Patent Application
20080196175
The present invention relates to particular dissymmetrical cationic disazo compounds, to dye compositions comprising such compounds as direct dye in a medium that is suitable for dyeing keratin fibres, and also to a process for dyeing keratin fibres using this composition and a multi-compartment device.
It is known practice to dye keratin fibres, and in particular human keratin fibres such as the hair, with dye compositions containing direct dyes. These compounds are coloured and colouring molecules with affinity for the fibres. It is known practice, for example, to use direct dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines and dyes of the azo, xanthene, acridine, azine or triarylmethane type.
These dyes are usually applied to the fibres, optionally in the presence of an oxidizing agent if it is desired to obtain simultaneous lightening of the fibres. Once the leave-in time has elapsed, the fibres are rinsed, optionally washed and dried.
The colorations resulting from the use of direct dyes are temporary or semi-permanent colorations since the nature of the interactions that bind the direct dyes to the keratin fibre, and their desorption from the surface and/or the core of the fibre, are responsible for their poor dyeing power and their poor relative resistance to washing or to perspiration.
Certain direct dyes may moreover have insufficient photostability properties.
An additional difficulty is also encountered which is associated with the fact that, in order to obtain a particular colour, it is necessary in most if not all cases to mix a plurality of dyes. However, not every dye has the same affinity for the fibre, which is reflected either in heterogeneous colorations or in changes in colour over time, for example after the fibres have been washed one or more times, exposed to sunlight, etc.
The aim of the present invention is to provide direct dyes that do not have the drawbacks of the existing direct dyes.
In particular, one of the aims of the present invention is to provide direct dyes with which strong and varied shades can be obtained that are resistant to external attacking factors (bad weather and shampooing), for which there is no observation of any problem of change in colour over time.
These aims and others are achieved by means of the present invention, one subject of which is thus dissymmetrical cationic polyazo compounds of formula (I) below:
Dye1-L-Dye2
in which formula:
Dye1 represents:
Dye2 represents:
in which:
A subject of the present invention is also dye compositions comprising such compounds, as direct dyes, in a medium that is suitable for dyeing keratin fibres.
The invention also relates to a process for dyeing keratin fibres which consists in placing a composition according to the invention in contact with the said wet or dry fibres, for a time that is sufficient to obtain the desired effect.
Finally, the invention relates to a multi-compartment device comprising, in a first compartment, the composition according to the invention, and, in a second compartment, an oxidizing composition.
It has been found that the compounds of formula (I) as defined above show good fastness with respect to external agents such as, especially, shampoos.
Furthermore, these compounds show good photostability.
Moreover, the compounds of formula (I) allow the range of colours obtained to be enhanced, since the members of formula (I) either side of L may be different in colour.
However, other characteristics and advantages of the present invention will emerge more clearly on reading the description and the examples that will be presented.
In the text hereinbelow, unless otherwise indicated, the limits delimiting a range of values are included in that range of values.
Moreover, the keratin fibres forming the subject of the treatment according to the invention are preferably human keratin fibres, in particular the hair.
For the purposes of the present invention, and unless otherwise indicated:
As indicated previously, a first subject of the invention consists of compounds corresponding to the abovementioned formula (I).
As regards the radicals R1, they represent, independently of each other, a C1-C15 alkyl radical; a C2-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a (C1-C6)alkoxy(C2-C6)alkyl radical; an optionally substituted aryl radical, such as phenyl; an optionally substituted arylalkyl radical, such as benzyl; a C2-C6 amidoalkyl radical; a C2-C6 aminoalkyl radical in which the amine is substituted with two optionally substituted C1-C4 alkyl radicals, which may be identical or different. Furthermore, the radical R1 is such that the atom directly linked to the nitrogen atom is a carbon atom.
Preferably, R1 represents a C1-C6 alkyl radical, a C2-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a (C1-C6)alkoxy(C2-C6)alkyl radical; a phenyl radical optionally substituted with at least one chlorine atom, a hydroxyl group, a group RCO—NH— in which R represents a C1-C4 alkyl radical, an amino radical substituted with two C1-C4 alkyl radicals, which may be identical or different; a benzyl radical; a C1-C6 aminoalkyl radical; a C1-C6 aminoalkyl radical in which the amine is substituted with two C1-C4 alkyl radicals, which may be identical or different.
The radicals R2, R3 and R4, independently of each other, more particularly represent:
More preferentially, the radicals R2, R3 and R4, independently of each other, represent:
According to one preferred variant of the invention, the radicals R2, R3 and R4, independently of each other, represent:
According to a second preferred variant of the invention, two radicals R2 borne by adjacent carbon atoms may form, together with the carbon atom to which each is attached, a fused ring optionally substituted preferably with a hydrogen; a methyl radical; a hydroxyl radical; a methoxy radical; an amino radical; a methylamino radical; a dimethylamino radical; a pyrrolidine radical; a sulfonylamino radical.
According to a third preferred variant of the invention, two radicals R3 borne by adjacent carbon atoms can form, together with the carbon atom to which each is attached, a fused ring optionally substituted preferably with a hydrogen; a methyl radical; a hydroxyl radical; a methoxy radical; an amino radical; a methylamino radical; a dimethylamino radical; a pyrrolidine radical; a sulfonylamino radical.
According to one particular document of the invention, the linker L is a chain that isolates each of the chromophores so as to stop the electron delocalization of each of the chromophores.
According to a first variant of the invention, in formula (I), L may be represented by formula (V) below:
in which:
Preferably, the linker represented by formula (V) is attached to the chromophores via a nitrogen or oxygen atom.
According to one particular embodiment of formula (VIa), R5 and R6, independently of each other, are preferably chosen from a C1-C6 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a (C1-C6)alkoxy(C2-C4)alkyl radical, a C2-C6 amidoalkyl radical or a C2-C6 dimethylaminoalkyl radical.
Even more preferably, R5 and R6, independently of each other, represent a methyl, ethyl or 2-hydroxy-ethyl radical.
According to this variant, D and D′, separately, are preferably a C1-C6 alkyl chain that may be substituted, and that is preferably unsubstituted.
According to one particular embodiment of formula (VIb), the ring members E, G, J and M form an imidazolium, pyrazolium, oxazolium or thiazolium ring. In accordance with one even more preferred embodiment of the invention, formula (VIb) represents an imidazolium ring.
According to this particular embodiment, z and t are equal to 0.
In accordance with this embodiment, D and D′ represent a linear or branched, preferably linear, C1-C6 alkyl chain that may be substituted, and that is preferably unsubstituted.
According to one preferred embodiment of formula (VIc), R′5 and R′6 have the same meanings as R5 and R6, independently of these two radicals.
According to this variant, D and D′, separately, are preferably a C1-C6 alkyl chain that may be substituted, and that is preferably unsubstituted.
Preferably, the coefficient v is equal to 1.
According to a second variant of the invention, in formula (I), L represents a C1-C60, preferably C2-C40 and preferably C2-C20 linear or branched divalent hydrocarbon-based chain, to form one or more optionally substituted, optionally aromatic 3- to 7-membered carbon-based rings, this chain being optionally substituted, optionally interrupted with one or more hetero atoms or with one or more groups bearing a hetero atom, preferably chosen from oxygen, nitrogen and sulfur; L not comprising any peroxide, nitro, diazo or nitroso groups. Finally, L does not bear a cationic charge.
According to one more particular embodiment, L is a hydrocarbon-based chain that isolates each of the two members of formula (I) so as to stop electron delocalization.
Examples of linkers L that may be mentioned include alkylene radicals (CnH2n) containing from 1 to 60 carbon atoms, preferably from 2 to 40 carbon atoms and more preferentially from 2 to 20 carbon atoms, optionally substituted and/or interrupted with one or more hetero atoms chosen from oxygen, nitrogen and sulfur and/or from an SO2 or CO group. These alkylene radicals are, for example, propylene, butylene, pentylene, hexylene, etc.
Even more preferably, L is a linear or branched C2-C40 and preferably C2-C20 hydrocarbon-based chain, optionally substituted and/or interrupted with one or more hetero atoms chosen from oxygen, nitrogen and sulfur.
Examples of linkers L that may also be mentioned include the alkylene radicals as defined above, interrupted with a divalent (hetero)aryl radical.
According to this variant, L may be represented by:
The (hetero)arylene radicals are, for example, phenylene or naphthylene, phenanthrylene, triazinyl, pyrimidinyl, pyridyl, pyridazinyl or quinoxalinyl.
It should be noted that L advantageously represents an alkylene radical interrupted with a (hetero)arylene group, optionally substituted and/or interrupted with one or more hetero atoms chosen from oxygen and nitrogen, and/or from one or more SO2 or CO groups.
As examples of alkylene radicals interrupted with a (hetero)arylene group, mention may be made of the following radicals:
in which:
Preferably, in the context of this variant, L represents
the radicals R10, R13, m and n″ being defined as above.
Linkers L that may also be mentioned include the triazines described in WO 03/029359, the alkylenes cited in U.S. Pat. No. 5,708,151 and the alkyl-aryl-alkyls cited in U.S. Pat. No. 5,708,151.
Preferably, L represents a linear or branched C1-C10 alkylene radical, optionally interrupted with one or more hetero atoms, chosen from oxygen, nitrogen and sulfur, optionally substituted with one or more radicals chosen from hydroxyl, C1-C2 alkoxy, C1-C2 dialkylamino, alkylcarbonyl (R—CO—) in which the radical R represents a C1-C4 alkyl radical, a carbamoyl group ((R)2N—CO—) in which the radicals R, independently of each other, represent a hydrogen atom or an alkylsulfonyl radical (R—SO2—) in which the radical R represents a C1-C4 alkyl radical.
More preferably, the linker L represents a C1-C10 alkylene radical, which is preferably linear, optionally interrupted with one or more hetero atoms chosen from oxygen, nitrogen and sulfur, and optionally substituted with one or more radicals chosen from hydroxyl and C1-C2 alkoxy radicals, and an alkylsulfonyl radical (R—SO2—) in which the radical R represents a C1-C4 alkyl radical.
The linker L preferably represents a C1-C10 alkylene radical.
In formula (I), An is an organic or mineral anion or mixture of anions chosen, for example, from halides such as chlorides, bromides, fluorides and iodides; hydroxides; sulfates; hydrogen sulfates; (C1-C6)alkyl sulfates, for instance methyl sulfate or ethyl sulfate; phosphates; carbonates; hydrogen carbonates, perchlorates; acetates; tartrates; citrates, oxalates; (C1-C6)alkylsulfonates such as methylsulfonate; arylsulfonates that are unsubstituted or substituted with a C1-C4 alkyl radical, for instance a 4-tolylsulfonate.
According to one preferred embodiment of the invention, the compounds correspond more particularly to the following formulae:
in which formulae:
These compounds may be obtained especially from similar preparation processes described, for example, in documents BE 662 856, GB 932 022, U.S. Pat. No. 3,173,907 and U.S. Pat. No. 5,708,151.
According to a first embodiment, the process for synthesizing the compounds used in the invention may consist in performing the following steps:
According to this process, a first step of diazotization of a 5- or 6-membered cationic heteroaromatic amine is performed in a manner known to those skilled in the art.
Thus, the said amine is placed in contact with sodium nitrite or nitrosylsulfuric acid. This reaction usually takes place at a temperature of between −15° C. and 30° C. and preferably between −10° C. and 20° C. and at a pH of between 0 and 12.
The reaction conventionally takes place in the presence of a suitable solvent, among which mention may be made of water, alcohols and especially aliphatic alcohols containing up to 4 carbon atoms, organic acids, for example a carboxylic or sulfonic acid containing up to 10 carbon atoms, and/or mineral acids such as hydrochloric acid or sulfuric acid.
Once the reaction has been performed, the product obtained is coupled with a compound of the type W3-L-W3, with W3 advantageously representing an optionally substituted aromatic nucleus. The synthesis of these compounds is known to those skilled in the art (see for example Org. Lett. 2002, 4(4), 581-584; Org. Lett. 2003, 5(6), 793-796).
This reaction is usually performed in the presence of a solvent, which may be the solvent from the preceding step.
The temperature is conventionally between −15° C. and 30° C. and preferably between −10° C. and 20° C. at a pH preferably of between 0 and 8.
The product may be isolated via techniques known to those skilled in the art (precipitation, evaporation, etc.).
According to a second embodiment, the process for synthesizing the compounds used in the invention may consist in performing the following steps:
According to this process, a first step of diazotization of a cationizable heteroaromatic amine is performed in a manner known to those skilled in the art. The conditions for performing such a step have been summarized previously.
Once the reaction has been performed, the product obtained is coupled with a compound of the type W3-L-W3, with W3 advantageously representing an optionally substituted aromatic nucleus. The conditions for performing such a step have been summarized previously.
The resulting product is then quaternized in a usual manner. For example, the product obtained may be placed in contact with an alkyl sulfate such as dimethyl sulfate, diethyl sulfate or dipropyl sulfate, or an alkyl halide or alkylaryl halide such as iodomethane, iodoethane, 2-bromoethanol or benzyl bromide, in the presence of a polar or apolar, protic or aprotic solvent such as dichloromethane, toluene, ethyl acetate or water, at the spontaneous or alkaline pH. The temperature is usually between 10° C. and 180° C. and preferably between 20° C. and 100° C.
The product may be isolated via the techniques known to those skilled in the art (precipitation, evaporation, etc.).
According to a third embodiment, the process for synthesizing the compounds used in the invention may consist in performing the following steps:
The conditions for performing such a synthesis have been summarized previously.
Another subject of the present invention consists of a composition comprising, in a medium that is suitable for dyeing keratin fibres, as direct dye, at least one dissymmetrical cationic polyazo compound of formula (I) below:
Dye1-L-Dye2
in which formula:
Dye1 represents:
Dye2 represents:
in which:
Everything that has been detailed previously regarding formula (I) obviously remains valid and will not be repeated in this part of the text.
The concentration of compounds of formula (I) may range between 0.001% and 5% by weight and preferably between about 0.05% and 2% by weight relative to the total weight of the dye composition.
The composition according to the invention may also comprise an oxidation base. This oxidation base may be chosen from the oxidation bases conventionally used in oxidation dyeing, for example para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Among the para-phenylenediamines that may be mentioned more particularly are, for example, para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxy-ethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxy-ethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)-amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylene-diamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylene-diamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine, N-(4′-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylene-diamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4-amino-phenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene, and the addition salts thereof with an acid.
Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-β-acetylaminoethyloxy-para-phenylenediamine, and the addition salts thereof with an acid, are particularly preferred.
Among the bis(phenyl)alkylenediamines that may be mentioned, for example, are N,N′-bis(β-hydroxy-ethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-ethylenediamine, N,N′-bis(4-aminophenyl)tetramethylene-diamine, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-amino-phenyl)tetramethylenediamine, N,N′-bis(4-methylamino-phenyl)tetramethylenediamine, N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the addition salts thereof with an acid.
Among the para-aminophenols that may be mentioned, for example, are para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethyl-aminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.
Among the ortho-aminophenols that may be mentioned, for example, are 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the addition salts thereof with an acid.
Among the heterocyclic bases that may be mentioned, for example, are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives, and derivatives of pyrazolo[1,2-a]pyrazol-1-one type.
Among the pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-amino-pyridine, 2,3-diamino-6-methoxypyridine, 2-(β-methoxy-ethyl)amino-3-amino-6-methoxypyridine and 3,4-diamino-pyridine, and the addition salts thereof with an acid.
Among the pyrimidine derivatives that may be mentioned are 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-tetraminopyrimidine, 4-hydroxy-2,5,6-triamino-pyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-pyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine; 3-aminopyrazolo[1,5-a]pyrimidin-7-ol; 3-aminopyrazolo-[1,5-a]pyrimidin-5-ol; 2-(3-aminopyrazolo-[1,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-amino-pyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]-pyrimidin-3-yl)(2-hydroxyethyl)amino]ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine and 3-amino-5-methyl-7-imidazolylpropylamino-pyrazolo[1,5-a]pyrimidine, and the addition salts thereof with an acid and the tautomeric forms thereof, when a tautomeric equilibrium exists.
Among the pyrazole derivatives that may be mentioned are the compounds described in patents DE 3 843 892 and 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-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diamino-pyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenyl-pyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triamino-pyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(β-hydroxyethyl)amino-1-methyl-pyrazole, and the addition salts thereof with an acid.
Among the derivatives of pyrazolo[1,2-a]pyrazol-1-one type, mention may be made of compounds such as 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one.
The composition according to the invention may also contain one or more couplers conventionally used for dyeing keratin fibres. Among these couplers, mention may be made especially of meta-phenylene-diamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers.
Examples that may be mentioned include 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(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-dimethylaminobenzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(β-hydroxyethyl)-amino-3,4-methylenedioxybenzene and 2,6-bis(β-hydroxy-ethylamino)toluene and the addition salts thereof with an acid.
In the composition of the present invention, the coupler(s) is (are) generally present in an amount ranging from 0.001% to 10% by weight, and more preferably from 0.005% to 6% by weight, relative to the total weight of the dye composition. The oxidation base(s) is (are) present in an amount preferably ranging from 0.001% to 10% by weight, and more preferably from 0.005% to 6% by weight, relative to the total weight of the dye composition.
In general, the addition salts with an acid that may be used in the context of the dye compositions of the invention for the oxidation bases and couplers are chosen especially from the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
The composition according to the invention may optionally comprise at least one additional direct dye other than the compounds of formula (I). This dye may be chosen from cationic and nonionic species.
Non-limiting examples that may be mentioned include nitrobenzene dyes, azo, azomethine, methine, tetraazapentamethine, anthraquinone, naphthoquinone, benzoquinone, phenothiazine, indigoid, xanthene, phenanthridine, phthalocyanin and triarylmethane-based dyes and natural dyes, alone or as mixtures.
It may be chosen, for example, from the following red or orange nitrobenzene dyes:
The additional direct dye may also be chosen from yellow and green-yellow nitrobenzene direct dyes; mention may be made, for example, of the compounds chosen from:
Mention may also be made of blue or violet nitrobenzene direct dyes, for instance:
in which:
Among the azo direct dyes that may be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714 954.
Among these compounds, mention may be made most particularly of the following dyes:
Among the azo direct dyes that may also be mentioned are the following dyes described in the Colour Index International 3rd edition:
Mention may also be made of 1-(4′-aminodiphenylazo)-2-methyl-4-[bis(β-hydroxy-ethyl)amino]benzene and 4-hydroxy-3-(2-methoxyphenyl-azo)-1-naphthalenesulfonic acid.
Among the quinone direct dyes that may be mentioned are the following dyes:
and also the following compounds:
Among the azine dyes that may be mentioned are the following compounds:
Among the triarylmethane dyes that may be used according to the invention, mention may be made of the following compounds:
Among the indoamine dyes that may be used according to the invention, mention may be made of the following compounds:
Among the dyes of tetraazapentamethine type that may be used according to the invention, mention may be made of the following compounds given in the table below, An being defined as above:
Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin and apigenidin. Extracts or decoctions containing these natural dyes may also be used, and especially henna-based poultices or extracts.
When they are present, the content of additional direct dye(s) in the composition generally ranges from 0.001% to 20% by weight relative to the weight of the composition and preferably from 0.01% to 10% by weight relative to the weight of the composition.
The medium that is suitable for dyeing, also known as the dye support, generally consists of water or of a mixture of water and of at least one organic solvent to dissolve the compounds that are not sufficiently water-soluble.
More particularly, the organic solvents are chosen from linear or branched, preferably saturated monoalcohols or diols containing from 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4-pentanediol), neopentyl glycol and 3-methyl-1,5-pentanediol; aromatic alcohols such as benzyl alcohol and phenylethyl alcohol; glycols or glycol ethers, for instance ethylene glycol monomethyl, monoethyl and monobutyl ether, propylene glycol and its ethers, for instance propylene glycol monomethyl ether, butylene glycol and dipropylene glycol; and also diethylene glycol alkyl ethers, especially of C1-C4, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.
The usual solvents described above, when they are present, usually represent from 1% to 40% by weight and more preferably from 5% to 30% by weight relative to the total weight of the composition.
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 or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric associative polymeric thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance silicones, which may or may not be volatile or modified, film-forming agents, ceramides, preserving agents and opacifiers.
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.
Needless to say, a person skilled in the art will take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
The pH of the dye composition in accordance with the invention is generally between about 3 and 12 and preferably between about 5 and 11. It may be adjusted to the desired value using acidifying or basifying agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems.
Among the acidifying agents that may be mentioned, for example, are mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.
Among the basifying agents that may be mentioned, for example, are aqueous ammonia, alkaline carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds having the following formula:
in which W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.
The dye composition according to the invention may be in various forms, such as in the form of liquids, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and especially human hair.
The composition according to the invention may also comprise at least one oxidizing agent. In this case, the composition is referred to as a ready-to-use composition.
For the purposes of the present invention, the term “ready-to-use composition” means a composition intended to be applied immediately to the keratin fibres, i.e. it may be stored in unmodified form before use or may result from the extemporaneous mixing of two or more compositions.
Usually, the said composition is obtained by mixing the composition according to the invention with an oxidizing composition.
The oxidizing agent may be any oxidizing agent conventionally used in the field. Thus, it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and also enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases, for instance laccases. The use of hydrogen peroxide is particularly preferred.
The content of oxidizing agent is generally between 1% and 40% by weight relative to the weight of the ready-to-use composition, and preferably between 1% and 20% by weight relative to the weight of the ready-to-use composition.
Generally, the oxidizing composition used is an aqueous composition and may be in the form of a solution or an emulsion.
Usually, the composition free of oxidizing agent is mixed with about 0.5 to 10 weight equivalents of the oxidizing composition.
It should be noted that the pH of the ready-to-use composition is more particularly between 4 and 12 and preferably between 7 and 11.5.
The pH of the composition may be adjusted using an acidifying or basifying agent chosen especially from those mentioned previously in the context of the description according to the invention.
A subject of the invention is also a dyeing process that includes the application of a dye composition according to the invention to wet or dry keratin fibres.
The application to the fibres of the dye composition comprising the compound(s) of formula (I) or the addition salts thereof with an acid, optionally at least one oxidation base optionally combined with at least one coupler, and optionally at least one additional direct dye, may be performed in the presence of an oxidizing agent.
This oxidizing agent may be added to the composition comprising the compound(s) of formula (I) and the optional oxidation bases, couplers and/or additional direct dyes, either at the time of use or directly onto the keratin fibre.
The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
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 fibres preferably ranges between 4 and 12 approximately and even more preferably between 7 and 11.5. It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres and as defined above.
The composition that is finally applied to the keratin fibres may be in various forms, such as in the form of liquids, creams or gels or in any other form that is suitable for dyeing keratin fibres, more particularly human keratin fibres and especially the hair.
According to one particular embodiment, the composition according to the invention is free of oxidation base and of coupler.
The composition applied may optionally comprise at least one oxidizing agent.
The composition is thus applied to the wet or dry keratin fibres and is then left for a leave-in time that is sufficient to obtain the desired coloration.
Whatever the variant adopted (with or without oxidizing agent) the leave-in time is generally between a few seconds and 30 minutes and preferably between 3 and 15 minutes.
The temperature at which the composition is left to act is generally between 15 and 220° C., more particularly between 15 and 80° C. and preferably between 15 and 40° C.
After the leave-in time, the composition is removed by rinsing with water, optionally followed by washing with a shampoo, and then optionally drying.
Another subject of the invention is a multi-compartment device or dyeing “kit” in which a first compartment contains the dye composition of the invention and a second compartment contains the oxidizing composition. This device may be equipped with a means for applying the desired mixture to the hair, such as the devices described in patent FR-2 586 913.
The examples that follow serve to illustrate the invention without, however, being limiting in nature.
Dye 1 is synthesized according to the third embodiment. The implementation conditions of a synthesis of this kind were summarized earlier on.
Compound 1 is brought into contact with NaNO2 and dilute hydrochloric acid at a temperature of between 0 and 5° C. for one hour.
Then 2 mol equivalents of N-methylimidazole are added and the pH is adjusted to 5 by adding aqueous sodium hydroxide solution, and compound 2 is recovered.
The product is separated by filtration.
This compound 2 is subsequently contacted with (CH3)2SO4 in ethyl acetate at 50° C. for 6 hours. At the outcome of the reaction, dye 1 is recovered.
Dye 1 is recovered by filtration.
The mixture obtained is applied to locks of grey hair containing 90% white hairs. After leaving in for 20 minutes, the locks of hair are rinsed, washed with a standard shampoo, rinsed again and then dried.
A chestnut shade is obtained and the colour is shampoo-fast and light-fast.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0452785 | Nov 2004 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP05/13981 | 11/24/2005 | WO | 00 | 11/26/2007 |
| Number | Date | Country | |
|---|---|---|---|
| 60634527 | Dec 2004 | US |
