EP1432393A1 - Dyeing composition comprising a diaminopyrazole-type oxidation base, a heterocyclic oxidation base and a coupling agent - Google Patents

Dyeing composition comprising a diaminopyrazole-type oxidation base, a heterocyclic oxidation base and a coupling agent

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Publication number
EP1432393A1
EP1432393A1 EP02800161A EP02800161A EP1432393A1 EP 1432393 A1 EP1432393 A1 EP 1432393A1 EP 02800161 A EP02800161 A EP 02800161A EP 02800161 A EP02800161 A EP 02800161A EP 1432393 A1 EP1432393 A1 EP 1432393A1
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EP
European Patent Office
Prior art keywords
composition
composition according
oxidation base
amino
pyrazolo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP02800161A
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German (de)
French (fr)
Inventor
Sylvain Kravtchenko
Alain Lagrange
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
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Publication date
Application filed by LOreal SA filed Critical LOreal SA
Publication of EP1432393A1 publication Critical patent/EP1432393A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • 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

Definitions

  • the subject of the invention is a dye composition comprising an oxidation base of the diaminopyrazole type, a heterocyclic oxidation base and a coupler.
  • the subject of the invention is also the use of this composition for dyeing keratin fibers as well as the dyeing process using this composition.
  • oxidation bases such as ortho or paraphenylenediamines, ortho or paraaminophenols and heterocyclic compounds.
  • oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored compounds.
  • couplers or color modifiers the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as as indole compounds.
  • the so-called "permanent" coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be without drawbacks from the toxicological point of view, it must make it possible to obtain nuances in the desired intensity and have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and rubbing.
  • the dyes must also make it possible to cover gray hair, and finally be the least selective possible, that is to say allow to obtain differences in weakest coloration possible throughout the same keratin fiber, which is generally sensitized differently (ie damaged) between its tip and its root.
  • Dye compositions are already known comprising, as the oxidation base, diaminopyrazole derivatives.
  • patent DE 3843892 describes dye compositions for dyeing keratin fibers comprising 4,5-diaminopyrazole derivatives which can be substituted in position 2 by alkyl or hydroxyalkyl radicals.
  • Patent application EP 692 245 describes dye compositions comprising 4,5-diaminopyrazole derivatives associated with particular meta-phenylenediamines.
  • Patent application DE 19643059 describes dye compositions combining 4,5-diaminopyrazole derivatives with metaaminophenol and metaphenylenediamine couplers.
  • Patent application DE 19646609 describes dye compositions combining 4,5-diaminopyrazole derivatives with benzoxazine couplers.
  • the object of the present invention is to provide new dye compositions for dyeing keratin fibers containing diaminopyrazole derivatives which do not have the drawbacks of those of the prior art.
  • the object of the present invention is to provide dye compositions containing diaminopyrazole derivatives which are not very selective and particularly resistant, while being capable of generating intense colorings in various shades.
  • R being a C r C 6 alkyl radical
  • At least one second heterocyclic oxidation base and • at least one coupler.
  • Another subject of the invention is the use of the composition of the present invention for dyeing keratin fibers, in particular human keratin fibers such as the hair.
  • the subject of the invention is also a device and a dyeing process using the composition of the invention.
  • alkyl means linear or branched radicals, for example methyl, ethyl, n-propyl, iso-propyl, butyl, etc.
  • the 4,5-diaminopyrazole oxidation base of formula (I) is such that R1 represents a C r C 4 , preferably C 2 -C 4 , alkyl radical substituted by an OR radical, R being an alkyl radical in C r C 4 , preferably in C1-C2.
  • the 4,5-diaminopyrazole oxidation base of formula (I) is preferably 4,5-diamino-1- (2'-methoxyethyl) -pyrazole.
  • heterocyclic oxidation bases in oxidation coloring other than the heterocyclic oxidation bases of formula (I) can be used in the dye composition of the present invention.
  • the heterocyclic oxidation base (s) useful in the context of the invention are chosen from pyridine, pyrimidine, pyrazole heterocyclic oxidation bases and their addition salts.
  • pyridine oxidation bases mention may be made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino 6-methoxy pyridine, 2- ( ⁇ -methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.
  • Other pyridine oxidation bases useful in the present invention are the 3-amino pyrazolo- [1,5-a] -pyridine oxidation bases or their addition salts described for example in patent application FR 2801308.
  • pyrazolo [1, 5-a] pyridin-3-ylamine 2-acetylamino pyrazolo- [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridine-3-ylamino; (3 ⁇ amino-pyrazolo [1,5-a] pyridine-7-yl) -methanol; 2- (3-amino-pyrazolo [1,5-a] pyridine-5-yl) -ethanol; 2- (3-amino-pyrazolo [1,5-a] pyridine-7-yl) - ethanol; (3-amino-pyrazolo [1,5-a] pyridine-2-yl) -methanol;
  • pyrimidine derivatives mention may be made of the compounds described for example in patents DE 2,359,399; JP 88-169,571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which may be mentioned pyrazolo - [1,5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; pyrazolo- [1,5-aj-pyrimidine-3,5-
  • pyrazole derivatives mention may be made of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE, 195 43 988 such as 4,5-diamino 1-methyl pyrazole, 4,5-diamino l- ( ⁇ -hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole , 4,5-diamino 1,3-dimethyl pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1, 3-dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino
  • the heterocyclic oxidation base useful in the composition of the present invention is a 3-amino pyrazolo- [1,5-a] -pyridines oxidation base.
  • the 3-amino pyrazolo- [1,5-a] -pyridine oxidation base is pyrazolo [1,5, a] pyridin-3-ylamine.
  • the composition of the present invention comprises at least one coupler.
  • the useful couplers can be chosen from metaphenylenediamines, metaaminophenols, metadiphenols, naphthalene couplers, heterocyclic couplers and their addition salts.
  • the coupler is a meta-aminophenol.
  • the amount of each of the couplers is between 0.001 and 10% by weight approximately of the total weight of the dye composition, preferably between 0.005 and 6%.
  • composition of the present invention may contain one or more additional oxidation bases chosen from the oxidation bases conventionally used in oxidation dyeing other than those described above.
  • additional oxidation bases are for example chosen from paraphenylenediamines, bisphenylalkylenediamines, para-aminophenols and ortho-aminophenols as well as their addition salts.
  • paraphenylenediamines mention may more particularly be made, for example, of paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine , 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyI paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- ( ⁇ -hydroxyethyl) paraphenylenediamine, 4-N, N-bis- ( ⁇ - hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- ( ⁇ -hydroxyethyl) amino 2-chloro aniline , 2- ⁇ -hydroxyethyl
  • paraphenylenediamine paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2- ⁇ -hydroxyethyl paraphenylenediamine, 2- ⁇ -hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- ( ⁇ -hydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2- ⁇ -acetylaminoethyloxy paraphenylenediamine, and their addition salts with an acid are particularly preferred .
  • bis-phenylalkylenediamines that may be mentioned by way of example,
  • para-aminophenol there may be mentioned by way of example, para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4- amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- ( ⁇ -hydroxyethyl aminomethyl) phenol, 4- amino 2-fluoro phenol, and their addition salts with an acid.
  • para-aminophenol 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4- amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- ( ⁇ -hydroxyethyl aminomethyl) phenol, 4- amino 2-fluoro phenol, and their addition salts with an acid.
  • ortho-aminophenols there may be mentioned by way of example, 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid.
  • the amount of each of the oxidation bases present in the composition of the invention is generally between 0.001 to 10% by weight approximately of the total weight of the dye composition, preferably between 0.005 and 6%.
  • the addition salts of the oxidation bases and of the couplers useful in the context of the invention are in particular chosen from addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as soda, potash, ammonia, amines or alkanolamines.
  • composition in accordance with the invention may also contain one or more direct dyes which can in particular be chosen from nitro dyes from the benzene series, azo direct dyes, methine direct dyes. These dyes can be of nonionic, anionic or cationic nature.
  • the medium suitable for dyeing also called dye support, generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water.
  • organic solvent mention may, for example, be made of lower CC 4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethyleneglycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
  • the solvents are preferably present in proportions of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.
  • the dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or their mixtures, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, and in particular associative thickeners anionic, cationic, nonionic and amphoteric, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.
  • the above adjuvants are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition.
  • the pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems.
  • the acidifying agents there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.
  • the basifying agents there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (II) below:
  • W is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical
  • R a , R, R c and R d which are identical or different, represent a hydrogen atom, a C r C 4 alkyl or C, -C 4 hydroxyalkyl radical.
  • the dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
  • the process of the present invention is a process in which the composition according to the present invention as defined above is applied to the fibers, and the color is revealed using an oxidizing agent.
  • the color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it , applied simultaneously or sequentially to the composition of the invention.
  • the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in enough to develop color.
  • the mixture obtained is then applied to the keratin fibers. After an exposure time of 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried.
  • the oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are for example hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and enzymes oxidases among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.
  • the oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
  • the ready-to-use composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers, and especially human hair.
  • the invention also relates to a device with several compartments or "kit” for dyeing in which a first compartment contains the dye composition defined above and a second compartment contains an oxidizing composition.
  • This device can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.
  • the compounds useful in the composition of the present invention are known compounds which can be obtained from general preparation methods known to those skilled in the art. For example, the synthetic approach shown below is described in the literature up to intermediary (2) (JHP Juffermanns, C. L; Habraken; J. Org. Chem., 1986, 51, 4656; Klebe and al.; Synthesis, 1973, 294; R. H ⁇ ttel, F. B ⁇ chele; Chem. Ber.; 1955, 88, 1586.). In the present case, the passage from compound 3 to compound 2 is carried out by means of a NH 3 / EtOH mixture.
  • Example 2 Dye composition containing 4,5-Diamino-1- (2-methoxyethvD-pyrazole dihydrochloride On.a. prepared, the following dye composition:
  • the composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight).
  • the mixture obtained is applied to locks of gray hair containing 90% natural or permanent whites at a rate of 10 g per 1 g of hair. After 30 min of laying, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.
  • the wicks are evaluated visually.
  • the reflection on the wick is an intense copper red.

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Abstract

The invention relates to a dyeing composition comprising a diaminopyrazole-type oxidation base, a heterocyclic oxidation base and a coupling agent. The invention also relates to the use of said composition for the dyeing of keratin fibres and to the dyeing method using said composition.

Description

Entrer le TEXTE DU BREVET ci-dessous Enter the PATENT TEXT below
COMPOSITION TINCTORIALE COMPRENANT UNE BASE D'OXYDATION DU TYPE DIAMINOPYRAZOLE, UNE BASE D'OXYDATION HETEROCYCLIQUE ET UN COUPLEUR. L'invention a pour objet une composition tinctoriale comprenant une base d'oxydation du type diaminopyrazole, une base d'oxydation hétérocyclique et un coupleur. L'invention a aussi pour objet l'utilisation de cette composition pour la teinture des fibres kératiniques ainsi que le procédé de teinture mettant en oeuvre cette composition. II est connu de teindre les fibres kératiniques et en particulier les cheveux humains avec des compositions tinctoriales contenant des précurseurs de colorant d'oxydation, appelés généralement bases d'oxydation, tels que des ortho ou paraphénylènediamines, des ortho ou paraaminophénols et des composés heterocycliques. Ces bases d'oxydation sont des composés incolores ou faiblement colorés qui, associés à des produits oxydants, peuvent donner naissance par un processus de condensation oxydative à des composés colorés.TINCTORIAL COMPOSITION COMPRISING AN OXIDATION BASE OF THE DIAMINOPYRAZOLE TYPE, A HETEROCYCLIC OXIDATION BASE AND A COUPLER. The subject of the invention is a dye composition comprising an oxidation base of the diaminopyrazole type, a heterocyclic oxidation base and a coupler. The subject of the invention is also the use of this composition for dyeing keratin fibers as well as the dyeing process using this composition. It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho or paraphenylenediamines, ortho or paraaminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored compounds.
On sait également que l'on peut faire varier les nuances obtenues avec ces bases d'oxydation en les associant à des coupleurs ou modificateurs de coloration, ces derniers étant choisis notamment parmi les métadiamines aromatiques, les metaaminophenols, les metadiphenols et certains composés heterocycliques tels que des composés indoliques.It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as as indole compounds.
La variété des molécules mises en jeu au niveau des bases d'oxydation et des coupleurs, permet l'obtention d'une riche palette de couleurs.The variety of molecules involved in the oxidation bases and couplers, allows obtaining a rich palette of colors.
La coloration dite "permanente" obtenue grâce à ces colorants d'oxydation, doit par ailleurs satisfaire un certain nombre d'exigences. Ainsi, elle doit être sans inconvénient sur le plan toxicologique, elle doit permettre d'obtenir des nuances dans l'intensité souhaitée et présenter une bonne tenue face aux agents extérieurs tels que la lumière, les intempéries, le lavage, les ondulations permanentes, la transpiration et les frottements. Les colorants doivent également permettre de couvrir les cheveux blancs, et être enfin les moins sélectifs possibles, c'est-à-dire permettre d'obtenir des écarts de coloration les plus faibles possibles tout au long d'une même fibre kératinique, qui est en général différemment sensibilisée (i.e. abîmée) entre sa pointe et sa racine.The so-called "permanent" coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be without drawbacks from the toxicological point of view, it must make it possible to obtain nuances in the desired intensity and have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and rubbing. The dyes must also make it possible to cover gray hair, and finally be the least selective possible, that is to say allow to obtain differences in weakest coloration possible throughout the same keratin fiber, which is generally sensitized differently (ie damaged) between its tip and its root.
Il est déjà connu des compositions tinctoriales comprenant à titre de base d'oxydation des dérivés diaminopyrazoles. Par exemple, le brevet DE 3843892 décrit des compositions tinctoriales pour la teinture de fibres kératiniques comprenant des dérivés 4,5-diaminopyrazoles pouvant être substitués en position 2 par des radicaux alkyles ou hydroxyalkyles. La demande de brevet EP 692 245 décrit des compositions tinctoriales comprenant des dérivés 4,5-diaminopyrazoles associés à des métaphénylènediamiiies particulières. La demande de brevet DE 19643059 décrit des compositions tinctoriales associant des dérivés 4,5-diaminopyrazoles avec des coupleurs metaaminophenols et métaphénylènediamine. La demande de brevet DE 19646609 décrit des compositions tinctoriales associant des dérivés 4,5- diaminopyrazoles avec des coupleurs benzoxazines.Dye compositions are already known comprising, as the oxidation base, diaminopyrazole derivatives. For example, patent DE 3843892 describes dye compositions for dyeing keratin fibers comprising 4,5-diaminopyrazole derivatives which can be substituted in position 2 by alkyl or hydroxyalkyl radicals. Patent application EP 692 245 describes dye compositions comprising 4,5-diaminopyrazole derivatives associated with particular meta-phenylenediamines. Patent application DE 19643059 describes dye compositions combining 4,5-diaminopyrazole derivatives with metaaminophenol and metaphenylenediamine couplers. Patent application DE 19646609 describes dye compositions combining 4,5-diaminopyrazole derivatives with benzoxazine couplers.
Le but de la présente invention est de fournir de nouvelles compositions tinctoriales pour la teinture de fibres kératiniques contenant des dérivés diaminopyrazoles ne présentant pas les inconvénients de celles de la technique antérieure. En particulier, le but de la présente invention est de fournir des compositions tinctoriales contenant des dérivés diaminopyrazoles qui sont peu sélectives et particulièrement résistantes, tout en étant capables d'engendrer des colorations intenses dans des nuances variées.The object of the present invention is to provide new dye compositions for dyeing keratin fibers containing diaminopyrazole derivatives which do not have the drawbacks of those of the prior art. In particular, the object of the present invention is to provide dye compositions containing diaminopyrazole derivatives which are not very selective and particularly resistant, while being capable of generating intense colorings in various shades.
Ce but est atteint avec la présente invention qui a pour objet une composition tinctoriale comprenant, dans un milieu de teinture approprié, • au moins une base d'oxydation 4,5-diaminopyrazole de formule (I) ou leurs sels d'addition,This object is achieved with the present invention which relates to a dye composition comprising, in an appropriate dyeing medium, • at least one 4,5-diaminopyrazole oxidation base of formula (I) or their addition salts,
dans laquelle R1 est un radical alkyle en CrC6 substitué par un ou plusieurs radicaux in which R1 is a C r C 6 alkyl radical substituted by one or more radicals
OR, R étant un radical alkyle en CrC6,OR, R being a C r C 6 alkyl radical,
• au moins une deuxième base d'oxydation hétérocyclique, et • au moins un coupleur.At least one second heterocyclic oxidation base, and • at least one coupler.
Un autre objet de l'invention est l'utilisation de la composition de la présente invention pour la teinture des fibres kératiniques, en particulier les fibres kératiniques humaines telles que les cheveux. L'invention a aussi pour objet un dispositif et un procédé de teinture mettant en œuvre la composition de l'invention.Another subject of the invention is the use of the composition of the present invention for dyeing keratin fibers, in particular human keratin fibers such as the hair. The subject of the invention is also a device and a dyeing process using the composition of the invention.
Dans le cadre de la présente invention, on entend par alkyle, des radicaux linéaires ou ramifiés, par exemple méthyle, éthyle, n-propyle, iso-propyle, butyle, etc.In the context of the present invention, the term “alkyl” means linear or branched radicals, for example methyl, ethyl, n-propyl, iso-propyl, butyl, etc.
Selon un mode de réalisation particulier, la base d'oxydation 4,5- diaminopyrazole de formule (I) est telle que R1 représente un radical alkyle en CrC4, de préférence en C2-C4 substitué par un radical OR, R étant un radical alkyle en CrC4, de préférence en C1-C2. La base d'oxydation 4,5-diaminopyrazole de formule (I) est de préférence le 4,5-diamino-1-(2'-méthoxyéthyl)-pyrazole.According to a particular embodiment, the 4,5-diaminopyrazole oxidation base of formula (I) is such that R1 represents a C r C 4 , preferably C 2 -C 4 , alkyl radical substituted by an OR radical, R being an alkyl radical in C r C 4 , preferably in C1-C2. The 4,5-diaminopyrazole oxidation base of formula (I) is preferably 4,5-diamino-1- (2'-methoxyethyl) -pyrazole.
Toutes les bases d'oxydation heterocycliques classiques en coloration d'oxydation autres que les bases d'oxydation heterocycliques de formule (I) peuvent être utilisées dans la composition tinctoriale de la présente invention. En particulier, la ou les base d'oxydation heterocycliques utiles dans le cadre de l'invention sont choisies parmi les bases d'oxydation heterocycliques pyridiniques, pyrimidiniques, pyrazoliques et leurs sels d'addition. Parmi les bases d'oxydation pyridiniques, on peut citer les composés décrits par exemple dans les brevets GB 1 026 978 et GB 1 153 196, comme la 2,5-diamino pyridine, la 2-(4-méthoxyphényl)amino 3-amino pyridine, la 2,3-diamino 6-méthoxy pyridine, la 2-(β-méthoxyéthyl)amino 3-amino 6-méthoxy pyridine, la 3,4- diamino pyridine, et leurs sels d'addition avec un acide. D'autres bases d'oxydation pyridiniques utiles dans la présente invention sont les bases d'oxydation 3-amino pyrazolo-[1 ,5-a]-pyridines ou leurs sels d'addition décrits par exemple dans la demande de brevet FR 2801308. A titre d'exemple, on peut citer la pyrazolo[1 ,5-a]pyridin-3-ylamine ; la 2-acétylamino pyrazolo-[1,5-a] pyridin-3-ylamine ; la 2-morpholin-4-yl-pyrazolo[1 ,5-a]pyridin-3-ylamine ; l'acide 3- amino-pyrazolo[1,5-a]pyridin-2-carboxylique ; la 2-méthoxy-pyrazolo[1 ,5-a]pyridine-3- ylamino ; le (3~amino-pyrazolo[1 ,5-a]pyridine-7-yl)-méthanol ; le 2-(3-amino- pyrazolo[1,5-a]pyridine-5-yl)-éthanol ; le 2-(3-amino-pyrazolo[1,5-a]pyridine-7-yl)- éthanol ; le (3-amino-pyrazolo[1,5-a]pyridine-2-yl)-méthanol ; la 3,6-diamino- pyrazolo[1 ,5-a]pyridine ; la 3,4-diamino-pyrazolo[1 ,5-a]pyridine ; la pyrazolo[1 ,5- a]pyridine-3,7-diamine ; la 7-morpholin-4-yl-pyrazolo[1 ,5-a]pyridin-3-ylamine ; la pyrazolo[1 ,5-a]pyridine-3,5-diamine ; la 5-morpholin-4-yl-pyrazolo[1 ,5-a]pyridin-3- ylamine ; le 2-[(3-amino-pyrazolo[1 ,5-a]pyridin-5-yl)-(2-hydroxyéthyl)-amino]-éthanol ; le 2-[(3-amino-pyrazolo[1 ,5-a]pyridin-7-yl)-(2-hydroxyéthyl)-amino]-éthanol ; la 3- amino-pyrazolo[1 ,5-a]pyridine-5-ol ; 3-amino-pyrazolo[1 ,5-a]pyridine-4-ol ; la 3- amino-pyrazolo[1,5-a]pyridine-6-ol ; la 3-amino-pyrazolo[1,5-a]pyridine-7-ol ; ainsi que leurs d'addition avec un acide ou avec une base. Parmi les dérivés pyrimidiniques, on peut citer les composés décrits par exemple dans les brevets DE 2 359 399 ; JP 88-169 571 ; JP 05 163 124 ; EP 0 770 375 ou demande de brevet WO 96/15765 comme la 2,4,5,6-tétra-aminopyrimidine, la 4-hydroxy 2,5,6-triaminopyrimidine, la 2-hydroxy 4,5,6-triaminopyrimidine, la 2,4-dihydroxy 5,6-diaminopyrimidine, la 2,5,6-triaminopyrimidine, et les dérivés pyrazolo-pyrimidiniques tels ceux mentionnés dans la demande de brevet FR-A-2 750 048 et parmi lesquels on peut citer la pyrazolo-[1,5-a]-pyrimidine-3,7-diamine ; la 2,5- diméthyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine ; la pyrazolo-[1,5-aj-pyrimidine-3,5- diamine ; la 2,7-diméthyl pyrazolo-[1 ,5-a]-pyrimidine-3,5-diamine ; le 3-amino pyrazolo- [1 ,5-a]-pyrimidin-7-ol ; le 3-amino pyrazolo-[1 ,5-a]-pyrimidin-5~ol ; le 2-(3-amino pyrazolo-[1 ,5-a]-pyrimidin-7-ylamino)-éthanol, le 2-(7-amino pyrazolo-[1 ,5-a]-pyrimidin- 3-ylamino)-éthanol, le 2-[(3-amino-pyrazolo[1 ,5-a]pyrimidin-7-yl)-(2-hydroxy-éthyl)- aminoj-éthanol, le 2-[(7-amino-pyrazolo[1 ,5-a]pyrimidin-3-yI)-(2-hydroxy-éthyl)-amino]- éthanol, la 5,6-diméthyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine, la 2,6-diméthyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine, la 2, 5, N 7, N 7-tetraméthyl pyrazolo-[1,5-a]- pyrimidine-3,7-diamine, la 3-amino-5-méthyl-7-imidazolylpropylamino pyrazolo-[1 ,5-a]- pyrimidine et leurs sels d'addition avec un acide et leurs formes tautomères, lorsqu'il existe un équilibre tautomérique.All the conventional heterocyclic oxidation bases in oxidation coloring other than the heterocyclic oxidation bases of formula (I) can be used in the dye composition of the present invention. In particular, the heterocyclic oxidation base (s) useful in the context of the invention are chosen from pyridine, pyrimidine, pyrazole heterocyclic oxidation bases and their addition salts. Among the pyridine oxidation bases, mention may be made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino 6-methoxy pyridine, 2- (β-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid. Other pyridine oxidation bases useful in the present invention are the 3-amino pyrazolo- [1,5-a] -pyridine oxidation bases or their addition salts described for example in patent application FR 2801308. By way of example, mention may be made of pyrazolo [1, 5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo- [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridine-3-ylamino; (3 ~ amino-pyrazolo [1,5-a] pyridine-7-yl) -methanol; 2- (3-amino-pyrazolo [1,5-a] pyridine-5-yl) -ethanol; 2- (3-amino-pyrazolo [1,5-a] pyridine-7-yl) - ethanol; (3-amino-pyrazolo [1,5-a] pyridine-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) -amino] -ethanol; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) -amino] -ethanol; 3-amino-pyrazolo [1,5-a] pyridine-5-ol; 3-amino-pyrazolo [1,5-a] pyridine-4-ol; 3-amino-pyrazolo [1,5-a] pyridine-6-ol; 3-amino-pyrazolo [1,5-a] pyridine-7-ol; as well as their addition with an acid or with a base. Among the pyrimidine derivatives, mention may be made of the compounds described for example in patents DE 2,359,399; JP 88-169,571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which may be mentioned pyrazolo - [1,5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; pyrazolo- [1,5-aj-pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 3-amino pyrazolo- [1,5-a] -pyrimidin-7-ol; 3-amino pyrazolo- [1,5-a] -pyrimidin-5 ~ ol; 2- (3-amino pyrazolo- [1,5-a] -pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo- [1,5-a] -pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1, 5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) - aminoj-ethanol, 2 - [(7-amino-pyrazolo [1 , 5-a] pyrimidin-3-yI) - (2-hydroxy-ethyl) -amino] - ethanol, 5,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, la 2, 5, N 7, N 7-tetramethyl pyrazolo- [1,5-a] - pyrimidine-3,7 -diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo- [1, 5-a] - pyrimidine and their addition salts with an acid and their tautomeric forms, when there is a tautomeric equilibrium.
Parmi les dérivés pyrazoliques, on peut citer les composés décrits dans les brevets DE 3 843 892, DE 4 133 957 et demandes de brevet WO 94/08969, WO 94/08970, FR-A-2 733 749 et DE, 195 43 988 comme le 4,5-diamino 1-méthyl pyrazole, le 4,5-diamino l-(β-hydroxyéthyl) pyrazole, le 3,4-diamino pyrazole, le 4,5- diamino 1-(4'-chlorobenzyl) pyrazole, le 4,5-diamino 1,3-diméthyl pyrazole, le 4,5-diamino 3-méthyl 1-phényl pyrazole, le 4,5-diamino 1-méthyl 3-phényl pyrazole, le 4-amino 1 ,3-diméthyl 5-hydrazino pyrazole, le 1-benzyl 4,5-diamino 3-méthyl pyrazole, le 4,5-diamino 3-tert-butyl 1-méthyl pyrazole, le 4,5-diamino 1-tert-butyl 3-méthyl pyrazole, le 4,5-diamino l-(β-hydroxyéthyl) 3-méthyl pyrazole, le 4,5-diamino 1-éthyl 3- méthyl pyrazole, le 4,5-diamino 1-éthyl 3-(4'-méthoxyphényl) pyrazole, le 4,5-diamino 1- éthyl 3-hydroxyméthyl pyrazole, le 4,5-diamino 3-hydroxyméthyl 1-méthyl pyrazole, le 4,5-diamino 3-hydroxyméthyl 1-isopropyl pyrazole, le 4,5-diamino 3-méthyl 1-isopropyl pyrazole, le 4-amino 5-(2'-aminoéthyl)amino 1 ,3-diméthyl pyrazole, le 3,4,5-triamino pyrazole, le 1-méthyl 3,4,5-triamino pyrazole, le 3,5-diamino 1-méthyl 4-méthylamino pyrazole, le 3,5-diamino 4-(β-hydroxyéthyl)amino 1-méthyl pyrazole, et leurs sels d'addition avec un acide.Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE, 195 43 988 such as 4,5-diamino 1-methyl pyrazole, 4,5-diamino l- (β-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole , 4,5-diamino 1,3-dimethyl pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1, 3-dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole, 4,5-diamino l- (β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1-ethyl 3- methyl pyrazole, 4,5-diamino 1-ethyl 3- (4'-methoxyphenyl) pyrazole, 4,5-diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-isopropyl pyrazole, 4,5-diamino 3-methyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4-methylamino pyrazole , 3,5-diamino 4- (β-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with an acid.
Selon un mode de réalisation particulier, la base d'oxydation hétérocyclique utile dans la composition de la présente invention est une base d'oxydation 3-amino pyrazolo-[1 ,5-a]-pyridines. De préférence, la base d'oxydation 3- amino pyrazolo-[1 ,5-a]-pyridine est la pyrazolo[1 ,5,a]pyridin-3-ylamine.According to a particular embodiment, the heterocyclic oxidation base useful in the composition of the present invention is a 3-amino pyrazolo- [1,5-a] -pyridines oxidation base. Preferably, the 3-amino pyrazolo- [1,5-a] -pyridine oxidation base is pyrazolo [1,5, a] pyridin-3-ylamine.
La composition de la présente invention comprend au moins un coupleur. Les coupleurs utiles peuvent être choisis parmi les métaphénylènediamines, les metaaminophenols, les metadiphenols, les coupleurs naphtaléniques, les coupleurs heterocycliques et leurs sels d'addition. A titre d'exemple, on peut citer le 2-méthyl 5-aminophénol, le 5~N-(β- hydroxyéthyl)amino 2-méthyl phénol, le 6-chloro-2-méthyl-5-aminophénol, le 3-amino phénol, le 1 ,3-dihydroxy benzène, le 1 ,3-dihydroxy 2-méthyl benzène, le 4-chloro 1 ,3- dihydroxy benzène, le 2,4-diamino l-(β-hydroxyéthyloxy) benzène, le 2-amino 4-(β- hydroxyéthylamino) 1-méthoxybenzène, le 1 ,3-diamino benzène, le 1 ,3-bis-(2,4- diaminophenoxy) propane, la 3-uréido aniline, le 3-uréido 1-diméthyIamino benzène, le sésamol, le 1-β-hydroxyéthylamino-3,4-méthylènedioxybenzène, l'α-naphtol, le 2 méthyl-1-naphtol, le 6-hydroxy indole, le 4-hydroxy indole, le 4-hydroxy N-méthyl indole, la 2-amino-3-hydroxy pyridine, la 6- hydroxy benzomorpholine la 3,5-diamino- 2,6-diméthoxypyridine, le 1-N-(β-hydroxyéthyl)amino-3,4-méthylène dioxybenzène, le 2,6-bis-(β-hydroxyéthylàmino)toluène et leurs sels d'addition.The composition of the present invention comprises at least one coupler. The useful couplers can be chosen from metaphenylenediamines, metaaminophenols, metadiphenols, naphthalene couplers, heterocyclic couplers and their addition salts. By way of example, mention may be made of 2-methyl 5-aminophenol, 5 ~ N- (β-hydroxyethyl) amino 2-methyl phenol, 6-chloro-2-methyl-5-aminophenol, 3-amino phenol, 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino l- (β-hydroxyethyloxy) benzene, 2- amino 4- (β- hydroxyethylamino) 1-methoxybenzene, 1, 3-diamino benzene, 1, 3-bis- (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene , sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2 methyl-1-naphtol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylàmino) toluene and their addition salts.
Selon un mode de réalisation particulier, le coupleur est un méta- aminophénol. Dans la composition de la prés.ente invention, la quantité de chacun des coupleurs est comprise entre 0,001 et 10 % en poids environ du poids total de la composition tinctoriale, de préférence entre 0,005 et 6 %.According to a particular embodiment, the coupler is a meta-aminophenol. In the composition of the present invention, the amount of each of the couplers is between 0.001 and 10% by weight approximately of the total weight of the dye composition, preferably between 0.005 and 6%.
En plus des composés précédemment décrits, la composition de la présente invention peut contenir une ou plusieurs bases d'oxydation additionnelles choisies parmi les bases d'oxydation classiquement utilisées en teinture d'oxydation autres que celles décrites précédemment. Ces bases d'oxydation additionnelles sont par exemple choisies parmi les paraphénylènediamines, les bis- phénylalkylènediamines, les para-aminophénols et les ortho-aminophénols ainsi que leurs sels d'addition.In addition to the compounds described above, the composition of the present invention may contain one or more additional oxidation bases chosen from the oxidation bases conventionally used in oxidation dyeing other than those described above. These additional oxidation bases are for example chosen from paraphenylenediamines, bisphenylalkylenediamines, para-aminophenols and ortho-aminophenols as well as their addition salts.
Parmi les paraphénylènediamines, on peut plus particulièrement citer à titre d'exemple, la paraphénylènediamine, la paratoluylènediamine, la 2-chloro paraphénylènediamine, la 2,3-diméthyl paraphénylènediamine, la 2,6-diméthyl paraphénylènediamine, la 2,6-diéthyl paraphénylènediamine, la 2,5-diméthyl paraphénylènediamine, la N,N-diméthyl paraphénylènediamine, la N,N-diéthyI paraphénylènediamine, la N,N-dipropyl paraphénylènediamine, la 4-amino N,N-diéthyl 3-méthyl aniline, la N,N-bis-(β-hydroxyéthyl) paraphénylènediamine, la 4-N,N-bis-(β- hydroxyéthyi)amino 2-méthyl aniline, la 4-N,N-bis-(β-hydroxyéthyl)amino 2-chloro aniline, la 2-β-hydroxyéthyl paraphénylènediamine, la 2-fluoro paraphénylènediamine, la 2-isopropyl paraphénylènediamine, la N-(β-hydroxypropyl) paraphénylènediamine, la 2-hydroxyméthyl paraphénylènediamine, la N,N-diméthyl 3-méthyl paraphénylènediamine, la N,N-(éthyl, β-hydroxyéthyl) paraphénylènediamine, la N-(β,γ- dihydroxypropyl) paraphénylènediamine, la N-(4'-aminophényl) paraphénylènediamine, la N-phényl paraphénylènediamine, la 2-β-hydroxyéthyloxy paraphénylènediamine, la 2- β-acétylaminoéthyloxy paraphénylènediamine, la N-(β-méthoxyéthyl) paraphénylènediamine, la 4 aminophenyl pyrrolidine, la 2 thiényl paraphénylène diamine, le 2-β hydroxyéthylamino 5-amino toluène, la 3-hydroxy 1-(4'- aminophényl)pyrrolidine et leurs sels d'addition avec un acide,.Among the paraphenylenediamines, mention may more particularly be made, for example, of paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine , 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyI paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β- hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- (β-hydroxyethyl) amino 2-chloro aniline , 2-β-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylen , N- (ethyl, β-hydroxyethyl) paraphenylenediamine, N - (β, γ- dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2- β-acetylaminoethyloxy paraphenylenediamine ) paraphenylenediamine, 4 aminophenyl pyrrolidine, 2 thienyl paraphenylene diamine, 2-β hydroxyethylamino 5-amino toluene, 3-hydroxy 1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid ,.
Parmi les paraphénylènediamines citées ci-dessus, la paraphénylènediamine, la paratoluylènediamine, la 2-isopropyl paraphénylènediamine, la 2-β-hydroxyéthyl paraphénylènediamine, la 2-β-hydroxyéthyloxy paraphénylènediamine, la 2,6-diméthyl paraphénylènediamine, la 2,6-diéthyl paraphénylènediamine, la 2,3-diméthyl paraphénylènediamine, la N,N-bis-(β- hydroxyéthyl) paraphénylènediamine, la 2-chloro paraphénylènediamine, la 2-β-acétylaminoéthyloxy paraphénylènediamine, et leurs sels d'addition avec un acide sont particulièrement préférées. Parmi les bis-phénylalkylènediamines, on peut citer à titre d'exemple, leAmong the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and their addition salts with an acid are particularly preferred . Among the bis-phenylalkylenediamines that may be mentioned by way of example,
N,N'-bis-(β-hydroxyéthyl) N,N'-bis-(4'-aminophényl) 1 ,3-diamino propanol, la N,N'-bis- (β-hydroxyéthyl) N,N'-bis-(4'-aminophényl) éthylènediamine, la N,N'-bis-(4- aminophényl) tétraméthylènediamine, la N,N'-bis-(β-hydroxyéthyl) N,N'-bis-(4- aminophényl) tétraméthylènediamine, la N,N'-bis-(4-méthyl-aminophényl) tétraméthylènediamine, la N,N'-bis-(éthyl) N,N'-bis-(4'-amino, 3'-méthylphényl) éthylènediamine, le 1,8-bis-(2,5-diamino phénoxy)-3,6-dioxaoctane, et leurs sels d'addition avec un acide.N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1, 3-diamino propanol, N, N'-bis- (β-hydroxyethyl) N, N'- bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts with an acid.
Parmi les para-aminophénols, on peut citer à titre d'exemple, le para- aminophénol, le 4-amino 3-méthyl phénol, le 4-amino 3-fluoro phénol, le 4-amino 3- hydroxyméthyl phénol, le 4-amino 2-méthyl phénol, le 4-amino 2-hydroxyméthyl phénol, le 4-amino 2-méthoxyméthyl phénol, le 4-amino 2-aminométhyl phénol, le 4-amino 2-(β- hydroxyéthyl aminométhyl) phénol, le 4-amino 2-fluoro phénol, et leurs sels d'addition avec un acide.Among the para-aminophenols, there may be mentioned by way of example, para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4- amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- (β-hydroxyethyl aminomethyl) phenol, 4- amino 2-fluoro phenol, and their addition salts with an acid.
Parmi les ortho-aminophénols, on peut citer à titre d'exemple, le 2-amino phénol, le 2-amino 5-méthyl phénol, le 2-amino 6-méthyl phénol, le 5-acétamido 2-amino phénol, et leurs sels d'addition avec un acide.Among the ortho-aminophenols, there may be mentioned by way of example, 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid.
La quantité de chacune des bases d'oxydation présente dans la composition de l'invention est en général comprise entre 0,001 à 10 % en poids environ du poids total de la composition tinctoriale, de préférence entre 0,005 et 6 %. D'une manière générale, les sels d'addition des bases d'oxydation et des coupleurs utiles dans le cadre de l'invention sont notamment choisis parmi les sels d'addition avec un acide tels que les chlorhydrates, les bromhydrates, les sulfates, les citrates, les succinates, les tartrates, les lactates, les tosylates, les benzènesulfonates, les phosphates et les acétates et les sels d'addition avec une base telles que la soude, la potasse, l'ammoniaque, les aminés ou lés alcanolamines.The amount of each of the oxidation bases present in the composition of the invention is generally between 0.001 to 10% by weight approximately of the total weight of the dye composition, preferably between 0.005 and 6%. In general, the addition salts of the oxidation bases and of the couplers useful in the context of the invention are in particular chosen from addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as soda, potash, ammonia, amines or alkanolamines.
La composition conforme à l'invention peut en outre contenir un ou plusieurs colorants directs pouvant notamment être choisis parmi les colorants nitrés de la série benzénique, les colorants directs azoïques, les colorants directs méthiniques. Ces colorants peuvent être de nature non ionique, anionique ou cationique.The composition in accordance with the invention may also contain one or more direct dyes which can in particular be chosen from nitro dyes from the benzene series, azo direct dyes, methine direct dyes. These dyes can be of nonionic, anionic or cationic nature.
Le milieu approprié pour la teinture appelé aussi support de teinture est généralement constitué par de l'eau ou par un mélange d'eau et d'au moins un solvant organique pour solubiliser les composés qui ne seraient pas suffisamment solubles dans l'eau. A titre de solvant organique, on peut par exemple citer les alcanols inférieurs en C C4, tels que l'éthanol et l'isopropanol ; les polyols et éthers de polyols comme le 2-butoxyéthanol, le propylèneglycol, le monomethylether de propylèneglycol, le monoethylether et le monomethylether du diethyleneglycol, ainsi que les alcools aromatiques comme l'alcool benzylique ou le phénoxyéthanol, et leurs mélanges.The medium suitable for dyeing, also called dye support, generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvent, mention may, for example, be made of lower CC 4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethyleneglycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
Les solvants sont de préférence présents dans des proportions comprises entre 1 et 40 % en poids environ par rapport au poids total de la composition tinctoriale, et encore plus préférentiellement entre 5 et 30 % en poids environ. La composition tinctoriale conforme à l'invention peut également renfermer divers adjuvants utilisés classiquement dans les compositions pour la teinture des cheveux, tels que des agents tensio-actifs anioniques, cationiques, non-ioniques, amphotères, zwittérioniques ou leurs mélanges, des polymères anioniques, cationiques, non-ioniques, amphotères, zwittérioniques ou leurs mélanges, des agents épaississants minéraux ou organiques, et en particulier les épaississants associatifs polymères anioniques, cationiques, non ioniques et amphotères, des agents antioxydants, des agents de pénétration, des agents séquestrants, des parfums, des tampons, des agents dispersants, des agents de conditionnement tels que par exemple des silicones volatiles ou non volatiles, modifiées ou non modifiées, des agents filmogènes, des céramides, des agents conservateurs, des agents opacifiants.The solvents are preferably present in proportions of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately. The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or their mixtures, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, and in particular associative thickeners anionic, cationic, nonionic and amphoteric, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.
Les adjuvants ci dessus sont en général présents en quantité comprise pour chacun d'eux entre 0,01 et 20 % en poids par rapport au poids de la composition. Bien entendu, l'homme de l'art veillera à choisir ce ou ces éventuels composés complémentaires de manière telle que les propriétés avantageuses attachées intrinsèquement à la composition de teinture d'oxydation conforme à l'invention ne soient pas ou substantiellement pas, altérées par la ou les adjonctions envisagées. Le pH de la composition tinctoriale conforme à l'invention est généralement compris entre 3 et 12 environ, et de préférence entre 5 et 11 environ. Il peut être ajusté à la valeur désirée au moyen d'agents acidifiants ou alcalinisants habituellement utilisés en teinture des fibres kératiniques ou bien encore à l'aide de systèmes tampons classiques.The above adjuvants are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition. Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the oxidation dye composition according to the invention are not or not substantially altered by the planned addition (s). The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems.
Parmi les agents acidifiants, on peut citer, à titre d'exemple, les acides minéraux ou organiques comme l'acide chlorhydrique, l'acide orthophosphorique, l'acide sulfurique, les acides carboxyliques comme l'acide acétique, l'acide tartrique, l'acide citrique, l'acide lactique, les acides sulfoniques. Parmi les agents alcalinisants on peut citer, à titre d'exemple, l'ammoniaque, les carbonates alcalins, les alcanolamines telles que les mono-, di- et triéthanolamines ainsi que leurs dérivés, les hydroxydes de sodium ou de potassium et les composés de formule (II) suivante :Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids. Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (II) below:
Ra \ χ Rb Ra \ χ Rb
dans laquelle W est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en C,-C4 ; Ra, R , Rc et Rd, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en CrC4 ou hydroxyalkyle en C,-C4. in which W is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; R a , R, R c and R d , which are identical or different, represent a hydrogen atom, a C r C 4 alkyl or C, -C 4 hydroxyalkyl radical.
La composition tinctoriale selon l'invention peut se présenter sous des formes diverses, telles que sous forme de liquides, de crèmes, de gels, ou sous toute autre forme appropriée pour réaliser une teinture des fibres kératiniques, et notamment des cheveux humains.The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
Le procédé de la présente invention est un procédé dans lequel on applique sur les fibres la composition selon la présente invention telle que définie précédemment, et qu'on révèle la couleur à l'aide d'un agent oxydant. La couleur peut être révélée à pH acide, neutre ou alcalin et l'agent oxydant peut être ajouté à la composition de l'invention juste au moment de l'emploi ou il peut être mis en œuvre à partir d'une composition oxydante le contenant, appliquée simultanément ou séquentiellement à la composition de l'invention. Selon un mode de réalisation particulier, la composition selon la présente invention est mélangée, de préférence au moment de l'emploi, à une composition contenant, dans un milieu approprié pour la teinture, au moins un agent oxydant, cet agent oxydant étant présent en une quantité suffisante pour développer une coloration. Le mélange obtenu est ensuite appliqué sur les fibres kératiniques. Après un temps de pose de 3 à 50 minutes environ, de préférence 5 à 30 minutes environ, les fibres kératiniques sont rincées, lavées au shampooing, rincées à nouveau puis séchées.The process of the present invention is a process in which the composition according to the present invention as defined above is applied to the fibers, and the color is revealed using an oxidizing agent. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it , applied simultaneously or sequentially to the composition of the invention. According to a particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in enough to develop color. The mixture obtained is then applied to the keratin fibers. After an exposure time of 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried.
Les agents oxydants classiquement utilisés pour la teinture d'oxydation des fibres kératiniques sont par exemple le peroxyde d'hydrogène, le peroxyde d'urée, les bromates de métaux alcalins, les persels tels que les perborates et persulfates, les peracides et les enzymes oxydases parmi lesquelles on peut citer les peroxydases, les oxydo-réductases à 2 électrons telles que les uricases et les oxygénases à 4 électrons comme les laccases. Le peroxyde d'hydrogène est particulièrement préféré.The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are for example hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and enzymes oxidases among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.
La composition oxydante peut également renfermer divers adjuvants utilisés classiquement dans les compositions pour la teinture des cheveux et tels que définis précédemment.The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
Le pH de la composition oxydante renfermant l'agent oxydant est tel qu'après mélange avec la composition tinctoriale, le pH de la composition résultante appliquée sur les fibres kératiniques varie de préférence entre 3 et 12 environ, et encore plus preferentiellement entre 5 et 11. Il peut être ajusté à la valeur désirée au moyen d'agents acidifiants ou alcalinisants habituellement utilisés en teinture des fibres kératiniques et tels que définis précédemment.The pH of the oxidizing composition containing the oxidizing agent is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11 It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.
La composition prête à l'emploi qui est finalement appliquée sur les fibres kératiniques peut se présenter sous des formes diverses, telles que sous forme de liquides, de crèmes, de gels ou sous toute autre forme appropriée pour réaliser une teinture des fibres kératiniques, et notamment des cheveux humains.The ready-to-use composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers, and especially human hair.
L'invention a aussi pour objet un dispositif à plusieurs compartiments ou "kit" de teinture dans lequel un premier compartiment renferme la composition tinctoriale définie ci-dessus et un deuxième compartiment renferme une composition oxydante. Ce dispositif peut être équipé d'un moyen permettant de délivrer sur les cheveux le mélange souhaité, tel que les dispositifs décrits dans le brevet FR-2 586 913 au nom de la demanderesse. Les composés utiles dans la composition de la présente invention sont des composés connus qui peuvent être obtenus à partir des procédés de préparation généraux connus de l'homme du métier. Par exemple, l'approche synthétique montrée ci-dessous est décrite dans la littérature jusqu'à l'intermédiaire (2) (J. H. P. Juffermanns, C. L ; Habraken ; J. Org. Chem., 1986, 51 , 4656 ; Klebe et al. ; Synthesis, 1973, 294 ; R. Hϋttel, F. Bϋchele ; Chem. Ber. ; 1955, 88, 1586.). Dans le cas présent, le passage du composé 3 au composé 2 s'effectue au moyen d'un mélange NH3/EtOH.The invention also relates to a device with several compartments or "kit" for dyeing in which a first compartment contains the dye composition defined above and a second compartment contains an oxidizing composition. This device can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant. The compounds useful in the composition of the present invention are known compounds which can be obtained from general preparation methods known to those skilled in the art. For example, the synthetic approach shown below is described in the literature up to intermediary (2) (JHP Juffermanns, C. L; Habraken; J. Org. Chem., 1986, 51, 4656; Klebe and al.; Synthesis, 1973, 294; R. Hϋttel, F. Bϋchele; Chem. Ber.; 1955, 88, 1586.). In the present case, the passage from compound 3 to compound 2 is carried out by means of a NH 3 / EtOH mixture.
- L'alkylation et l'amination pour arriver aux composés de formule (I) selon l'invention sont mentionnées dans le document DE 42 34 885.- The alkylation and amination to arrive at the compounds of formula (I) according to the invention are mentioned in document DE 42 34 885.
Les exemples qui suivent servent à illustrer l'invention sans toutefois présenter un' caractère limitatif. The examples which follow serve to illustrate the invention without, however, being limiting in nature.
EXEMPLES Exemple 1. Synthèse du 4,5-Diamino-1-(2'-méthoxyéthyl)-pyrazole dichlorhydrateEXAMPLES Example 1. Synthesis of 4,5-Diamino-1- (2'-methoxyethyl) -pyrazole dihydrochloride
Un mélange de 5-benzylamino-3-bromo-1-(2'-méthoxyéthyl)-4- nitropyrazole (4 g, 2,8 mmoles) dans l'ethanol (500 ml) contenant un catalyseur de 10%Pd/C (Johnson-Mattey Type 487, poids sec 0,5 g) et 36% d'acide chlorhydrique (0.57 g, 5,6 mmoles) est hydrogéné dans un Parr Autoclave (1 I) à 1 MPa pendant 1h. Le catalyseur est ensuite enlevé par filtration, lavé à l'ethanol et le filtrat évaporé sous pression réduite. On obtient ainsi un solide orange brut (2,8 g) qui a été trituré dans l'AcOEt (20 ml) pendant 1 h. Le solide est ensuite filtré et lavé avec de l'AcOEt à froid (20 ml) puis séché sous vide afin de donner la 4,5-Diamino-1-(2'- méthoxyéthyl)-pyrazole sous forme de solide beige (0,7 g, 27%). HPLC (pureté) : 99,5% P^F. : 168,1-173,0°C RMN : 1H (400 MHz, d6-DMSO) : 7,34 (1 H, s, NHaro , 5,18 (1 H, slarge, NH), 4,09 (2 H, t, J = 5.5 Hz, CH2N), 3,61 (2 H, t, J = 5.5 Hz, CH2O), 3,23 (3 H, s, OCH3).A mixture of 5-benzylamino-3-bromo-1- (2'-methoxyethyl) -4- nitropyrazole (4 g, 2.8 mmol) in ethanol (500 ml) containing a 10% Pd / C catalyst ( Johnson-Mattey Type 487, dry weight 0.5 g) and 36% hydrochloric acid (0.57 g, 5.6 mmol) is hydrogenated in a Parr Autoclave (1 I) at 1 MPa for 1 hour. The catalyst is then removed by filtration, washed with ethanol and the filtrate evaporated under reduced pressure. A crude orange solid (2.8 g) is thus obtained which has been triturated in AcOEt (20 ml) for 1 h. The solid is then filtered and washed with cold AcOEt (20 ml) then dried under vacuum to give 4,5-Diamino-1- (2'- methoxyethyl) -pyrazole in the form of a beige solid (0, 7 g, 27%). HPLC (purity): 99.5% P ^ F. : 168.1-173.0 ° C NMR: 1 H (400 MHz, d 6 -DMSO): 7.34 (1 H, s, NH aro , 5.18 (1 H, s broad , NH), 4 , 09 (2 H, t, J = 5.5 Hz, CH 2 N), 3.61 (2 H, t, J = 5.5 Hz, CH 2 O), 3.23 (3 H, s, OCH 3 ).
Exemple 2. Composition tinctoriale contenant du 4,5-Diamino-1-(2- méthoxyéthvD-pyrazole dichlorhydrate On.a préparé, la .composition tinctoriale suivante:Example 2. Dye composition containing 4,5-Diamino-1- (2-methoxyethvD-pyrazole dihydrochloride On.a. prepared, the following dye composition:
Support de teintureDye support
Alcool benzylique 2 Polyéthylène glycol 8 OE 3 g Ethanol 18 gBenzyl alcohol 2 Polyethylene glycol 8 EO 3 g Ethanol 18 g
Alkyl (C8-C10) polyglucoside en solution aqueuse à 60% de matière active tamponné par du citrate d'ammonium vendu. sous la dénomination ORAMIX CG110 par SEPPIC 5 g en l'étatAlkyl (C8-C10) polyglucoside in aqueous solution at 60% of active material buffered by ammonium citrate sold. under the name ORAMIX CG110 by SEPPIC 5 g as is
Ammoniaque à 20% de NH3 10 gAmmonia at 20% NH3 10 g
Métabisulfite de sodium 0.205 gSodium metabisulfite 0.205 g
Séquestrant q.s.Sequestering q.s.
Au moment de l'emploi, la composition est mélangée avec un poids égal d'eau oxygénée à 20 volumes (6% en poids).At the time of use, the composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight).
Le mélange obtenu est appliqué sur des mèches de cheveux gris à 90 % de blancs naturels ou permanentes à raison de 10g pour 1g de cheveux. Après 30 min de pose, les mèches sont rincées, lavées avec un shampooing standard, rincées à nouveau puis séchées.The mixture obtained is applied to locks of gray hair containing 90% natural or permanent whites at a rate of 10 g per 1 g of hair. After 30 min of laying, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.
L'évaluation des mèches est effectuée de manière visuelle. Le reflet sur mèche est un rouge cuivré intense. The wicks are evaluated visually. The reflection on the wick is an intense copper red.

Claims

REVENDICATIONS
1. Composition tinctoriale comprenant, dans un milieu de teinture approprié,1. Dye composition comprising, in an appropriate dyeing medium,
• au moins une base d'oxydation 4,5-diaminopyrazole de formule (I) ou les sels d'addition correspondants• at least one 4,5-diaminopyrazole oxidation base of formula (I) or the corresponding addition salts
dans laquelle R1 est un radical alkyle en CrC6 substitué par un ou plusieurs radicaux OR, R étant un radical alkyle en CrC6, • au moins une deuxième base d'oxydation hétérocyclique, et • au moins un coupleur. in which R1 is a C r C 6 alkyl radical substituted by one or more OR radicals, R being a C r C 6 alkyl radical, • at least one second heterocyclic oxidation base, and • at least one coupler.
2. Composition selon la revendication 1 dans laquelle la base d'oxydation hétérocyclique est choisie parmi les bases d'oxydation heterocycliques pyridiniques, pyrimidiniques, pyrazoliques et leurs sels d'addition.2. Composition according to claim 1 in which the heterocyclic oxidation base is chosen from pyridine, pyrimidine, pyrazole heterocyclic oxidation bases and their addition salts.
3. Composition selon la revendication 2 dans laquelle la base d'oxydation hétérocyclique est choisie parmi les bases d'oxydation 3-amino pyrazolo-[1,5-a]- pyridines ou leurs sels d'addition.3. Composition according to claim 2 in which the heterocyclic oxidation base is chosen from the 3-amino pyrazolo- [1,5-a] -pyridine oxidation bases or their addition salts.
4. Composition selon la revendication 3 dans laquelle la base d'oxydation 3-amιno pyrazoιo-[1 ,5-a]-pyridine est cnoisie parmi la pyrazolo [ï75,a]pyridin-3-yiamιne.4. Composition according to claim 3 wherein the oxidation base 3-amιno pyrazoιo- [1,5-a] -pyridine is selected from pyrazolo [ï75, a] pyridin-3-yiamιne.
5. Composition selon l'une quelconque des revendications précédentes dans laquelle le ou les coupleurs sont choisis parmi les métaphénylènediamines, les méta-aminophénols, les metadiphenols, les coupleurs naphtaléniques, les coupleurs heterocycliques et leurs sels d'addition.5. Composition according to any one of the preceding claims, in which the coupler (s) are chosen from metaphenylenediamines, meta-aminophenols, metadiphenols, naphthalene couplers, heterocyclic couplers and their addition salts.
6. Composition selon la revendication 5 dans laquelle le coupleur est choisi parmi les méta-aminophénols. 6. Composition according to claim 5 in which the coupler is chosen from meta-aminophenols.
7. Composition selon l'une quelconque des revendications précédentes dans laquelle R1 représente un radical alkyle en CrC4 substitué par un radical OR, R étant un radical alkyle en C^. 7. Composition according to any one of the preceding claims, in which R1 represents a C r C 4 alkyl radical substituted by an OR radical, R being a C ^ alkyl radical.
8. Composition selon la revendication 7 dans laquelle la base d'oxydation de formule (I) est le 4,5-diamino-1-(2'-méthoxyéthyl)-pyrazole.8. Composition according to claim 7 in which the oxidation base of formula (I) is 4,5-diamino-1- (2'-methoxyethyl) -pyrazole.
9. Composition selon l'une quelconque des revendications 1 à 8 comprenant une base d'oxydation additionnelle choisie parmi les paraphénylènediamines, les bis-phénylalkylènediamines, les para-aminophénols, les ortho-aminophénols et leurs sels d'addition.9. Composition according to any one of claims 1 to 8 comprising an additional oxidation base chosen from paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and their addition salts.
10. Composition selon l'une quelconque des revendications précédentes dans laquelle la quantité de chacune des bases d'oxydation est comprise entre 0,001 à 10 % en poids environ du poids total de la composition tinctoriale. 10. Composition according to any one of the preceding claims, in which the amount of each of the oxidation bases is between 0.001 to 10% by weight approximately of the total weight of the dye composition.
11. Composition selon l'une quelconque des revendications dans laquelle la quantité de chacun des coupleurs est comprise entre 0,001 et 10 % en poids environ du poids total de la composition tinctoriale.11. Composition according to any one of claims in which the amount of each of the couplers is between 0.001 and 10% by weight approximately of the total weight of the dye composition.
12. Composition selon l'une quelconque des revendications 1 à 11 comprenant un agent oxydant. 12. Composition according to any one of claims 1 to 11 comprising an oxidizing agent.
13. Composition selon la revendication 12 dans laquelle l'agent oxydant est choisi parmi le peroxyde d'hydrogène, le peroxyde d'urée, les bromates de métaux alcalins, les persels, les peracides et les enzymes oxydases13. A composition according to claim 12 in which the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes
14. Procédé de teinture d'oxydation des fibres kératiniques caractérisé en ce qu'on applique sur les fibres au moins une composition telle que définie à l'une quelconque des revendications 1 à 11 , et qu'on révèle la couleur à l'aide d'un agent oxydant.14. Process for the oxidation dyeing of keratin fibers, characterized in that at least one composition as defined in any one of claims 1 to 11 is applied to the fibers, and the color is revealed using an oxidizing agent.
15. Procède selon la revendication 14 dans lequel l'agent oxydant est cnoisi parmi le peroxyde d'hydrogène, le peroxyde d'urée, les bromates de métaux alcalins, les persels, les peracides et les enzymes oxydases. 15. The method of claim 14 wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.
16. Procédé selon la revendication 13 ou 14 dans lequel l'agent oxydant est mélangé au moment de l'emploi à la composition telle que définie selon l'une quelconque des revendications 1 à 11.16. The method of claim 13 or 14 wherein the oxidizing agent is mixed at the time of use with the composition as defined according to any one of claims 1 to 11.
17. Procédé selon l'une quelconque des revendications 14 ou 15 dans lequel l'agent oxydant est appliqué sur les fibres sous forme de composition oxydante simultanément ou séquentiellement à la composition telle que définie selon l'une quelconque des revendications 1 à 11. 17. Method according to any one of claims 14 or 15 in which the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously or sequentially with the composition as defined according to any one of claims 1 to 11.
18. Dispositif à plusieurs compartiments ou "kit" de teinture à plusieurs compartiments, dans lequel un premier compartiment contient une composition tinctoriale telle que définie à l'une quelconque des revendications 1 à 11 et un deuxième compartiment contient une composition oxydante.18. Multi-compartment device or multi-compartment dye "kit", in which a first compartment contains a dye composition as defined in any one of claims 1 to 11 and a second compartment contains an oxidizing composition.
19. Utilisation de la composition tinctoriale définie aux revendications 1 à 13 pour la teinture de fibres kératiniques. 19. Use of the dye composition defined in claims 1 to 13 for the dyeing of keratin fibers.
EP02800161A 2001-09-28 2002-09-27 Dyeing composition comprising a diaminopyrazole-type oxidation base, a heterocyclic oxidation base and a coupling agent Withdrawn EP1432393A1 (en)

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FR0112527 2001-09-28
FR0112527A FR2830190B1 (en) 2001-09-28 2001-09-28 DYE COMPOSITION COMPRISING AN OXIDATION BASE OF THE DIAMINOPYRAZOLE TYPE, A HETEROCYCLIC OXIDATION BASE AND A COUPLER
PCT/FR2002/003317 WO2003028688A1 (en) 2001-09-28 2002-09-27 Dyeing composition comprising a diaminopyrazole-type oxidation base, a heterocyclic oxidation base and a coupling agent

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FR2856293B1 (en) * 2003-06-19 2005-08-26 Oreal TINCTORIAL COMPOSITION COMPRISING 4,5-DIAMINO-1- (B-HYDROXYETHYL) -1H-PYRAZOLE AS OXIDATION BASE AND 2,6-BIS- (B-HYDROXYETHYL) -AMINO-TOLUENE AS A COUPLER
US7135046B2 (en) * 2003-06-19 2006-11-14 L'oreal S.A. Dye composition comprising at least one oxidation base chosen from 4,5-diamino-1-(β-hydroxyethyl)-1H-pyrazole and 4,5-diamino-1-(β-methoxyethyl)-1H-pyrazole and the addition salts thereof and at least one coupler chosen from 6-hydroxyindole and the addition salts thereof
FR2915887B1 (en) * 2007-05-09 2009-07-03 Oreal TINCTORIAL COMPOSITION COMPRISING AN AMINOPYRAZOLOPYRIDINE OXIDATION BASE AND A PARTICULAR CARBONYL COMPOUND
FR2915881B1 (en) * 2007-05-09 2009-08-21 Oreal TINCTORIAL COMPOSITION COMPRISING AN AMINOPYRAZOLOPYRIDINE OXIDATION BASE, A COUPLER AND A CATIONIC DIRECT DYE
FR2915886B1 (en) * 2007-05-09 2014-05-09 Oreal TINCTORIAL COMPOSITION COMPRISING A PARTICULAR AMINOPYRAZOLOPYRIDINE OXIDATION BASE, A COUPLER AND A PARTICULAR SURFACTANT
FR2920090A1 (en) * 2007-08-24 2009-02-27 Oreal Composition for coloring keratin fibers, preferably human hair, comprises amino pyrazolopyridine oxidation bases, couplers, and surfactants comprising alkyl ether carboxylic acid and alkyl polyglucosides
FR2920091A1 (en) * 2007-08-24 2009-02-27 Oreal Composition for coloring keratin fibers, preferably human hair, comprises amino pyrazolopyridine oxidation bases, couplers and polyols comprising hydrocarbon chain carrying two hydroxyl functions, where the chain is free from ether function
CN103442682B (en) 2011-02-22 2016-08-31 宝洁公司 Comprise 1-hexyl/heptyl-4,5-diamino-pyrazole and naphthalene-1-phenol and the oxidative dye compositions of derivant thereof
CN103458863B (en) 2011-02-22 2016-05-04 宝洁公司 Comprise 1-hexyl/heptyl-4, the oxidative coloration composition of 5-diamino-pyrazole and benzo [1,3] dioxole-5-base amine and derivative thereof
WO2013058816A1 (en) 2011-02-22 2013-04-25 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a 2-aminophenol and derivatives thereof
MX2013009690A (en) 2011-02-22 2013-12-06 Procter & Gamble Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-di aminopyrazole and a benzene-1,3-diamine and derivatives thereof.
EP2677993B1 (en) 2011-02-22 2018-08-22 Noxell Corporation Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a m-aminophenol and derivatives thereof
US8444714B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-Hexy1/Hepty1-4,5-diaminopyrazole and a benzene-1,3-diol and derivatives thereof
MX2013009685A (en) 2011-02-22 2013-10-28 Procter & Gamble Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-di aminopyrazole and a pyridine and derivatives thereof.
EP2628731B1 (en) 2012-02-16 2014-04-23 The Procter and Gamble Company 1-Hexyl-1H-pyrazole-4,5-diamine hemisulfate, and its use in dyeing compositions
EP2628730B1 (en) 2012-02-16 2017-12-06 Noxell Corporation Telescoping synthesis of 5-amino-4-nitroso-1-alkyl-1h-pyrazole salts
FR3060333B1 (en) * 2016-12-20 2020-01-17 L'oreal SOLID ANHYDROUS COMPOSITION FOR COLORING KERATINIC FIBERS COMPRISING A METABISULPHITE

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE30199E (en) * 1973-11-29 1980-01-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Oxidation hair dyes based upon tetraaminopyrimidine developers
US4003699A (en) * 1974-11-22 1977-01-18 Henkel & Cie G.M.B.H. Oxidation hair dyes based upon tetraaminopyrimidine developers
FR2586913B1 (en) * 1985-09-10 1990-08-03 Oreal PROCESS FOR FORMING IN SITU A COMPOSITION CONSISTING OF TWO SEPARATELY PACKED PARTS AND DISPENSING ASSEMBLY FOR THE IMPLEMENTATION OF THIS PROCESS
DE3843892A1 (en) * 1988-12-24 1990-06-28 Wella Ag OXIDATION HAIR AGENTS CONTAINING DIAMINOPYRAZOL DERIVATIVES AND NEW DIAMINOPYRAZOLE DERIVATIVES
DE4133957A1 (en) * 1991-10-14 1993-04-15 Wella Ag HAIR DYE CONTAINING AMINOPYRAZOLE DERIVATIVES AND NEW PYRAZOLE DERIVATIVES
DE4234887A1 (en) * 1992-10-16 1994-04-21 Wella Ag Oxidation hair dye containing 4,5-diaminopyrazole derivatives as well as new 4,5-diaminopyrazole derivatives and process for their preparation
US5663366A (en) * 1992-10-16 1997-09-02 Wella Aktiengesellschat Process for the synthesis of 4,5-diaminopyrazole derivatives useful for dyeing hair
DE4422603A1 (en) * 1994-06-28 1996-01-04 Wella Ag Agent for oxidative dyeing of hair based on 4,5-diaminopyrazoles and m-phenylenediamine derivatives
DE4440957A1 (en) * 1994-11-17 1996-05-23 Henkel Kgaa Oxidation dye
FR2733749B1 (en) * 1995-05-05 1997-06-13 Oreal COMPOSITIONS FOR DYEING KERATINIC FIBERS CONTAINING DIAMINO PYRAZOLES, DYEING PROCESS, NOVEL DIAMINO PYRAZOLES, AND PREPARATION METHOD THEREOF
DE19543988A1 (en) * 1995-11-25 1997-05-28 Wella Ag Oxidative hair dye composition
FR2750048B1 (en) * 1996-06-21 1998-08-14 Oreal KERATIN FIBER DYEING COMPOSITIONS CONTAINING PYRAZOLO- (1, 5-A) -PYRIMIDINE DERIVATIVES, DYEING PROCESS, NOVEL PYRAZOLO- (1, 5-A) -PYRIMIDINE DERIVATIVES AND THEIR PREPARATION METHOD
US6554871B2 (en) * 1996-10-18 2003-04-29 Wella Ag Oxidative hair dye precursor compositions containing 4-5-diaminopyrazole, 5-amino-2-methylphenol and m-phenylenediamine compounds and method of dyeing hair
FR2767688B1 (en) * 1997-09-01 1999-10-01 Oreal COMPOSITION FOR OXIDATION DYEING OF KERATINIC FIBERS COMPRISING A DIAMINO PYRAZOLE OR A TRIAMINO PYRAZOLE AND A HALOGENATED META-AMINOPHENOL, AND DYEING METHOD
DE19754281A1 (en) * 1997-12-08 1999-06-10 Henkel Kgaa Hair dye preparation
DE19927074A1 (en) * 1999-06-15 2000-12-21 Henkel Kgaa Oxidation color for coloring keratin fibers, especially human hair, contains 5-amino-2-(N-aminoalkyl)amino-pyridine derivative as developer and specified coupler
FR2799961B1 (en) * 1999-10-21 2002-07-19 Oreal KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME
FR2801308B1 (en) * 1999-11-19 2003-05-09 Oreal KERATINIC FIBER DYEING COMPOSITIONS CONTAINING 3-AMINO PYRAZOLO- [1, (- a] -PYRIDINES, DYEING PROCESS, NEWS 3-AMINO PYRAZOLO- [1,5-a] -PYRIDINES
ATE312808T1 (en) * 1999-12-18 2005-12-15 Wella Ag 2-AMINOALKYL-1,4-DIAMINOBENZENE DERIVATIVES AND DYES CONTAINING THESE COMPOUNDS
US6800097B2 (en) * 1999-12-18 2004-10-05 Wella Aktiengesellschaft Substituted 2-aminoalkyl-1,4-Diaminobenzene compounds and oxidation dye precursor compositions containing same
DE19962871A1 (en) * 1999-12-24 2001-06-28 Henkel Kgaa Oxidation color for coloring keratinous fibers, e.g. fur, wool, feathers and especially human hair, with 4,5-diaminopyrazole derivative as developer contains halogenated m-aminophenol as coupler
DE19962872A1 (en) * 1999-12-24 2001-06-28 Henkel Kgaa Oxidation color for coloring keratinous fibers, e.g. fur, wool, feathers and especially human hair, with 4,5-diaminopyrazole derivative as developer contains halogenated m-aminophenol as coupler
DE10032135B4 (en) * 2000-07-01 2004-06-03 Wella Ag Agent containing 2,4-diamino-1- (2-methoxyethoxy) benzene and process for coloring human hair
DE10037158A1 (en) * 2000-07-28 2002-02-07 Wella Ag Oxidative colorant for keratin fibers, especially hair colorant, contains combination of 2,5-diamino-1-(1'-hydroxyalkyl)benzene(s) and 1-substituted 4,5-diaminopyrazole
FR2817551B1 (en) * 2000-12-06 2005-07-01 Oreal NOVEL DIAMINOPYRAZOLE DERIVATIVES AND THEIR USE IN KERATIN FIBER OXIDATION DYE

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO03028688A1 *

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JP2005514331A (en) 2005-05-19
FR2830190B1 (en) 2004-10-01
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FR2830190A1 (en) 2003-04-04
WO2003028688A1 (en) 2003-04-10
CN1596098A (en) 2005-03-16

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