CN1907253A - Composition comprising amino heterocyclic compound for hair dyeing and dyeing method - Google Patents
Composition comprising amino heterocyclic compound for hair dyeing and dyeing method Download PDFInfo
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- CN1907253A CN1907253A CNA2006100303156A CN200610030315A CN1907253A CN 1907253 A CN1907253 A CN 1907253A CN A2006100303156 A CNA2006100303156 A CN A2006100303156A CN 200610030315 A CN200610030315 A CN 200610030315A CN 1907253 A CN1907253 A CN 1907253A
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- amino
- tetrahydroquinoline
- indoline
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- 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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- 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
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
- A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
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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
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
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Abstract
The invention discloses a component with amino heterocyclic compound for the hair, which comprises one or more of amino tetrahydrochysene quinoline from general formula (I), additional salt of amino tetrahydrochysene quinoline and acid from general formula (I), dihydro-indole with amino from general formula (II), additional salt with dihydro-indole of amino from general formula (II).
Description
Technical field
The present invention relates to a kind of compositions that contains amino heterocyclic compound that is used for dyeing keratinous fibres, and the colouring method that adopts said composition.
Background technology
People have known that so-called Permanent Hair Dyeing Agent is to adopt enough little material to be diffused in the epidermis of hair, and these materials are not dyestuff, just form dyestuff behind the hair but enter in dyeing course.
A key component of this series products is called the oxidation dye developer, they are Ammonia or phenol derivatives such as p-phenylenediamine (PPD), para-aminophenol, and these materials can not dye, but can be oxidized to intermediate fast, the latter reacts with other chemical compounds again, generates the macromole dyestuff.So since these macromole dyestuffs be after entering hair, form be difficult to flush away with shampoo, can reach permanent on certain meaning, so claim Permanent Hair Dyeing Agent, again owing to form the process of dyestuff and be actually owing to oxidation reaction generates colored compound, so be called oxidative hair dyes again.
We know, can change the resulting tone of oxidation dye developer by combining with dye developer or modifier, and these colour formers or modifier specifically are selected from diamidogen between aromatic series, a bit amino phenol, resorcinol and some heterocyclic compound.
We also know, should satisfy certain needs by the resulting so-called permanent color of these oxidation dyes, therefore it should be no problem on toxicology figure, and should be able to obtain different tones with needed intensity, and under various extraneous factors (as illumination, adverse weather, washing, permanent hair-waving, perspiration, friction etc.), all show good outward appearance.Simultaneously, these dyestuffs also should be able to be covered the hair of white, also as far as possible little selectivity will be arranged at last, Here it is, and said wanting on keratin fiber can access as far as possible little colour-difference, and is different (being dyeing speck) at the sensitization degree of sending out between the tip and the root of hair in fact.
Be applied to the oxidation dye of keratin fiber permanent stain, normally be designed to some and have substituent monocycle or dinuclear aromatics such as amino, hydroxyl.Monocycle or dicyclo but not more polycyclic design are because usually only the molecular diameter of the aromatic compound of monocycle or dicyclo is just enough little, and have only the chemical compound of enough little molecular diameter just to have an opportunity to spread and the top layer of angle of penetration azelon.On the aromatic rings except that the amino that replaces, hydroxyl isoreactivity group, should leave one or more unsubstituted positions, in when, in order to the inside at keratin fiber oxidative coupling taking place, form enough coloring matters of big Pi-conjugated systems, its molecular diameter of the coloring matter of this moment becomes big, thereby be difficult to " flee from " from keratin fiber inside, can reach the purpose of " permanent ".
We find, in some documents and patent before, the report of the chemical compound of some multi-ring (surpassing two rings) as oxidation dye arranged, in the dying operation of reality, still may use the method for forcing angle of flare azelon top layer, as stronger basic dyeing environment, help the surfactant of infiltration etc., keratin fiber is successfully dyeed.French Patent (FRP) Fr2844272---" New tricyclic indole or tetrahydroquinoline derivatives useful as developers inoxidation dye compositions for dyeing keratinic fibers, especially human hair "---proposed with " tricyclic compound " that contain indole or tetrahydroquinoline as the report that is the oxidation dye constituent.Its general structure is:
The inventor notices, existing and commonly used oxidation dye, and its result that oxidative coupling takes place often obtains dark tone, as red, brown and even nearly black.This is because in the presence of enough oxidants, and the active group on the aromatic rings is as amino, hydroxyl, can and aromatic rings on complicated oxidative coupling do not take place between the position of substitution, form the Pi-conjugated systems of " too big ", cause occurring the tone of dark color.The amount of controlled oxidation agent is difficult in dyeing course, and the existence of airborne still more oxygen and water usually is enough to make most oxidation dye generation oxidative couplings.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of compositions that contains amino-heterocyclic compounds and colouring method that is used for coloring hairs, to overcome the defective that prior art exists.
The present invention is in order to obtain stable light tone, as blueness, green coloration result, need then to find that some can finally form the oxidation dye of the Pi-conjugated systems of " less " by oxidative coupling, for this reason, the inventor has proposed the view to such dye molecule design, as follows: as no matter to be phenyl ring or heteroaromatic ring, except essential amino, outside the hydroxyl isoreactivity group, not the position of substitution on ring is by more nonactive group, after methyl substituted, the space that oxidative coupling can take place on the ring just is compressed, and this can cause forming littler Pi-conjugated systems, thereby obtains stable light tone.Certainly, the nonactive group of adjacent position can saturated rings replace, and reaches the spatial purpose that " sealing " part can react equally.
The inventor finds after deliberation, use some amino tetrahydroquinoline that contains as following defined general formula (I), and as following defined general formula (II) contain amino indoline, not only be suitable as the oxidation dye parent, and can also obtain the colouring compositions of the very pure blue to green tone of a kind of color, and be difficult for fading, have good stability.At last, it is synthetic easily that these chemical compounds are proved to be, and these find to constitute basis of the present invention.
The compositions that contains amino-heterocyclic compounds that is used for coloring hairs of the present invention, it includes at least in being suitable for painted medium and contains amino heterocyclic compound, one or more in the addition salts that contains amino indoline and acid that contains amino indoline, general formula (II) of the said addition salts that contains the amino tetrahydroquinoline of amino tetrahydroquinoline that amino heterocyclic compound is selected from general formula (I), general formula (I) and acid, general formula (II);
Said hair refers to human body or horn azelon;
In formula (I) and formula (II): R
1But be positioned on the position of substitution of nitrogen-atoms, R
2Be positioned on the saturated rings on the commutable position, R
3On position and the phenyl ring on the commutable position except that amino, while or independently represent hydrogen, amino, substituted-amino, C
1-C
18Alkyl, alkoxyl, halogen, ester group, carboxyl or nitro, R
2And R
3Can be expressed as 1 to 3 identical or different substituted radical respectively.
In general, said addition salts with acid is selected from hydrochlorate, hydrobromate, sulfate, tartrate, lactate or acetate especially;
The amino tetrahydroquinoline that contains of preferred formula (I) is:
The amino tetrahydroquinoline of N-methyl-7-,
The amino tetrahydroquinoline of N-benzyl-7-,
7-amino-3-methylol-1-(2 '-methoxyphenyl) tetrahydroquinoline,
7-amino-3-methylol-1-(3 '-methoxyphenyl) tetrahydroquinoline,
7-amino-3-methylol-1-(4 '-methoxyphenyl) tetrahydroquinoline,
The amino tetrahydroquinoline of N-ethyl-7-,
The amino tetrahydroquinoline of N-ethoxy-7-,
The amino tetrahydroquinoline of N-isobutyl group-7-,
7-amino-3-methyl isophthalic acid-(2 '-methoxyphenyl) tetrahydroquinoline,
7-amino-3-methyl isophthalic acid-(3 '-methoxyphenyl) tetrahydroquinoline,
7-amino-3-methyl isophthalic acid-(4 '-methoxyphenyl) tetrahydroquinoline,
The amino tetrahydroquinoline of the N-tert-butyl group-7-,
1, the amino tetrahydroquinoline of 3-dimethyl-7-,
7-amino-3-methylol-1-isobutyl group tetrahydroquinoline,
7-amino-3-dimethylaminomethyl-1-methyl tetrahydroquinoline,
7-amino-3-dimethylaminomethyl-1-ethyl tetrahydroquinoline,
7-amino-3-dimethylaminomethyl-1-tert-butyl group tetrahydroquinoline,
7-amino-3-dimethylaminomethyl-1-isopropyl tetrahydroquinoline,
7-amino-3-methyl isophthalic acid-ethoxy tetrahydroquinoline,
7-amino-3-methylol-1-tert-butyl group tetrahydroquinoline,
7-amino-3-methyl isophthalic acid-tert-butyl group tetrahydroquinoline,
The amino tetrahydroquinoline of N-isopropyl-7-,
7-amino-3-methyl isophthalic acid-isopropyl tetrahydroquinoline,
7-amino-3-methylol-1-isopropyl tetrahydroquinoline,
7-amino-3-the tert-butyl group-1-methyl tetrahydroquinoline,
7-amino-3-the tert-butyl group-1-isopropyl tetrahydroquinoline,
7-amino-3-ethyl-1-isopropyl tetrahydroquinoline,
7-amino-3-ethyl-1-methyl tetrahydroquinoline,
7-amino-3-ethylamino methyl isophthalic acid-methyl tetrahydroquinoline,
7-amino-3-ethylamino methyl isophthalic acid-ethyl tetrahydroquinoline,
7-amino-3-ethylamino methyl isophthalic acid-tert-butyl group tetrahydroquinoline,
7-amino-3-ethylamino methyl isophthalic acid-isopropyl tetrahydroquinoline,
7-amino-3-isopropyl-1-ethoxy tetrahydroquinoline,
The amino 3-tert-butyl group of 7--1-ethyl tetrahydroquinoline,
7-amino-3-methylamino methyl isophthalic acid-methyl tetrahydroquinoline,
7-amino-3-methylamino methyl isophthalic acid-ethyl tetrahydroquinoline,
7-amino-3-methylamino methyl isophthalic acid-tert-butyl group tetrahydroquinoline,
7-amino-3-methylamino methyl isophthalic acid-isopropyl tetrahydroquinoline,
7-amino-3-methoxyl group-1-methyl tetrahydroquinoline,
7-amino-3-ethyoxyl-1-ethyl tetrahydroquinoline and
Above-claimed cpd and sour addition salts;
In above-mentioned amino tetrahydroquinoline, more particularly preferred:
The amino tetrahydroquinoline of N-methyl-7-,
The amino tetrahydroquinoline of N-benzyl-7-,
The amino tetrahydroquinoline of N-ethyl-7-,
The amino tetrahydroquinoline of N-ethoxy-7-,
The amino tetrahydroquinoline of N-isobutyl group-7-,
The amino tetrahydroquinoline of the N-tert-butyl group-7-,
1, the amino tetrahydroquinoline of 3-dimethyl-7-,
7-amino-3-methylol-1-isobutyl group tetrahydroquinoline,
7-amino-3-methyl isophthalic acid-ethoxy tetrahydroquinoline,
7-amino-3-methylol-1-tert-butyl group tetrahydroquinoline,
7-amino-3-methyl isophthalic acid-tert-butyl group tetrahydroquinoline,
The amino tetrahydroquinoline of N-isopropyl-7-,
7-amino-3-methyl isophthalic acid-isopropyl tetrahydroquinoline,
7-amino-3-methylol-1-isopropyl tetrahydroquinoline,
7-amino-3-the tert-butyl group-1-methyl tetrahydroquinoline,
7-amino-3-the tert-butyl group-1-isopropyl tetrahydroquinoline,
7-amino-3-ethyl-1-isopropyl tetrahydroquinoline,
7-amino-3-ethyl-1-methyl tetrahydroquinoline,
7-amino-3-isopropyl-1-ethoxy tetrahydroquinoline,
The amino 3-tert-butyl group of 7--1-ethyl tetrahydroquinoline,
7-amino-3-methoxyl group-1-methyl tetrahydroquinoline,
7-amino-3-ethyoxyl-1-ethyl tetrahydroquinoline,
With they addition salts with acid;
The amino indoline that contains of preferred formula (II) is:
The amino indoline of N-methyl-6-,
The amino indoline of N-benzyl-6-,
The amino indoline of N-ethyl-6-,
6-amino-3-methylol-1-isobutyl group indoline,
6-amino-3-methyl isophthalic acid-ethoxy indoline,
6-amino-3-methylol-1-(2 '-methoxyphenyl) indoline,
6-amino-3-methylol-1-(3 '-methoxyphenyl) indoline,
6-amino-3-methylol-1-(4 '-methoxyphenyl) indoline,
6-amino-3-methylol-1-tert-butyl group indoline,
The amino indoline of N-ethoxy-6-,
The amino indoline of N-isobutyl group-6-,
The amino indoline of the N-tert-butyl group-6-,
1, the amino indoline of 3-dimethyl-6-,
6-amino-3-dimethylaminomethyl-1-methyl indoline,
6-amino-3-dimethylaminomethyl-1-ethyl indoline,
6-amino-3-dimethylaminomethyl-1-tert-butyl group indoline,
6-amino-3-dimethylaminomethyl-1-isopropyl indoline,
6-amino-3-the tert-butyl group-1-isopropyl indoline,
6-amino-3-ethyl-1-isopropyl indoline,
The amino 3-ethylamino of 6--1-methyl indoline,
The amino 3-ethylamino of 6--1-ethyl indoline,
The amino 3-ethylamino of 6--1-tert-butyl group indoline,
The amino 3-ethylamino of 6--1-isopropyl indoline,
6-amino-3-ethyl-1-methyl indoline,
The amino 3-tert-butyl group of 6--1-ethyl indoline,
6-amino-3-methoxyl group-1-methyl indoline,
6-amino-3-methyl isophthalic acid-tert-butyl group indoline,
The amino indoline of N-isopropyl-6-,
6-amino-3-methylamino-1-methyl indoline,
6-amino-3-methylamino-1-ethyl indoline,
6-amino-3-methylamino-1-propyl group indoline,
6-amino-3-methylamino-1-tert-butyl group indoline,
6-amino-3-methylamino-1-isopropyl indoline,
6-amino-3-methyl isophthalic acid-isopropyl indoline,
6-amino-3-methylol-1-isopropyl indoline,
6-amino-3-the tert-butyl group-1-methyl indoline,
6-amino-3-isopropyl-1-ethoxy indoline,
6-amino-3-ethyoxyl-1-ethyl indoline,
With they addition salts with acid
In these amino indoline, more particularly preferred:
The amino indoline of N-methyl-6-,
The amino indoline of N-benzyl-6-,
The amino indoline of N-ethyl-6-,
6-amino-3-methylol-1-isobutyl group indoline,
6-amino-3-methyl isophthalic acid-ethoxy indoline,
6-amino-3-methylol-1-tert-butyl group indoline,
The amino indoline of N-ethoxy-6-,
The amino indoline of N-isobutyl group-6-,
The amino indoline of the N-tert-butyl group-6-,
1, the amino indoline of 3-dimethyl-6-,
6-amino-3-the tert-butyl group-1-isopropyl indoline,
6-amino-3-ethyl-1-isopropyl indoline,
6-amino-3-ethyl-1-methyl indoline,
The amino 3-tert-butyl group of 6--1-ethyl indoline,
6-amino-3-methoxyl group-1-methyl indoline,
6-amino-3-methyl isophthalic acid-tert-butyl group indoline,
The amino indoline of N-isopropyl-6-,
6-amino-3-methyl isophthalic acid-isopropyl indoline,
6-amino-3-methylol-1-isopropyl indoline,
6-amino-3-the tert-butyl group-1-methyl indoline,
6-amino-3-isopropyl-1-ethoxy indoline,
6-amino-3-ethyoxyl-1-ethyl indoline,
With they addition salts with acid
Formula as previously described (I) a kind of or several contains amino tetrahydroquinoline or formula (II), and a kind of or several to contain amino indoline consumption be 0.0005%～12% of said composition total weight, more preferably for this reason about 0.005%～6% of weight.
Be used for painted suitable medium (being carrier) and generally comprise the water or the mixture of water and at least a organic solvent, this solvent is used for being dissolved in the not enough chemical compound of dissolubility in the water.As organic solvent, the lower alcohol that can enumerate C1-C4 is such as the ether of ethanol and isopropyl alcohol, glycerol, two pure and mild glycol, such as the single ether and the methyl ether of propylene glycol, butoxy ethanol, propylene glycol monomethyl ether, diethylene glycol, and aromatic alcohol is such as benzyl alcohol or phenyl phenol, similar compounds and composition thereof.
The consumption of solvent is 1%～95% of a said total composition, more preferably 5%～30% of this weight.
Between the general about 3-12 of the pH value of said compositions, preferably between 5-11.The acidulant or the basifier that can often use when dyeing keratinous fibres are adjusted to required numerical value with it.
In acidulant, can enumerate mineral acid or organic acid as an example, such as acidic materials such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acid such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acid.
In basifier, can enumerate ammonia, alkali carbonate, alkanolamine as an example, such as monoethanolamine, diethanolamine, triethanolamine and their derivant, alkaline matters such as sodium hydroxide or potassium hydroxide.
Except dyestuff as defined above, said compositions can also contain at least a additional oxidation dye developer, a kind of colour former or at least a direct staining agent or be one or more the mixture in the various auxiliary agents that use in the hair colouring compositions;
The oxidation dye developer is selected from the traditional oxidation dye developer that uses in oxidation dyeing method, wherein can enumerate p-phenylenediamine (PPD) especially, contain amino tetrahydroquinoline and contain the amino different heterocyclic compound of indoline to toluenediamine, para-aminophenol, o-aminophenol with used in the present invention;
In the p-phenylenediamine (PPD) classification, can enumerate p-phenylenediamine (PPD) as an example especially, to toluenediamine, 2,6-dimethyl-p-phenylenediamine, 2-beta-hydroxyethyl p-phenylenediamine (PPD), 2-n-pro-pyl p-phenylenediamine (PPD), 2-isopropyl p-phenylenediamine (PPD), N-(β-hydroxypropyl)-p-phenylenediamine (PPD), N, two (the beta-hydroxyethyl)-p-phenylenediamine (PPD) of N-, 4-amino-N-('beta '-methoxy ethyl)-aniline, at French Patent (FRP) FR2, the addition salts of the p-phenylenediamine (PPD) compounds of narrating in 630,438 the application and they and they and acid.
In the para-aminophenol classification, can enumerate the amino 2-methoxy phenol of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methyl phenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-amino methyl phenol, 4-and they and sour addition salts as an example especially.
In the o-aminophenol classification, adducible especially as an example is the addition salts of 2-amino-phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetyl group-2-amino-phenol and they and acid.
In the heterocycle classification, can enumerate the addition salts of pyridine derivate, pyrimidine derivatives, pyrazole derivatives and they and acid as an example especially.
When using these additional oxidation dye developers, their content is preferably 0.0005%～12% of said composition total weight, especially preferably accounts for 0.005%～6% of gross weight.
Said colour former or direct staining agent, be to make gloss abundant in order to change color harmony, colour former can be selected from the colour former that tradition is used in oxidation dyeing method, wherein can enumerate m-diaminobenzene. especially, meta-aminophenol, between diphenol and heterocycle colour former, such as indole derivatives, pyridine derivate and pyrazolone, and they and sour addition salts, these colour formers can be selected from 2-methyl-5-amino-phenol especially, 5-N-(beta-hydroxyethyl)-amino-2-methyl phenol, the 2-amino-phenol, 1, the 3-dihydroxy benzenes, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1, the 3-dihydroxy benzenes, 2,4-diaminostilbene-(beta-hydroxyethyl)-benzene, 2-amino-4-(beta-hydroxyethyl amino)-1-methoxybenzene, 1, the 3-diaminobenzene, 1,3-two (2, the 4-diamino phenoxy)-propane, sesamol, the 1-naphthols, the 6-oxyindole, the 4-oxyindole, 4-hydroxy-n-methylindole, 2,6-dihydroxy-4-picoline, 1-H-3-methylpyrazole-5-ketone, 1-phenyl-3-methylpyrazole-5-ketone and they and sour addition salts;
Said colour former or direct staining agent consumption are preferably 0.0001% to 10% of said composition total weight, and more preferably 0.005% of gross weight to 5%;
Said various auxiliary agent, such as anion surfactant, cationic surfactant, non-ionic surface active agent, amphoteric surfactant or their mixture, anionic polymer, cationic polymer, non-ionic polymers, amphiphilic polymers, zwitterion polymer or their mixture, inorganic or organic thickening agent, antioxidant, penetrating agent, sequestering agent, spice, buffer agent, dispersant, conditioner is such as polymethyl siloxane, film former, antiseptic, opacifier, the consumption of auxiliary agent are preferably 0.0001% to 20% of colouring compositions gross weight;
Certainly, one of skill in the art must select these additional compounds that can add arbitrarily in such a way, compositions promptly of the present invention inherent excellent properties not by or do not changed substantially by the additive of these imaginations.
Compositions of the present invention can be different shape, such as solid-state, liquid, paste, gel or variously be suitable for carrying out keratin fiber, particularly is suitable for painted other shapes of human hair.
Another target of the present invention is that the defined compositions in front is carried out process for dyeing keratin fibers, particularly the colouring method of Ren Lei keratin fiber such as hair.
In this way, said compositions is coated on this fiber, in air or nationality helps oxidant or is aided with the slaine that is used for catalytic oxidation, in air or nationality help oxidant, keep the time that is enough to produce required color.
First kind of form according to implementing example of the present invention can not add oxidant, only just contacts with airborne oxygen and can implement adding lustre to of fiber.In this case, can add oxidation catalyst arbitrarily in the compositions, with the process of accelerated oxidation.
Said slaine, such as, the salt of manganese, cobalt, copper, ferrum, silver and zinc.
Such chemical compound can be such as being two manganese acetate tetrahydrates, manganous chloride and hydrate thereof, carbonic acid dihydro manganese, acetopyruvic acid manganese, three manganese acetates and hydrate thereof, manganic chloride, zinc dichloride, two zinc acetate dihydrates, zinc carbonate, dinitric acid zinc, zinc sulfate, ferrous chloride, iron sulfate, two iron acetates, two cobaltous acetate tetrahydrates, cobalt carbonate, cobalt dichloride, dinitric acid cobalt, cobaltous sulfate heptahydrate, chlorinated ketone, silver nitrate ammonia complex etc., and manganese salt is particularly preferred.
When using these slaines, its consumption is generally the 0.001-4% of composition total weight, and preferably 0.005% of composition total weight to 2%.
According to implementing second kind of form of the present invention, be coated on the fiber as the defined compositions in front at least a, nationality helps the oxidant that adds simultaneously when using compositions, show color under acid, neutral or alkaline pH value, this oxidant may reside among the applied oxidising composition or adds subsequently.
According to this second kind of form of implementing colouring method of the present invention, when being preferably in use, to mix with the compositions that in suitable dyeing medium, contains at least a oxidant as above-mentioned compositions, the content of this oxidant will be enough to produce color, and the weight of preferred oxidant accounts for 0.1% to 15% of composition total weight.
Then the mixture that obtains is coated on the keratin fiber, through about 3-50 minute, preferably approximately 5-30 minute, with post rinse, with shampoo washing, rinsing and drying up once more.
The oxidant that exists in the said oxidising composition is selected from the oxidant that tradition is used in the method for dyeing keratinous fibres, wherein can enumerate hydrogen peroxide, urea peroxide, alkali metal bromate, supersalt such as perborate and persulfate, preferred especially hydrogen peroxide.
Contain the oxidising composition of oxidant as defined above, after its pH value will make it and colouring compositions mixes, the pH value that is coated on the compositions on the keratin fiber that obtains is preferably approximately between the 7-12, more be selected between the 5-11, it is that nationality helps as front defined tradition is used in process for dyeing keratin fibers acidulant or basifier that pH value is adjusted to desirable value.
Oxidizing agent composition can also also have the various auxiliary agents that often use as defined above in hair colouring compositions as defined above.
The physical mixed method that preparation of compositions method of the present invention is a kind of routine is mixed each component, promptly obtains.
Another target of the present invention is a diverse hair care system that has the dyeing installation of a plurality of chambers or box or have a plurality of chambers, wherein in first chamber defined compositions is housed, and in second chamber oxidizing agent composition as defined above is housed.These equipment can be equipped with the device that can be coated with required mixture on hair.
The preparation method that contains amino indoline of the amino tetrahydroquinoline of said general formula (I) and general formula (II), at document:
Feer；Koenigs；Chem.Ber.；18；1885；2391.
V；Braun；Grabowski；Rawicz；Chem.Ber.；46；1913；3182.
Preobrashenskaja；Dokl.Akad.Nauk?SSSR；118；1958；302，304；Dokl.Chem.(Engl.Transl.)；118-123<1958>49，51.
Preobrashenskaja；Zh.Obshch，Khim.；29；1959；317，322；engl.Ausg.S.322，326
In be disclosed disclosure, the relevant personnel if needed, can be prepared with reference to the document, it is Reducing agent that this method adopts metal, hydrogen or the conduct of other reductants, to by reduction reaction nitroreduction be become amino with chemical compound (I) chemical compound that contain nitro corresponding with (II), the present invention repeats no more.
Evidence, compositions of the present invention not only is suitable as the oxidation dye parent, and can also obtain the colouring compositions of the very pure blue to green tone of a kind of color, and is difficult for fading, and has good stability.
The specific embodiment
Each following embodiment is used for illustrating the present invention, and it is not constituted any restriction.
Preparation embodiment
Embodiment 1: the amino tetrahydroquinoline hydrochlorate of synthetic N-methyl-7-
Earlier 22.4g (0.4mol) iron powder and 2ml concentrated hydrochloric acid (36%) are added reaction bulb, stir and also add 240ml ethanol and 80ml water, be warming up to backflow then, add 19.2g (0.1mol) N-methyl-7-nitro tetrahydroquinoline after cold slightly in batches.Behind the reaction 2.5hr., stopped reaction, sucking filtration while hot, and with the ferrum mud in hot ethanol rinsing bottle 2-3 time, concentrated filtrate, the filtrate after concentrated is used CH
2Cl
2Extract 3 times, vacuum rotary steam is removed CH
2Cl
2The back adds 20ml ethanol, has solid to separate out behind the feeding HCl gas, obtains 15.37g light red solid after the drying, yield 77.4%.
1H-NMR(CDCl
3)：δ1.98(q，2H)，2.77(t，2H)，2.87(s，3H)，3.22(t，2H)，6.50(t，1H)，6.65(d，1H)，6.96(d，1H)。
Embodiment 2: the amino tetrahydroquinoline hydrochlorate of synthetic N-ethyl-7-
Earlier 22.4g (0.4mol) reduced iron powder and 2ml concentrated hydrochloric acid (36%) are but gone into reaction bulb, stir and also add 240ml ethanol and 80ml water, be warming up to backflow then, add 20.6g (0.1mol) N-ethyl-7-nitro tetrahydroquinoline after cold slightly in batches.Behind the reaction 2.5hr., stopped reaction, sucking filtration while hot, and with the ferrum mud in hot ethanol rinsing bottle 2-3 time, concentrated filtrate, the filtrate after concentrated is used CH
2Cl
2Extract 3 times, vacuum rotary steam is removed CH
2Cl
2The back adds 20ml ethanol, has solid to separate out behind the feeding HCl gas, and dry back obtains the 17.68g white solid with recrystallizing methanol, yield 83.2%.
1H-NMR(DMSO)：δ1.06(t，3H)，1.84(q，2H)，2.65(t，2H)，3.21(t，2H)，3.31(q，2H)，6.45(d，1H)，6.57(s，1H)，6.93(d，1H)，10.31(s，2H)。
Embodiment 3: the amino tetrahydroquinoline hydrochlorate of synthetic N-isobutyl group-7-
Earlier 22.4g (0.4mol) reduced iron powder and 2ml concentrated hydrochloric acid (36%) are added reaction bulb, stir and also add 240ml ethanol and 80ml water, be warming up to backflow then, add 23.4g (0.1mol) N-isobutyl group-7-nitro tetrahydroquinoline after cold slightly in batches.Behind the reaction 2.5hr., stopped reaction, sucking filtration while hot, and with the ferrum mud in hot ethanol rinsing bottle 2-3 time, concentrated filtrate, the filtrate after concentrated is used CH
2Cl
2Extract 3 times, vacuum rotary steam is removed CH
2Cl
2The back adds 20ml ethanol, has solid to separate out behind the feeding HCl gas, and dry back obtains the 17.5g white solid with recrystallizing methanol, yield 85.8%.
1H-NMR(CDCl
3)：δ0.91(d，6H)，1.91(q，2H)，2.06(sex，1H)，2.75(t，2H)，2.98(d，2H)，3.27(t，2H)，6.48(t，1H)，6.55(d，1H)，6.97(d，1H)。
Embodiment 4: the amino tetrahydroquinoline hydrochlorate of synthetic N-ethoxy-7-
Earlier 22.4g (0.4mol) reduced iron powder and 2ml concentrated hydrochloric acid (36%) are added reaction bulb, stir and adding 240ml ethanol and 80ml water, add 22.2g (0.1mol) N-ethoxy-7-nitro tetrahydroquinoline, be warming up to backflow then.Behind the reaction 3.5hr., stopped reaction, sucking filtration while hot, and with the ferrum mud in hot ethanol rinsing bottle 2-3 time, concentrated filtrate, the filtrate after concentrated is used CH
2Cl
2Extract 3 times, vacuum rotary steam is removed CH
2Cl
2The back adds 20ml ethanol, has solid to separate out behind the feeding HCl gas, obtains the 15.5g white solid after the drying, yield 80.7%.
1H-NMR(D
2O)：δ2.19(m，2H)，2.98(t，2H)，3.64(m，4H)，3.87(t，2H)，7.34(d，2H)，7.47(t，1H)。
Embodiment 5: the amino indoline hydrochlorate of synthetic N-methyl-6-
Earlier 22.4g (0.4mol) reduced iron powder and 2ml concentrated hydrochloric acid (36%) are added reaction bulb, stir and also add 240ml ethanol and 80ml water, add 17.8g (0.1mol) N-methyl-6-nitro indoline after cold slightly in batches, be warming up to backflow then.Behind the reaction 2.5hr., stopped reaction, sucking filtration while hot, and with the ferrum mud in hot ethanol rinsing bottle 2-3 time, concentrated filtrate, the filtrate after concentrated is used CH
2Cl
2Extract 3 times, vacuum rotary steam is removed CH
2Cl
2The back adds 20ml ethanol, has solid to separate out behind the feeding HCl gas, obtains the 10.5g pale solid after the drying, yield 70.9%.
1H-NMR(D
2O)：δ3.21(s，3H)，3.317(t，2H)，3.95(t，2H)，7.42(d，1H)，7.48(s，1H)，7.576(t，1H)。
Embodiment 6: the amino indoline hydrochlorate of synthetic N-ethyl-6-
Earlier 22.4g (0.4mol) reduced iron powder and 2ml concentrated hydrochloric acid (36%) are added reaction bulb, stir and adding 240ml ethanol and 80ml water, add 19.2g (0.1mol) N-ethyl-6-nitro indoline, be warming up to backflow then.Behind the reaction 2.5hr., stopped reaction, sucking filtration while hot, and with the ferrum mud in hot ethanol rinsing bottle 2-3 time, concentrated filtrate, the filtrate after concentrated is used CH
2Cl
2Extract 3 times, vacuum rotary steam is removed CH
2Cl
2The back adds 20ml ethanol, has solid to separate out behind the feeding HCl gas, obtains the 9.5g pale solid after the drying, yield 58.6%.
1H-NMR(D
2O)：δ1.15(t，3H)，2.96(t，2H)，3.19(m，2H)，3.47(t，2H)，6.647(s，1H)，6.71(d，1H)，7.17(t，1H)。The application implementation row, wherein, concentration is weight concentration as not being specifically noted.
Embodiment 7: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution, weight) 3.00g
P-phenylenediamine (PPD) (PPD) 0.10g
The amino tetrahydroquinoline hydrochlorate of N-methyl-7-0.005g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5.Each above-mentioned component is mixed, promptly obtain.
During use, be earlier that 6% aqueous hydrogen peroxide solution (B component) mixes with above-mentioned dye composite of 10g (component A) and 10g weight concentration.Then, the compositions (pH 10) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains the blue colour tone in pure Prussia.
Embodiment 8: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
P-phenylenediamine (PPD) (PPD) 0.10g
The amino tetrahydroquinoline hydrochlorate of N-methyl-7-6.0g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, be earlier that 6% aqueous hydrogen peroxide solution (B component) mixes with above-mentioned dye composite of 10g (component A) and 10g weight concentration.Then, the compositions (pH 9) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains the blue colour tone in pure Prussia.
Embodiment 9: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
P-phenylenediamine (PPD) (PPD) 0.10g
The amino tetrahydroquinoline hydrochlorate of N-methyl-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, be earlier that 6% aqueous hydrogen peroxide solution (B component) mixes with above-mentioned dye composite of 10g (component A) and 10g weight concentration.Then, the compositions (pH 9.5) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains the blue colour tone in pure Prussia.
Embodiment 10: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
To toluenediamine sulfate (TDS) 0.50g
The amino tetrahydroquinoline hydrochlorate of N-methyl-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 8.5) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains the blue colour tone in pure Prussia.
Embodiment 11: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
Para-aminophenol (PAP) 0.50g
The amino tetrahydroquinoline hydrochlorate of N-methyl-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 8.5) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains pure aubergine colour tone.
Embodiment 12: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
P-phenylenediamine (PPD) (PPD) 0.10g
The amino tetrahydroquinoline hydrochlorate of N-ethyl-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 10) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains the blue colour tone in pure Prussia.
Embodiment 13: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
To toluenediamine sulfate (TDS) 0.50g
The amino tetrahydroquinoline hydrochlorate of N-ethyl-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 8) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains the blue colour tone in pure Prussia.
Embodiment 14: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
Para-aminophenol (PAP) 0.50g
The amino tetrahydroquinoline hydrochlorate of N-ethyl-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 9) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains pure aubergine colour tone.
Embodiment 15: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
P-phenylenediamine (PPD) (PPD) 0.10g
The amino tetrahydroquinoline hydrochlorate of N-isobutyl group-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 9) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains the blue colour tone in pure Prussia.
Embodiment 16: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
To toluenediamine sulfate (TDS) 0.50g
The amino tetrahydroquinoline hydrochlorate of N-isobutyl group-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 9.5) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains the blue colour tone in pure Prussia.
Embodiment 17: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
Para-aminophenol (PAP) 0.50g
The amino tetrahydroquinoline hydrochlorate of N-isobutyl group-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 8.5) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains pure aubergine colour tone.
Embodiment 18: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
P-phenylenediamine (PPD) (PPD) 0.10g
The amino tetrahydroquinoline hydrochlorate of N-ethoxy-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 8.5) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains the blue colour tone in pure Prussia.
Embodiment 19: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
To toluenediamine sulfate (TDS) 0.50g
The amino tetrahydroquinoline hydrochlorate of N-ethoxy-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 10) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains the blue colour tone in pure Prussia.
Embodiment 20: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
Para-aminophenol (PAP) 0.50g
The amino tetrahydroquinoline hydrochlorate of N-ethoxy-7-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 9) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains pure aubergine colour tone.
Embodiment 21: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
P-phenylenediamine (PPD) (PPD) 0.10g
The amino indoline hydrochlorate of N-methyl-6-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 8) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains pure blue dyeing tone.
Embodiment 22: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
To toluenediamine sulfate (TDS) 0.50g
The amino indoline hydrochlorate of N-methyl-6-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 9) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains pure blue dyeing tone.
Embodiment 23: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
Para-aminophenol (PAP) 0.50g
The amino indoline hydrochlorate of N-methyl-6-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 8) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains pure aubergine colour tone.
Embodiment 24: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
P-phenylenediamine (PPD) (PPD) 0.10g
The amino indoline hydrochlorate of N-ethyl-6-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 8.5) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains pure blue dyeing tone.
Embodiment 25: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
To toluenediamine sulfate (TDS) 0.50g
The amino indoline hydrochlorate of N-ethyl-6-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 8) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains pure blue dyeing tone.
Embodiment 26: prepare compositions of the present invention as follows
The hair oxidation dye, alkalescence
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
Para-aminophenol (PAP) 0.50g
The amino indoline hydrochlorate of N-ethyl-6-0.20g
Demineralized water is to 100g
The pH value of this hair dyestuff is 10.5, and each above-mentioned component is mixed, and promptly obtains.
During use, earlier the above-mentioned dye composite of 10g (component A) is mixed with the aqueous hydrogen peroxide solution (B component) of 10g 6%.Then, the compositions (pH 8) that obtains is applied on the hair, said composition was kept on hair 30 minutes.This hair is through the circulating water rinsing, and shampoo washing after drying obtains pure aubergine colour tone comparative example 1～6
According to routine dyestuff under the following formulation:
The comparative example 1
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
P-phenylenediamine (PPD) (PPD) 0.10g
2-amino-4-hydroxyethylamino methyl phenyl ethers anisole (AHEAS) 0.20g
Demineralized water is to 100g
The comparative example 2
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
To diaminotoluene sulphate (TDS) 0.50g
2-amino-4-hydroxyethylamino methyl phenyl ethers anisole (AHEAS) 0.20g
Demineralized water is to 100g
The comparative example 3
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
Para-aminophenol (PAP) 0.50g
2-amino-4-hydroxyethylamino methyl phenyl ethers anisole (AHEAS) 0.20g
Demineralized water is to 100g
The comparative example 4
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
P-phenylenediamine (PPD) (PPD) 0.10g
2, and 4-diamino phenoxy ethanol (2,4-DAPE) 0.20g
Demineralized water is to 100g
The comparative example 5
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
Para-aminotoluene sulfate (TDS) 0.50g
2, and 4-diamino phenoxy ethanol (2,4-DAPE) 0.20g
Demineralized water is to 100g
The comparative example 6
16/octadecanol 17.00g
Sodium lauryl tri(oxyethyl) sulfate (28%) 3.50g
Ascorbic acid 0.60g
Sodium sulfite 0.80g
Ammonia (25% aqueous solution) 3.00g
Para-aminophenol (PAP) 0.50g
2, and 4-diamino phenoxy ethanol (2,4-DAPE) 0.20g
Demineralized water is to 100g
With the hair after embodiment 9-20 and the 21-26 dyeing, sodium lauryl tri(oxyethyl) sulfate solution (K-12) with 0.5% in 50 ℃ under agitation soak put half an hour after, rinsing dries up (this process be equivalent to daily shampoo wash protect 2 months), colored hair contrast with not rinsing, found that the keratin fiber (embodiment 9-20 and 21-26) that uses after the dye composite that contains the present invention's (amino tetrahydroquinoline and amino indoline) dyes does not fade substantially, has good stable, and the keratin fiber (comparative example 1～6) that does not contain after the dye composite dyeing of the present invention fades obviously less stable.
Claims (10)
1. compositions that contains amino-heterocyclic compounds that is used for coloring hairs, it is characterized in that, it includes in being suitable for painted medium at least contains amino heterocyclic compound, one or more in the addition salts that contains amino indoline and acid that contains amino indoline, general formula (II) of the said addition salts that contains the amino tetrahydroquinoline of amino tetrahydroquinoline that amino heterocyclic compound is selected from general formula (I), general formula (I) and acid, general formula (II);
In formula (I) and formula (II): R
1But be positioned on the position of substitution of nitrogen-atoms, R
2Be positioned on the saturated rings on the commutable position, R
3On position and the phenyl ring on the commutable position except that amino, while or independently represent hydrogen, amino, substituted-amino, C
1-C
18Alkyl, alkoxyl, halogen, ester group, carboxyl or nitro, R
2And R
3Can be expressed as 1 to 3 identical or different substituted radical respectively.
2. the amino heterocyclic compound compositions that contains that is used for dyeing keratinous fibres according to claim 1 is characterized in that said addition salts with acid is selected from hydrochlorate, hydrobromate, sulfate, tartrate, lactate or acetate.
3. the amino heterocyclic compound compositions that contains that is used for dyeing keratinous fibres according to claim 1 is characterized in that, the amino tetrahydroquinoline that contains of formula (I) is:
The amino tetrahydroquinoline of N-methyl-7-,
The amino tetrahydroquinoline of N-benzyl-7-,
7-amino-3-methylol-1-(2 '-methoxyphenyl) tetrahydroquinoline,
7-amino-3-methylol-1-(3 '-methoxyphenyl) tetrahydroquinoline,
7-amino-3-methylol-1-(4 '-methoxyphenyl) tetrahydroquinoline,
The amino tetrahydroquinoline of N-ethyl-7-,
The amino tetrahydroquinoline of N-ethoxy-7-,
The amino tetrahydroquinoline of N-isobutyl group-7-,
7-amino-3-methyl isophthalic acid-(2 '-methoxyphenyl) tetrahydroquinoline,
7-amino-3-methyl isophthalic acid-(3 '-methoxyphenyl) tetrahydroquinoline,
7-amino-3-methyl isophthalic acid-(4 '-methoxyphenyl) tetrahydroquinoline,
The amino tetrahydroquinoline of the N-tert-butyl group-7-,
1, the amino tetrahydroquinoline of 3-dimethyl-7-,
7-amino-3-methylol-1-isobutyl group tetrahydroquinoline,
7-amino-3-dimethylaminomethyl-1-methyl tetrahydroquinoline,
7-amino-3-dimethylaminomethyl-1-ethyl tetrahydroquinoline,
7-amino-3-dimethylaminomethyl-1-tert-butyl group tetrahydroquinoline,
7-amino-3-dimethylaminomethyl-1-isopropyl tetrahydroquinoline,
7-amino-3-methyl isophthalic acid-ethoxy tetrahydroquinoline,
7-amino-3-methylol-1-tert-butyl group tetrahydroquinoline,
7-amino-3-methyl isophthalic acid-tert-butyl group tetrahydroquinoline,
The amino tetrahydroquinoline of N-isopropyl-7-,
7-amino-3-methyl isophthalic acid-isopropyl tetrahydroquinoline,
7-amino-3-methylol-1-isopropyl tetrahydroquinoline,
7-amino-3-the tert-butyl group-1-methyl tetrahydroquinoline,
7-amino-3-the tert-butyl group-1-isopropyl tetrahydroquinoline,
7-amino-3-ethyl-1-isopropyl tetrahydroquinoline,
7-amino-3-ethyl-1-methyl tetrahydroquinoline,
7-amino-3-ethylamino methyl isophthalic acid-methyl tetrahydroquinoline,
7-amino-3-ethylamino methyl isophthalic acid-ethyl tetrahydroquinoline,
7-amino-3-ethylamino methyl isophthalic acid-tert-butyl group tetrahydroquinoline,
7-amino-3-ethylamino methyl isophthalic acid-isopropyl tetrahydroquinoline,
7-amino-3-isopropyl-1-ethoxy tetrahydroquinoline,
The amino 3-tert-butyl group of 7--1-ethyl tetrahydroquinoline,
7-amino-3-methylamino methyl isophthalic acid-methyl tetrahydroquinoline,
7-amino-3-methylamino methyl isophthalic acid-ethyl tetrahydroquinoline,
7-amino-3-methylamino methyl isophthalic acid-tert-butyl group tetrahydroquinoline,
7-amino-3-methylamino methyl isophthalic acid-isopropyl tetrahydroquinoline,
7-amino-3-methoxyl group-1-methyl tetrahydroquinoline,
7-amino-3-ethyoxyl-1-ethyl tetrahydroquinoline and
Above-claimed cpd and sour addition salts;
The amino indoline that contains of formula (II) is:
The amino indoline of N-methyl-6-,
The amino indoline of N-benzyl-6-,
The amino indoline of N-ethyl-6-,
6-amino-3-methylol-1-isobutyl group indoline,
6-amino-3-methyl isophthalic acid-ethoxy indoline,
6-amino-3-methylol-1-(2 '-methoxyphenyl) indoline,
6-amino-3-methylol-1-(3 '-methoxyphenyl) indoline,
6-amino-3-methylol-1-(4 '-methoxyphenyl) indoline,
6-amino-3-methylol-1-tert-butyl group indoline,
The amino indoline of N-ethoxy-6-,
The amino indoline of N-isobutyl group-6-,
The amino indoline of the N-tert-butyl group-6-,
1, the amino indoline of 3-dimethyl-6-,
6-amino-3-dimethylaminomethyl-1-methyl indoline,
6-amino-3-dimethylaminomethyl-1-ethyl indoline,
6-amino-3-dimethylaminomethyl-1-tert-butyl group indoline,
6-amino-3-dimethylaminomethyl-1-isopropyl indoline,
6-amino-3-the tert-butyl group-1-isopropyl indoline,
6-amino-3-ethyl-1-isopropyl indoline,
The amino 3-ethylamino of 6--1-methyl indoline,
The amino 3-ethylamino of 6--1-ethyl indoline,
The amino 3-ethylamino of 6--1-tert-butyl group indoline,
The amino 3-ethylamino of 6--1-isopropyl indoline,
6-amino-3-ethyl-1-methyl indoline,
The amino 3-tert-butyl group of 6--1-ethyl indoline,
6-amino-3-methoxyl group-1-methyl indoline,
6-amino-3-methyl isophthalic acid-tert-butyl group indoline,
The amino indoline of N-isopropyl-6-,
6-amino-3-methylamino-1-methyl indoline,
6-amino-3-methylamino-1-ethyl indoline,
6-amino-3-methylamino-1-propyl group indoline,
6-amino-3-methylamino-1-tert-butyl group indoline,
6-amino-3-methylamino-1-isopropyl indoline,
6-amino-3-methyl isophthalic acid-isopropyl indoline,
6-amino-3-methylol-1-isopropyl indoline,
6-amino-3-the tert-butyl group-1-methyl indoline,
6-amino-3-isopropyl-1-ethoxy indoline,
6-amino-3-ethyoxyl-1-ethyl indoline,
With they addition salts with acid.
4. the amino heterocyclic compound compositions that contains that is used for dyeing keratinous fibres according to claim 1 is characterized in that the said heterocyclic compound consumption that contains amino is 0.0005%～12% of a composition total weight.
5. the amino heterocyclic compound compositions that contains that is used for dyeing keratinous fibres according to claim 1, it is characterized in that, saidly be suitable for the mixture that painted medium comprises water or water and at least a organic solvent, the consumption of solvent is 1%～95% of a total composition.
6. the amino heterocyclic compound compositions that contains that is used for dyeing keratinous fibres according to claim 1 is characterized in that the pH value of compositions is 3-12.
7. the amino heterocyclic compound compositions that contains that is used for dyeing keratinous fibres according to claim 1, it is characterized in that said compositions also contains at least a additional oxidation dye developer, a kind of colour former or at least a direct staining agent or is one or more the mixture in the various auxiliary agents that use in the hair colouring compositions;
Said oxidation dye developer is selected from the traditional oxidation dye developer that uses in oxidation dyeing method, content is 0.0005%～12% of composition total weight;
Said colour former or at least a direct staining agent are selected from colour former or the direct staining agent that tradition is used in oxidation dyeing method, and its consumption is 0.0001% to 10% of a colouring compositions gross weight;
Said is that the various auxiliary dosages that use in the hair colouring compositions are 0.0001% to 20 of colouring compositions gross weight.
8. adopt each described amino heterocyclic compound compositions that contains that is used for dyeing keratinous fibres of claim 1～7 to carry out process for dyeing keratin fibers, it is characterized in that, said colouring compositions is coated on this fiber, in air or nationality helps oxidant or is aided with the slaine that is used for catalytic oxidation, the time that maintenance is enough to produce required color, said oxidant is selected from oxidant or the oxidizing agent composition that tradition is used in the method for dyeing keratinous fibres, and weight metal accounts for the 0.001-4% of colouring compositions gross weight.
9. method according to claim 8 is characterized in that, the weight of oxidant accounts for 0.1% to 15% of composition total weight.
10. " box " that has the equipment of a plurality of chambers or have a plurality of chambers wherein is equipped with any defined colouring compositions among the claim 1-7 in first chamber, in second Room oxidizing agent composition is housed.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100303156A CN1907253A (en) | 2006-08-23 | 2006-08-23 | Composition comprising amino heterocyclic compound for hair dyeing and dyeing method |
| PCT/CN2007/002505 WO2008025240A1 (en) | 2006-08-23 | 2007-08-20 | Composition comprising amino heterocyclic compound for hair dyeing and dyeing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100303156A CN1907253A (en) | 2006-08-23 | 2006-08-23 | Composition comprising amino heterocyclic compound for hair dyeing and dyeing method |
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| Publication Number | Publication Date |
|---|---|
| CN1907253A true CN1907253A (en) | 2007-02-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006100303156A Pending CN1907253A (en) | 2006-08-23 | 2006-08-23 | Composition comprising amino heterocyclic compound for hair dyeing and dyeing method |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1907253A (en) |
| WO (1) | WO2008025240A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103987694A (en) * | 2011-12-16 | 2014-08-13 | 莱雅公司 | Coupler with 7-amino-1,2,3,4-tetrahydroquinoline structure, dyeing composition comprising same, processes and uses |
| CN108495846A (en) * | 2015-12-23 | 2018-09-04 | 欧莱雅 | Substituted dihydro-isoquinoline salt is used to handle purposes, composition and the implementation of keratin material |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2984318B1 (en) | 2011-12-16 | 2014-06-27 | Oreal | CATIONIC AMINO-1,2,3,4-TETRAHYDROQUINOLINE 7 STRUCTURE COUPLER, TINCTORIAL COMPOSITION COMPRISING THE SAME, METHODS AND USES |
| FR3046169B1 (en) | 2015-12-23 | 2022-05-20 | Oreal | USE OF DIHYDROISOQUINOLINIUM SALTS FOR THE TREATMENT OF KERATINIC MATERIALS, COMPOSITIONS AND METHODS OF IMPLEMENTATION |
| FR3046170B1 (en) | 2015-12-23 | 2020-02-07 | L'oreal | USE OF DUAL DIHYDROISOQUINOLINIUM DERIVATIVES FOR THE TREATMENT OF KERATINIC MATERIALS, COMPOSITIONS AND METHODS OF USE |
| FR3072286B1 (en) * | 2017-10-13 | 2022-08-12 | Oreal | PARTICULAR 7-AMINO-1,2,3,4-TETRAHYDROQUINOLEINS, METHOD AND COMPOSITION |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2714955A1 (en) * | 1977-04-02 | 1978-10-12 | Henkel Kgaa | Oxidn. hair dye compsn. - contains quinoline or tetra:hydro-quinoline deriv. coupler and tetra:amino-pyrimidine developer |
| HUP0102869A2 (en) * | 1998-06-23 | 2002-02-28 | Henkel Kommanditgesellschaft Auf Aktien | Colorant for colouring keratin fibres |
| DE10103657A1 (en) * | 2001-01-27 | 2002-08-01 | Henkel Kgaa | New coupler component for oxidants |
| FR2844272A1 (en) * | 2002-09-09 | 2004-03-12 | Oreal | New tricyclic indole or tetrahydroquinoline derivatives useful as developers in oxidation dye compositions for dyeing keratinic fibers, especially human hair |
-
2006
- 2006-08-23 CN CNA2006100303156A patent/CN1907253A/en active Pending
-
2007
- 2007-08-20 WO PCT/CN2007/002505 patent/WO2008025240A1/en active Application Filing
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103987694A (en) * | 2011-12-16 | 2014-08-13 | 莱雅公司 | Coupler with 7-amino-1,2,3,4-tetrahydroquinoline structure, dyeing composition comprising same, processes and uses |
| CN103987694B (en) * | 2011-12-16 | 2017-10-13 | 莱雅公司 | Colour coupler with the tetrahydroquinoline structure of 7 amino 1,2,3,4, the colouring compositions comprising them, method and purposes |
| CN108495846A (en) * | 2015-12-23 | 2018-09-04 | 欧莱雅 | Substituted dihydro-isoquinoline salt is used to handle purposes, composition and the implementation of keratin material |
| CN108495846B (en) * | 2015-12-23 | 2022-02-22 | 欧莱雅 | Use, composition and implementation method of substituted dihydroisoquinolinium salt for treating keratin materials |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008025240A1 (en) | 2008-03-06 |
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