointed out that also that in addition in the present invention, the concentration of amphoteric surfactant and weight ratio are benchmark with the surfactant of fit form not, the counter ion counterionsl gegenions of any anion surfactant are all thought the part of anion surfactant constituent content.
Preferably the example of (b) class amphoteric surfactant comprises: the poly-carboxymethyl amine of N-alkyl polytrimethylene that BerolNobel sells with trade name Ampholak X07 and Ampholak 7CX, and salt, especially the salt of tri ethanol ammonium salt and N-lauryl Beta-alanine and N-lauryl-imino group-dipropionic acid.These materials are products that Henkel sells with trade name Mirataine with trade name Deriphat and Rh  ne-Poulenc.(ⅳ) zwitterionic surfactant
Be applicable to that the auxiliary water soluble amphoteric ion surfactant that adds the present composition comprises: formula R 5R 6R 7N +(CH 2) nCO 2The amido betaines of the alkyl betaine of M and following structural formula (X V):
Figure A9618011600341
R in the formula 5Be C 11-C 22Alkyl or alkenyl, R 6And R 7Be C independently 1-C 3Alkyl, M are H, respectively the do for oneself number of 1-4 of alkali metal, alkaline-earth metal, ammonium or alkanol ammonium, n, m.Preferred betanin comprises: Cortex cocois radicis acylamino-propyl-dimethyl carboxymethyl betaine, amino propyl-dimethyl carboxymethyl betaine of lauroyl and Tego betanin (RTM).
Be applicable to that the auxiliary water solublity sulfobetaines surfactant that adds in the present composition comprises the alkyl sulfobetaines of following structural formula (X VI): R in the formula 1Be C 7-C 22Alkyl or alkenyl, R 2And R 3Be C independently 1-C 3Alkyl, M are H, respectively the do for oneself number of 1-4 of alkali metal, alkaline-earth metal, ammonium or alkanol ammonium, n, m.Being preferred for sulfobetaines of the present invention comprises: Cortex cocois radicis acylamino-propyl hydroxy sulfobetaines.
Be applicable to that the auxiliary water-soluble amine oxides surfactant that adds in the present composition comprises alkyl amine oxide R 5R 6R 7The acylamino-amine oxide of NO and following structural formula (X VII):
Figure A9618011600352
R in the formula 5Be C 11-C 22Alkyl or alkenyl, R 6And R 7Be C independently 1-C 3Alkyl, M are H, alkali metal, and alkaline-earth metal, ammonium or alkanol ammonium, m are the number of 1-4.Preferred amine oxide comprises: Cortex cocois radicis acylamino-propyl group amine oxide, lauryl dimethyl amine oxide and myristyl dimethyl amine oxide.
Optional material
In addition, many optional material can be added in the compositions of the present invention, its consumption be respectively composition weight about 0.001% to about 5%, preferably from about 0.01% to about 3%, more preferably from about 0.05% to about 2% weight.Described these materials comprise: protein and polypeptide and derivant thereof; But the antiseptic of water solublity or solubilization as, DMDM glycolylurea, Germall115, the methyl of hydroxy benzoic acid, ethyl, propyl group and butyl ester, EDTA, Euxyl (RTM) K400, natural antiseptic such as benzyl alcohol, potassium sorbate and bisabolol; Sodium benzoate and 2-phenyl phenol; Antioxidant such as sodium sulfite, hydroquinone, sodium sulfite, sodium pyrosulfite and first gland glycolic, sodium dithionite, erythrobicacid and other sulfur alcohol; Dyestuff remover such as oxalic acid, sulfated castor oil, salicylic acid and sodium thiosulfate; H2O2 stabilizing agent such as tin compound, as sodium stannate, stannic hydroxide and stannous octoate, monoacetylaniline, phenacetin silica sol such as magnesium silicate, oxyquinoline sulfate, sodium phosphate, and tetrasodium pyrophosphate; And right-hydroxybenzoate; Wetting agent such as hyaluronic acid, chitin and starch-grafted sodium polyacrylate such as Sanwet (RTM) IM-100, IM-1500 and IM-2500, these materials derive from CelaneseSuperabsorbentMaterials, Portsmith, VA, USA also is described in US-A-4, in 076,663; Solvent; Antibacterial such as Oxeco (phenoxy group isopropyl alcohol); Low temperature phase modifier such as ammonium ion source (NH for example 4Cl); Viscosity-control additive such as magnesium sulfate and other electrolyte; Quaternary ammonium compound such as distearyl-, dilauryl-, dihydro Adeps Bovis seu Bubali base-, alkyl dimethyl ammonium chloride, two cetyl diethyl ethyl sulfuric acid ammoniums, two Adeps Bovis seu Bubali base dimethyl methyl ammonium sulfate, two soybean-based (disoya) alkyl dimethyl ammonium chloride and dicoco dimethyl ammonium chloride; Hair conditioner such as siloxanes, higher alcohol, cationic polymer etc.; Enzyme stabilizers such as water-soluble calcium source or borate family; Stain; TiO 2And TiO 2The Muscovitum of coating; Spice and spice stabilizing agent; And zeolite such as ValfourBV400 and derivant thereof, Ca 2+/ Mg 2+Sequestering agent such as polycarboxylate, aminopolycarboxylic salt, polyphosphonate, amino polyphosphonate etc., water softener such as sodium citrate.Water also can be present in the compositions of the present invention in addition, and its consumption is from about 2% to about 99.9%, preferably from about 5% to about 99%, more preferably at least from about 10% to about 95%, especially from about 15% to about 90% weight.
Embodiment represents the present invention below by indefiniteness.Except as otherwise noted, in these embodiments, all concentration all are as the criterion with 100% active group, all percentage ratios all by weight, abbreviation has following definition: oxidant 1 peracetic acid oxidant 2 is crossed lactic acid oxidative dyestuffs 1 p-phenylenediamine (PPD) oxidative dyestuff 2 para-aminophenol oxidative dyestuffs 3 m-aminophenol oxidative dyestuffs 4 2-amino-non-oxidizable dyestuff 1 alkalescence of 3-pyridone red 76 non-oxidizable dyestuff 2 bismarck browns 16 chelating agen ethylenediaminetetraacetic acid enzyme Cochlearia Armoracia oil peroxidase surfactants 1 Cetereth-25 surfactant 2 AMPHORAM C30 surfactants 3 sodium lauryl sulfate thickening agents 1 spermol thickening agent 2 stearyl alcohol antioxidant sodium sulfite.
Embodiment I-VI
Following is to send out compositions with the taste of composition for hair dying form, and these compositionss are typical examples of the present invention.In these embodiments, water is the solvent of using always, yet water can be partly, about 50% substituted by liquid such as lower alcohol at the most, described lower alcohol for example, ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol, carbiphene, propylene glycol, 1, ammediol, ethanol, isopropyl alcohol, glycerol, butyl cellosolve, ethoxydiglycol, hexanediol, polyglyceryl-2-oleyl ether and composition thereof.
Batching ????Ⅰ ????Ⅱ ????Ⅲ ????Ⅳ ????Ⅴ ????Ⅵ
Oxidant 1 ????0.5 ????1 ????1.5 ????- ?????- ????-
Oxidant 2 ?????- ?????- ????- ????0.5 ????1 ????1.5
Oxidative dyestuff 1 ???0.24 ?????- ????0.3 ????0.4 ????0.2 ????0.3
Oxidative dyestuff 2 ???0.09 ???0.05 ???0.12 ???0.09 ???0.06 ???0.06
Oxidative dyestuff 3 ???0.06 ???0.05 ???0.03 ???0.06 ???0.06 ????-
Oxidative dyestuff 4 ???0.06 ???0.05 ???0.05 ???0.06 ???0.03 ????-
Non-oxidizable dyestuff 1 ????- ???0.25 ????- ????- ???0.12 ????-
Non-oxidizable dyestuff 2 ????- ???0.35 ????- ????- ????0.2 ????-
Enzyme ????- ????- ????0.5 ?????- ????- ???-
Surfactant 1 ????1.5 ????1 ????3 ????- ????1 ????1
Surfactant 2 ?????- ????2 ????1 ????2 ????0.5 ????-
Surfactant 3 ?????- ????1 ????0.5 ????1 ????- ????2
Chelating agen ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
Thickening agent 1 ????2.3 ????2.3 ????2.3 ????2.3 ????2.3 ????2.3
Thickening agent 2 ????2.3 ????2.3 ????2.3 ????2.3 ????2.3 ????2.3
Antioxidant ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
Water Aequum
The available oxygen computing method
As previously mentioned, the oxidation efficiency of composition for hair dying of the present invention can its available oxygen amount (also being referred to as active oxygen AO) be described.
Per-compound contain one of them oxygen atom be active peroxide bond (O-O-).This activity can be measured by the Oxidation of iodo-iodine under the acid condition, or measures by the ceric sulfate titration.AO content (representing with percentage ratio usually) is: the atomic weight of active oxygen is divided by the molecular weight of chemical compound.Computing formula by the theoretical available oxygen of any specific compound determination is as follows:
AO%=100 * (active oxygen quantity) * (molal weight of 16/ chemical compound)
Peracetic acid of the present invention, the available oxygen theoretical value of preformed peroxy acid and conventional hydrogen peroxide oxidant is respectively 21 and 47.
Manufacture method
Many preformed organic peroxide acids that are used for composition for hair dying of the present invention are unsettled, are unsettled especially in aqueous solution.Therefore, in order to obtain the desirable Oxidation of hair, these solution of use are crucial in short time after preparation.In addition, because oxidant must contact a period of time with hair and not drip and may make eyes or chafing from hair, therefore, it also is crucial preformed organic peroxide acid being be easy to the state for preparing and make things convenient for user to use.
For achieving the above object, the form that compositions of the present invention can complete (each component of independent packaging) provides keeping stability, and user mixed before being used on the hair immediately.A component in the packaging kit comprises the preformed peroxy acid oxidation component of independent packaging.Another complete component can comprise the mixture of the preformed peroxy acid oxidant of independent packaging and hair dye or comprise two individual packages of preformed peroxy acid oxidation promoter and hair dye.In one embodiment of the invention, oxidation component comprises preformed organic peroxide acid, and its consumption is as the criterion from about 0.05% to about 5% weight with the ultimate density that is used for chemical compound on the hair, and/or foregoing additive; Second component comprises the mixture of suitable hair dye.Said composition can be mixed before being used on the hair immediately by user, or used on hair individually.The example of described complete component is as follows:
I. assembling comprises the complete component of hair dyeing of unitary package, comprising: (1) one bottle comprises preformed organic peroxy acid oxidant (50ml), (2) one bottles (50ml) comprises one or more oxidative coloration of hair agent and other additive (50ml), described additive comprises: surfactant, antioxidant, thickening agent etc.Described complete component can also comprise (3) the one bottles of 50ml hydrogen peroxide of optional components (H2O2 of 10% weight) as other.Oxide hair dye is applied on the hair so that begin the hair dyeing process, and, simultaneously or with after the hair dyeing mixture process immediately or at the most after 20 minutes, with preformed peroxy acid solution (with if present, other additive such as peroxide) be applied on the hair.
Using method
Compositions described in the present invention can be used to have hair dyed.Depend on required hair dyeing degree, composition for hair dying of the present invention can be applied on the hair and keep 1-60 minute.The preferred time was at 5-30 minute.
Product of the present invention provides excellent hair dyeing and service efficiency, is included in the damage that reduces under the low pH value hair.

Claims (16)

1. composition for hair dying comprises:
(a) preformed organic peroxy acid oxidant; With
(b) one or more oxide hair dyes.
2. according to the compositions of claim 1; wherein preformed organic peroxide acid is selected from: alkyl or benzoyl phenolsulfonate that ammonium or alkylammonium replace; the caprolactam of N-acyl groupization and the tetra-acetylated glucose benzoyl peroxide of a benzoyl and composition thereof.
3. according to the compositions of claim 1 or 2, wherein preformed organic peroxy acid oxidant is selected from: peracetic acid, mistake lactic acid and composition thereof.
4. according to the compositions of one of claim 1-3, wherein, the consumption of preformed peroxy acid oxidant in the present composition be from about 0.01% to about 5%, preferably from about 0.1% to about 4%, more preferably from about 0.2% to about 3% weight.
5. according to each compositions of claim 1-4, wherein, the consumption of each oxide hair dye is from about 0.001% to about 6%, preferably from about 0.01% to about 2% weight.
6. according to each compositions of claim 1-5, wherein, the total amount of oxide hair dye is from about 0.01% to about 15%, preferably from about 0.1% to about 10%, more preferably from about 0.5% to about 5% weight.
7. according to each compositions of claim 1-6, also comprise one or more buffer agents and/or hair extender in addition.
8. according to the compositions of claim 7, wherein, buffer agent is selected from: ammonium hydroxide, ethamine, di-n-propylamine, triethylamine and alkane diamine be as 1, the 3-diaminopropanes, anhydrous alkaline alkanolamine such as monoethanolamine or diethanolamine, preferred amino those amines such as the dimethylaminoethanol that is replaced fully, polyalkylenepolyamines class such as diethylenetriamines or heterocyclic amine such as morpholine, and alkali-metal hydroxide such as sodium hydroxide and potassium hydroxide, the hydroxide of alkaline-earth metal such as magnesium hydroxide and calcium hydroxide, basic amino acid such as L-alginic acid, lysine, oxidation lysine and histidine, alkanolamine such as dimethylaminoethanol and aminoalkyl propylene glycol, Na 2CO 3, NaHCO 3, K2CO 3, (NH 4) 2CO 3, NH 4HCO 3, CaCO 3And Ca (HCO 3) 2, and composition thereof.
9. according to the compositions of one of claim 1-8, also comprise one or more surfactants in addition.
10. according to the compositions of claim 9, wherein surfactant is selected from: anion, nonionic, cation, amphion, amphoteric surfactant and composition thereof.
11., also comprise enzyme in addition according to the compositions of one of claim 1-10.
12. the compositions according to one of claim 1-11 is used for human or animal's hair is carried out painted purposes.
13. one kind is carried out painted method to human or animal's hair, comprising: will comprise the preformed organic peroxide acid that is suitable for the hair dyeing component that contacts with human body skin and be applied on the hair.
14. according to claim 13 human or animal's hair is carried out painted method, wherein, composition for hair dying comprises:
(a) from about 0.01% preformed organic peroxy acid oxidant to about 5% weight;
(b) one or more oxide hair dyes, the consumption of every kind of hair dye from about 0.001% to about 6% weight; With
(c) from about 15% inert diluent to about 99.9% weight;
Wherein the pH value of composition for hair dying from about 6 to about 12.
15. hair dyeing suit, comprise an individual packages, comprising having: (1) one bottle of 50ml comprises preformed organic peroxy acid oxidant and comprises one or more oxidative coloration of hair agent and other additive such as surfactant, antioxidant, thickening agent etc. with (2) one bottles of 50ml.
16. according to the hair dyeing suit of claim 15, be used for hair is carried out painted purposes, wherein, preformed peroxy acid and oxide hair dye are mixed and be applied on the hair.
CN 96180116 1995-12-29 1996-12-17 Hair coloring compositions Pending CN1209052A (en)

Applications Claiming Priority (2)

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GB9526711.8 1995-12-29
GBGB9526711.8A GB9526711D0 (en) 1995-12-29 1995-12-29 Hair colouring composition

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MX9805303A (en) 1998-10-31
JPH11509235A (en) 1999-08-17
GB9526711D0 (en) 1996-02-28
EP0918503A1 (en) 1999-06-02
BR9612322A (en) 1999-07-13
EP0918503A4 (en) 2000-07-12

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