Tinctorial composition comprising at least one direct dye with mixed chromophores

Translation of description of equivalent WO 2004112737 A2

DYEING COMPOSITION CONTAINING AT LEAST ONE DIRECT DYE A MIXED CHROMOPHORES

The invention relates to a dyeing composition comprising a direct dye consisting of different chromophores. The invention also relates to the dyeing process using this composition and the use of this composition for dyeing keratin fibers.

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 para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, combined with oxidizing products, can give rise, by a process of oxidative condensation, to colored compounds.

We also know that one can vary the shades obtained by combining these oxidation bases with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds.

The variety of molecules used in oxidation bases and couplers allows to obtain a rich palette of colors.

This oxidation dyeing method consists in applying to the keratin fibers, bases or a mixture of bases and couplers with hydrogen peroxide as oxidizing agent, in leaving to stand and then rinsing the fibers. The colorations resulting therefrom are permanent, strong and resistant to external agents, including light, bad weather, washing, perspiration and rubbing. Generally applied at basic pH, it enables a dyeing and simultaneously lightening of the fiber which is reflected in practice by the possibility of obtaining a lighter final color than the original color. In addition, the lightening of the fiber has the advantageous effect of generating a unified color in the case of gray hair, and in the case of naturally pigmented hair, of bringing out the color, that is, to make it more visible.

It is also known to dye keratin fibers by direct dyeing. The process conventionally used in direct dyeing comprises applying to the keratin fibers direct dyes, which are colored and coloring molecules that have affinity for the fibers, leaving the pause, and then rinsing the fibers. It is known for example, to use direct dyes nitro benzene-type, anthraquinone dyes, nitropyridine dyes of the azo, xanthene, acridine, azine or triarylmethane.

Some direct dyes may be combined with oxidizing agents which allows to obtain a lightening of the fiber at the time of coloring. For example, EP 810 851 describes dye compositions containing direct dyes comprising at least one quaternized nitrogen atom of the azo or azomethine, which can be mixed extemporaneously at basic pH with an oxidizing composition. The colorations resulting from the use of direct dyes are temporary or semi-permanent colorings since the nature of the interactions that bind the direct dyes to the keratin fiber, and their desorption from the surface and / or the heart of the fiber are responsible their low dyeing power and their poor resistance to washing or perspiration. These direct dyes may be comprised of one or more chromophores, which are identical or different. consist of several dye chromophores are described for example in FR 1540423, EP 1133975, EP 1133976, US 5708151, WO 02-078596. All these dyes allow to obtain chromatic colors, ie colors very reflections as raw orange, yellow wines, red wines, etc.

For a non-chromatic color, direct dyes are used in mixture. In particular, for obtaining basic colors, ie colors ranging from black to natural blond through the chestnuts are used dye compositions generally comprising a mixture of blue or violet direct dyes and direct dyes yellow or orange. The problem with these blends is that different dyes do not have the same affinity for the hair or the same resistance to external agents which results in time an alteration of the initial color. For example, after several shampoos, a shift can be observed coloration to purple or yellow depending on the affinity of each of the dyes to the keratin fiber.

The purpose of the present invention is to provide direct dyes to overcome the drawbacks of existing direct dyes. In particular, an object of the present invention is to provide direct dyes to obtain basic shades without color shift problem in time. Another object of the invention is to provide direct dyes that can dye keratin fibers as strongly as oxidation dyes, which are as stable as they light, weatherproof, washing and perspiration, and also sufficiently stable in the presence of oxidizing and reducing agents to be able to simultaneously obtain lightening of the fiber.

This object is achieved with the present invention which relates to a dye composition comprising, in a suitable dyeing medium, a mixed dye consisting of several chromophores linked together by a connecting arm, at least two of these chromophores being different, the chromophore being selected such that the mixed dye, in a composition to 4,7x10^"4 mol of dye for 100 g of composition, results in a standardized coloration test on a lock of hair containing 90% white hairs, the following values ​​in the colorimetric system L * a * b * if a *> 0 and b * ≥ 0, then a * belongs to the range [0; 20] and b * belongs to the range [0; +40] If a * <0 and b * ≥ 0, then a * belongs to the range [-27; 0] and b * belongs to the range [0; 40] if a * ≥ 0 and b * <0, then a * belongs to the range [0; 9] and b * belongs to the range [-10; 0] if a * <0 and b * <0, then a * belongs to the range [-14; 0] and b * belongs to the range [-21; 0]. The invention also relates to a dyeing method using this composition.

Another object 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, in particular to obtain good shampoo fastness.

Finally, the invention relates to mixed dyes as defined above.

The composition of the present invention makes it possible to obtain a coloration of keratin fibers in basic shades ranging from black to natural blond and resistant to various external agents, especially shampoos. It also enables to avoid color change problems in time.

The measurement of L * a * b * as defined herein must be performed from a reference composition which con itient:

mixed dye useful for the invention 4.7x 10 ι-4 mol

(C8 / C10 50:50) polyglucoside (2) 10 g aqueous 60% solution buffered sold under the <img id="imgf000005_0002" he="33" wi="133" file="imgf000005_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

The reference composition is applied at room temperature on natural hair strands 90% white (T = 23 ° C ± 3 ° C). After 20 minutes, the locks are rinsed and dried. The values ​​of L * a * b^* are measured using a CM2002 colorimeter, illuminant D65-10⁰ SCI.

In the L * a * b *, the three parameters denote respectively the intensity (L *), hue (a *) and saturation (b *). Under this system, the more the value of L *, the greater the color lighter or less intense. Conversely, the more the value of L * is small, the color is dark or very intense, a * and b * indicate two color axes, a * indicates the axis of green / red color axis and b * color blue / yellow.

According to a preferred embodiment, the values ​​of L * a * b of the mixed dye useful in the present invention are such that: if a *&gt; 0 and b *&gt; 0, then a * belongs to the range [0; 15] and b * belongs to the range [0; +30] If a * &lt;0 and b *&gt; 0, then a * belongs to the range [-20; 0] and b * belongs to the range [0; 30] if a *&gt; 0 and b * &lt;0, then a * belongs to the range [0; 6] and b * belongs to the range [-6; 0] if a * &lt;0 and b * &lt;0, then a * belongs to the range [-10; 0] and b * belongs to the range [-15; 0].

Preferably, the chromaticity C * calculated using the formula below is less than 20. <img id="imgf000005_0001" he="9" wi="58" file="imgf000005_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

According to the present invention, the term "chromophore" means a radical derived from a dye, ie a radical derived from a molecule absorbing in the visible range of the radiation (between 400 and 800 nm).

Within the meaning of the present invention, the chromophores are said to be different when they differ in their chemical structure. Such chromophores may be chromophores from different families or one family on the condition that have different chemical structures. For example, the chromophore may be selected from the family of azo dyes but differ in the chemical structure of the constituting radicals. By way of useful chromophores in the present invention include the radicals derived from acridine dyes, acridones, anthranthrones, anthrapyrimidines, anthraquinones, azines, azos (azo), azomethines, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles , benzoquinones, bisazines, bis isoindolines, carboxanilides, coumarins, cyanines (azacarbocyanine, diazacarbocyanine, diazahémicyanine, hemicyanin, tétraazacarbocyanine), diazines, diketopyrrolopyrrole, dioxazine, diphenylamines, diphenylmethanes, dithiazines, flavonoids such as flavanthrones and flavones, fluorindines, formazans, hydrazones in especially arylhydrazones, hydroxyketones, indamines, indanthrones, indigo and pseudo-iondigoïdes, indophenols, indoanilines, isoindolines, isoindoline, isoindolinone, isoviolanthrones, lactones, methines, naphthalimides, naphthanilides, naphtholactames, naphthoquinones, nitro include nitro (hetero) aromatic, oxadiazoles, oxazines, périlones, perinone, perylene, phenazines, phenothiazines, phthalocyanine, polyene / carotenoids, porphyrins, pyranthrones, pyrazolanthrones, pyrazolones, pyrimidinoanthrones, pyronines, quinacridones, quinolines, quinophthalones, squaranes, stilbene, tétrazoliums, thiazine, thioindigo, thiopyronines, triarylmethane, xanthene.

As of useful chromophores in the present invention can still be made more particularly the radicals derived from acridine dyes, acridone, anthranthrones, anthraquinone, azine, azos (azo), azomethine, benzanthrones, benzoquinones, bisazines, cyanines (azacarbocyanine, diazacarbocyanine, diazahémicyanine, hemicyanin, tétraazacarbocyanine), diazines, diketopyrrolopyrrole, dioxazine, diphenylmethanes, dithiazines, flavonoids such as flavanthrones and flavones, formazans, especially hydrazones arylhydrazones, indamines, indanthrones, indigo and pseudo-iondigoïdes, indophenols, indoanilines, isoviolanthrones, methines, naphthalimides, naphtholactames, naphthoquinones, nitro including nitro- (hetero) aromatic, phenazines, phenothiazines, phthalocyanin, polyenes / carotenoids, porphyrins, pyrazolones, quinacridone, quinophthalone, ftétrazoliums, thiazine, thioindigo, thiopyronines, triarylmethanes, xanthenes.

From nitro chromophores used in the invention include but not limited to radicals derived from the following dyes: -1, 4-diamino-2-nitrobenzene -1-amino-2 nitro-4-β- hydroxyéthylaminobenzène -1- amino-2 nitro-4-bis (β-hydroxyethyl) -aminobenzene -1,4-bis (β-hydroxyethylamino) -2-nitrobenzene -1-β-hydroxyethylamino-2-nitro-4-bis (β-hydroxyethylamino) -benzene -1-Β-hydroxyethylamino-2-nitro-4-aminobenzene

-1-Β-hydroxyethylamino-2-nitro-4- (ethyl) (β-hydroxyethyl) -aminobenzene

-1-Amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene

-1-Amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene-1, 2-Diamino-4-nitrobenzene

-1-Amino-2-β-hydroxyethylamino-5-nitrobenzene

-1,2-Bis- (β-hydroxyethylamino) -4-nitrobenzene

-1-Amino-2-tris (hydroxymethyl) methylamino-5-nitrobenzene

-1-Hydroxy-2-amino-5-nitrobenzene -1 -hydroxy-2-amino-4-nitrobenzene

-1-Hydroxy-3-nitro-4-aminobenzene

-1-Hydroxy-2-amino-4,6-dinitrobenzene

-1-Β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene

-1-Methoxy-2-β-hydroxyethylamino-5-nitrobenzene -1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene

-1-Β, γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene

-1-Β-hydroxyethylamino-4-β, γ-dihydroxypropyloxy-2-nitrobenzene

-1-Β, γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene

-1-Β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene -1 -β-hydroxyethylamino-3-methyl-2-nitrobenzene

-1-Β-aminoethylamino-5-methoxy-2-nitrobenzene

-1-Hydroxy-2-chloro-6-ethylamino-4-nitrobenzene

-1-Hydroxy-2-chloro-6-amino-4-nitrobenzene

-1-Hydroxy-6-bis (β-hydroxyethyl) -amino-3-nitrobenzene -1 -β-hydroxyethylamino-2-nitrobenzene

-1-Hydroxy-4-β-hydroxyethylamino-3-nitrobenzene.

Among the azo chromophores used in the invention include radicals derived from the cationic azo dyes described in patent applications WO 95/15144, WO-95/01772 and EP-714954. It may also be made from azo chromophores the following compounds, described in the Colour Index International 3^e edition:

Disperse Red 17

-Acid Yellow 9

-Acid 1 -Basic Black Red 22

-Basic Red 76

-Basic Yellow 57 -Basic Brown 16

-Acid Yellow 36

-Acid Orange 7

-Acid -Acid Red 33 Red 35

-Basic Brown 17

-Acid Yellow 23

-Acid Orange 24

Disperse Black 9. It is also made of 1- (4'-aminodiphenylazo) -2-methyl-4bis- (β- hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-méthoxyphényIazo) -1-naphthalene sulfonic.

Among the quinone chromophores include the radicals derived from the following dyes: Disperse Red 15

-Solvent Violet 13

-Acid Violet 43

Disperse Violet 1

Disperse Violet 4 Disperse Blue 1

Disperse Violet 8

Disperse Blue 3

Disperse Red 11

-Acid Disperse Blue 62 Blue 7

Basic Blue 22

Disperse Violet 15

Basic Blue 99 and the following compounds: -N -1-méthylmorpholiniumpropylamino-4-hydroxyanthraquinone

-1-Aminopropylamino-4-méthylaminoanthraquinone

-1-Aminopropylaminoanthraquinone

-5-Β-hydroxyethyl-1,4-diaminoanthraquinone

-2-Aminoéthylaminoanthraquinone -1, 4-Bis (β, γ-dihydroxypropylamino) anthraquinone.

Among the azine chromophores include the radicals derived from the following dyes: Basic Blue 17

-Basic Red 2.

Among the triarylmethane chromophores used in the invention include the radicals derived from the following dyes: Basic Green 1

-Acid Blue 9

-Basic Violet 3

-Basic Violet 14

Basic Blue 7 Violet -Acid 49

Basic Blue 26

-Acid Blue 7

Among the indoamine chromophores used in the invention include the radicals derived from the following dyes: 2-β-hydroxyethylamino-5- [bis (β-4'-hydroxyethyl) amino] anilino-1, 4-benzoquinone

-2-Β-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1, 4-benzoquinone

-3-N (2'-Chloro-4'-hydroxy) phenyl-acetylamino-6-methoxy-1, 4-benzoquinone imine

-3-N (3'-Chloro-4'-methylamino) phenyl-ureido-6-methyl-1, 4-benzoquinone imine

-3- [4'-N- (Ethyl carbamylméthyl) -amino] -phenyl-ureido-6-methyl-1, 4-benzoquinone imine.

We can also mention the chromophores disclosed in US

5888252, EP 1133975, WO 03/029359, EP 860 636, WO 95/01772, WO 95/15144,

EP 714954. It also included those mentioned in the encyclopedia "The chemistry of synthetic dye" K. VENKATARAMAN, 1952 Academy press vol 1 to 7 in the encyclopedia "Kirk Othmer" "Chemical technology" Chapter "dyes and Dye intermediate, "1993, Wiley and sons, and various section of the encyclopedia

"Ullmann's Encyclopedia of Industrial Chemistry" 7th edition, Wiley and sons.

Preferably, the chromophores are selected from chromophores azos (azo) dyes, xanthene dyes, hydrazones and including arylhydrazones, phenothiazines, acridines, cyanines as tetraazacarbocyanines, anthraquinones, methines, azomethines, diketopyrrolopyrroles, the indigo, especially nitro the nitro (hetero) aromatic.

According to one embodiment even more particular, the chromophores are selected from chromophores azos (azo), hydrazones and including arylhydrazones, cyanines as tetraazacarbocyanines, anthraquinones, methines, azomethines, nitro including nitro -

(Hetero) aromatic. According to one particular embodiment, the mixed dye comprises at least one chromophore which, alone, has a value of a * and b positive * or null and at least one chromophore which, alone, has a value of a * and b * negative. According to a second particular embodiment, the mixed dye comprises at least one chromophore which only has a value of a positive * or zero and a value of b negative * or null and at least one chromophore which, alone, has a value of * a negative and positive value of b *.

In a third particular embodiment, the mixed dye comprises at least one chromophore, which alone has a value of a * and b * is positive or zero and at least one chromophore having a value of a positive * or null and a value b * negative.

In a fourth embodiment, the mixed dye comprises at least one chromophore which, alone, has a value of a * and b positive * or null and at least one chromophore which, alone, has a value of a negative * and positive value of b *.

In a fifth embodiment, the mixed dye comprises at least one chromophore which, alone, has a value of a positive * or zero and a value of b negative or zero * and at least one chromophore which alone has a value a * and b * negative.

According to a sixth particular embodiment, the mixed dye comprises at least one chromophore which, alone, has a value of a * and b negative * or null and at least one chromophore which, alone, has a value of a negative * and positive value of b *. According to the present invention, the mixed dye preferably comprises two to four different chromophores, preferably two or three different chromophores.

Preferably, the mixed dye of the invention corresponds to the formula

Col1 Col-L-2 wherein L is a cationic linker or not, and Col 1 Col 2 are different chromophores.

In a particular embodiment of the invention, the mixed dye is a cationic dye. Is meant within the scope of the invention by cationic mixed dye a dye whose cationic charge may be an integral part of the chromophore and / or of the connecting arm, or a dye whose cationic charge is present via a substituent of the chromophore and / or the connecting arm. According to a particular embodiment, the mixed dye comprises at least one cationic chromophore, preferably at least two cationic chromophores, the cationic charge forms an integral part of the chromophore or being carried by a substituent, the linking arm being or noncationic , According to another particular embodiment, the mixed dye is at least di-cationic, the cationic charge being borne by the chromophore and / or by the linker. In a variant of this embodiment, at least two chromophores are cationic chromophores, the link arm being cationic or not. The cationic chromophores are usually chromophores comprising, directly or as a substituent, a quaternized nitrogen atom.

These cationic chromophores are, for example chromophores comprising, directly or as a substituent, a radical alkyl ammonium, imidazolium, pyridinium, quinolinium, acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium (or indazolium) benzopyridazinium, benzoquinolium, benzothiazolium benzotriazolium, benzoxazolium, bi -pyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, indolium, isoquinolinium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, phenazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinoimidazolium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium , thiopyrylium, triazolium, xanthylium.

Preferably, such chromophores include, directly or as a substituent, a radical alkyl ammonium, imidazolium, pyridinium, acridinium, benzimidazolium, benzopyrazolium (or indazolium) benzopyridazinium, bi-pyridinium bis-tetrazolium, imidazopyridinium, indolium, naphthoimidazolium, naphthopyrazolium, phenazinium, pyrazinium, pyrazolium, pyridinoimidazolium, xanthylium.

Examples of useful cationic chromophores in the present invention have been mentioned above, other examples are given in the patent applications WO 95/01772, WO 95/15144, EP714 954, EP 318 294, WO 03/029359,

Alternatively, the mixed dye comprises cationic azo chromophores. Such chromophores are described for example in EP 0 850 636, FR2788433, EP 920 856, WO 9948465, FR2757385, EP-850 637, EP 918 053, WO9744004, FR2570946, FR2285851, DE 2538363, FR2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943, FR 1221122, DE4220388, DE4137005, WO0166646, US5708151, WO9501772, WO9515144, GB 1,195,386, US 3,524,842, US 5,879,413, EP1062940, EP1133976, GB 738,585, DE 2,527,638, FR 2275462, GB 1974-27645, Acta Histochem. (1978), 61 (1), 48-52, Tsitologiya (1968), 10 (3), 403-5, Zh. Obshch. Khim. (1970), 40 (1), 195-202, Ann. Chim. (Rome) (1975), 65 (5-6), 305-14, Journal of the Chinese Chemical Society (Taipei) (1998), 45 (1), 209-211, Rev. Roum. Chim. (1988), 33 (4), 377-83, Text. Res. J. (1984), 54 (2), 105-7, Chem. Ind. (Milan) (1974), 56 (9), 600-3, Khim. Tekhnol. (1979), 22 (5), 548-53, Ger. Monatsh. Chem. (1975), 106 (3), 643-8, MRL Bull. Res. Dev. (1992), 6 (2), 21-7, ϋhua Jianyan, Huaxue Fence (1993), 29 (4), 233-4, Ann. Chim. (Rome) (1975), 65 (5-6), 305-14, Dyes Pigm. (1992), 19 (1), 69-79, Dyes Pigm. (1989), 11 (3), 163-72. In the context of the present invention, the term "arm" an atom or group of atoms separating the chromophores from the mixed dye. The atoms of the linker arm must be such that the position on the scale of wavelengths of the absorption maxima or chromophores constituting the mixed dye must not be modified by more than 30 nanometers relative to the maxima absorption of each of the chromophores taken separately, ie not connected by the connecting arm, more particularly more than 15 n, preferably more than 10 nm. The linker arm may be cationic or noncationic.

Alternatively, the linker arm D is an atom or group of atoms that isolates each of the chromophores so as to stop the electron delocalization of each of the chromophores.

The linker is for example a hydrocarbon chain Cι-C₂₀, Preferably C Cι₄Even more preferably CC₆Linear, branched or cyclic, optionally substituted, one or more of the carbon atoms of the chain may be replaced by at least one heteroatom such as sulfur, nitrogen, oxygen, and / or by at least one group comprising a heteroatom such as the carbonyl group, the hydrocarbon chain may be unsaturated or contain at least one optionally substituted alkylene radical; an optionally substituted arylene radical; a divalent terephthalamide optionally substituted; an optionally substituted heterocyclic divalent radical, such as for example a divalent triazine radical, a radical -NH-CO-.

The hydrocarbon chain, but also of alkyl (ene) may be substituted (e) (s) for example by at least one hydroxy, alkoxy especially C1-C6 alkyl, a (poly) hydroxyalkoxy, C1-C6, amino, alkylamino having one or more alkyl radicals C1-C6 identical or not, optionally bearing at least one hydroxyl group, at least one halogen, etc. As an example of connecting arms include alkylene radicals (C_notH_2n) Comprising more especially 1 to 14 carbon atoms, and preferably 1 to 6 carbon atoms, for example methylene, ethylene, propylene, etc., optionally substituted as indicated above, optionally interrupted by at least one heteroatom such as sulfur, nitrogen, oxygen, and / or a group comprising a heteroatom such as carbonyl group; the radicals (hetero) arylene optionally substituted, for example phenylene or naphthylene, phenanthrylene, triazinyl, pyrimidinyl, pyridinyl, pyridazinyl, quinoxalinyl, optionally substituted; alkyl-aryl-alkyl, alkyl-heteroaryl-alkyl, the alkyl radicals of parts comprising more particularly from 1 to 6 carbon atoms.

The radicals (hetero) arylene above mentioned may be substituted by one or more alkyl C1-C6; C1-C6; (Poly) hydroxyalkoxy, C2-C6; amino; amino substituted by one or more alkyl radicals identical or not optionally bearing C1-C6 alkyl with at least one hydroxy group and / or aryl radical C 6 optionally substituted by one or more alkyl C1-C6 alkoxy, C1 C6 (poly) hydroxyalkoxy, C2-C6, amino, amino substituted by one or more alkyl radicals identical or different C1-C6 alkyl optionally bearing at least one hydroxyl group; trifluoromethyl; cyano; alkylamido including C1 through C6; RCOO- R is alkyl C1-C6. By way of more specific examples there may be mentioned:

<img id="imgf000013_0001" he="64" wi="156" file="imgf000013_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000014_0001" he="75" wi="155" file="imgf000014_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" /> wherein R may be H, CF₃, CO₂Me, CO₂And, CN, CONH₂, R 'represents a hydrogen atom, an alkyl radical -C₈Optionally substituted by one or more hydroxyl, alkoxy CC₂(Poly) hydroxyalkoxy C₂-C₄, Amino, (di) alkylamino CC₂ or optionally substituted aryl, and R "represents a hydrogen atom, an alkyl radical CC₄Optionally substituted by one or more hydroxyl, alkoxy CC₂(Poly) hydroxyalkoxy C₂-C₄, Amino, (di) alkylamino, C_rC₂ Optionally substituted aryl, n is greater than 0, more particularly between 1 and 10, preferably between 1 and 5; Pélectroneutralité compounds being provided by one or more cosmetically acceptable anions.

By way of link arms, there may be mentioned triazines described in WO03 / 029 359, the alkylene cited in US 5 708 151, the Alkyl-aryl-Alkyl cited in US 5 708 151.

Note that any alkylene group in the main chain connecting Col1 / Col2 within the meaning of the present invention is considered a connecting arm.

An is an organic or inorganic anion, for example selected from the halides such as chlorides, bromides, fluorides, iodides; the hydroxide; sulfates; hydrogensulfates; alkyl (CC₆) Sulfates such as for example methyl or

Péthylsulfate; phosphates; carbonates; hydrogencarbonates; perchlorates; acetates; tartrates; citrates, oxalates; the alky Cr C₆) Sulfonates such as methylsulfonate; substituted aryl sulphonates or not by alkyl CC such as for example 4-toluylsulfonate.

For example, the mixed dye may be represented by the formula <img id="imgf000015_0001" he="33" wi="99" file="imgf000015_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein L is a linker as defined above, R1 and R1 'are independently selected from alkyl, preferably C1-C6, optionally substituted by one or more hydroxyl, alkoxy, C-_t-C₂(Poly) hydroxyalkoxy C₂-C₄, Amino, (di) alkylamino, C ^ C "or optionally substituted aryl and R2 and R2 'are independently selected from an alkyl radical -C₆Optionally substituted by one or more hydroxy, alkoxy, C-ι-C₂(Poly) hydroxyalkoxy C₂C, amino, (di) alkylamino dC₂ ; an optionally substituted phenyl radical; An represents one or more identical or different anions, monovalent or polyvalent, as defined previously.

Examples of dyestuffs of this formula include;

<img id="imgf000015_0002" he="77" wi="96" file="imgf000015_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

<img id="imgf000016_0001" he="137" wi="94" file="imgf000016_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

The composition of the present invention generally contains an amount of mixed dye of between 0.001 and 20% based on the total weight of the composition. Preferably, this amount is between 0.005 and 10% and even more preferably between 0.01 and 5% relative to the total weight of the composition.

The dyes of the invention may be prepared by chemical reactions known per se from functionalized chromophores capable of reacting with the chosen linker arm. For example, when the linker is a triazine group then the chromophore must contain a reactive amino group, OH or SH and synthesis can be performed in the diagrams below. <img id="imgf000017_0001" he="66" wi="144" file="imgf000017_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

In a first step, a first chromophore is mixed with the compound forming or capable of forming the linker, for example cyanuric chloride. When this reaction is complete, the reaction mixture is added a second chromophore. This sequence may be repeated as many times as there are reactive groups on the compound forming or capable of forming the linker.

For the preparation of a mixed dye C0H C0I-L-2, the molar ratio relative to dye 1 by connecting arm is generally between 10: 1 and 0.5: 1, preferably 1: 1. This report may be modified when more than one linker or several chromophores.

The reaction temperature is generally between -10 ° C and

+ 130 ° C, preferably between -5 ° C and 100 ° C. The reaction time depends on the reactivity of the species present and the reaction temperature. In general, the reaction time is between 10 minutes and 8 hours, preferably between 30 minutes and 4 hours.

The pH of the reaction is generally between 3 and 10, preferably between 4 and 8.

The reaction may be conducted in water and / or organic solvents, alone or as mixtures. Several publications describe the reaction of chemical association between identical chromophores. Include such documents ISBN 0901956759, WO 0278596, DE19845640,

WO03 / 029359, US 5,708,151.

In addition, the reactions or the reactions of a linker with two different compounds, dyes, or not, have been described in the literature, for example in WO03 / 029359, DE3335956, WO0330909, WO0318021, Journal of Medicinal Chemistry 43 (9 ), 2000, 1892-1897; Chemiker Zeitung 117 (7-8), 1987, 241-5. The dye composition according to the invention can further contain one or more direct dyes conventionally used in the field of dyeing keratin fibers. As such, there may be mentioned nitro dyes of the benzene series, azo direct dyes, methine direct dyes. These direct dyes may be nonionic, anionic or cationic in nature. Preferably, these additional direct dyes are cationic in nature.

The dye composition of the invention can contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratin fibers.

Among the oxidation bases, mention may be made of para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts

Among these couplers, mention may be made especially phenylenediamines, meta-arninophénols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

In the composition of the present invention, the couplers are each present in an amount between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%. The oxidation bases present in the composition of the invention are generally present in an amount ranging from 0.001 to 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%.

In general, the addition salts of the oxidation bases and couplers used in the context of the invention are chosen from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, alkyl sulfates such as methyl or ethyl sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the addition salts with a base, such as sodium hydroxide, potassium hydroxide, the ammonia, amines or alkanolamines. The medium suitable for dyeing, also called dye carrier is a cosmetic medium consisting of water or a mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently soluble in the water. As organic solvent, there can be mentioned for example lower alkanols CC, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyéthanoI, propylene glycol, propylene glycol monomethyl, monoethyl and monomethyl ether, and aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvents are preferably present in proportions preferably 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.

The dye composition according to the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic surfactants, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and especially associative thickeners anionic, cationic, nonionic and amphoteric surfactants, antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersants, conditioning agents such as for example, volatile or nonvolatile silicones, modified or unmodified, film-forming agents, ceramides, preservatives and opacifiers.

The above adjuvants are generally present in an amount for each ranging from 0.01 to 20% by weight relative to the weight of the composition. Of course, the man of the art care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the oxidation dye composition according to the invention are not, or not substantially impaired by the envisaged addition.

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 using acidifying or alkalizing agents usually used for dyeing keratin fibers, or alternatively using standard buffer systems.

Among the acidifying agents, mention may, for example, the inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, and sulphonic acids.

Among the alkalizing agents include, for example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium or potassium hydroxides and compounds formula (II): N WN κ \

^R°%!) In which W is a propylene residue optionally substituted with a hydroxyl group or an alkyl radical CC₄ ; R_at, R_c and R_d, Identical or different, represent a hydrogen atom, an alkyl radical CC₄ or hydroxyalkyl, Cι ~ C₄.

The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels or any other form suitable for dyeing keratin fibers, and especially human hair. The method of the present invention is a method which comprises applying to the fibers the composition according to the present invention as defined above. In a particular embodiment, the composition of the invention is applied to the keratin fibers in the presence of an oxidizing agent for a sufficient time to obtain the desired lightening. The oxidizing agent may 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, in a composition containing, in a medium appropriate for dyeing, at least one oxidizing agent, said oxidizing agent being present in an amount sufficient to achieve the desired lightening. The mixture obtained is then applied to the keratin fibers. After an exposure time of 3 to 50 minutes, preferably 5 to about 30 minutes, 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 persulphates, peracids and oxidase enzymes among which may be mentioned peroxidases, oxidoreductases with 2 electrons such as uricases and oxygenases with 4 electrons 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 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 keratinous fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11 . It can be adjusted to the desired value using acidifying or alkalizing agents usually used for dyeing keratin fibers and as defined above.

The ready-to-use which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels or any other form suitable for dyeing keratin fibers, especially human hair.

The invention also relates to a multi-compartment device or "kit" in which a first compartment contains the dye composition of the present invention defined above and a second compartment contains an oxidizing agent. This device can be equipped with a means for applying to the hair the desired mixture, such as the devices described in patent FR 2 586 913 in the name of the Applicant.

The following examples serve to illustrate the invention without being limiting in nature.

EXAMPLES

SYNTHESIS EXAMPLES Step 1:

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In a 500 ml three-necked flask is added at ambient temperature with stirring 2.4 g of cyanuric chloride in 50 ml of acetone. The reaction medium is transparent. Was added a mixture of water and ice in 50ml respective proportion and 100 ml and the reaction medium is placed at 0 ° C in an ice bath.

After a few seconds of stirring, a white suspension is obtained. The pH value is 2.8. Using a dropping funnel, a solution containing 3.2 g is added to (i) dissolved in 100 ml of water, taking care to maintain the pH of the reaction mixture between 4 and 6 using of a saturated solution of K₂CO₃ and keeping the reaction medium at a temperature below 5 ° C.

After this addition, the pH stabilized at 4.8 by regular addition of the K solution₂CO₃ saturated. Thereafter, is allowed to return to room temperature. HPLC (relative purity: 94%) and a control mass (m / z: 363-365-367) show the almost exclusive formation of the product (ii) reaction

A solution consisting of 3.42 g of (iii) previously dissolved in 50 ml of H2O / EtOH (1/1) is then added to the previous reaction medium, taking care to maintain the pH between 4 and 6. After addition , the pH is maintained at 4.9 to 5 for 15 minutes. The reaction medium is then heated at 44 ° C for 2.5 hours. Is allowed to return the reaction mixture to room temperature and then poured into an Erlenmeyer flask containing 1 liter of a solution consisting of isopropanol and acetone. A precipitate appears. This is filtered, dried and analyzed dryer. 6.08 g (yield = 86%) of a brown powder (product (iv)) of a purity of 98% (relative purity, HPLC).

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In a three-necked flask with a condenser, a pH probe, and an addition funnel containing 1N sodium hydroxide solution, 9 g has (iv) which was dissolved in 300 ml of water . The reaction medium is then heated at 85 ° C (oil bath temperature: 96 ° C) and the pH is adjusted between 7.7 and 8 using sodium hydroxide solution. then added very slowly amine (3 ml) diluted in 20 ml of water, being careful to control the pH (pH &lt;8). Once the addition is complete, the temperature of the reaction medium is raised to 92 ° C (oil bath temperature: 118 ° C.) and stirred until the pH stabilizes at a value of between 7 , 7 and 8.

After one hour of reaction, the reaction medium is cooled and then poured into an Erlenmeyer flask containing 1 liter of acetone. The product precipitates. It is then filtered, dried and analyzed dryer. Is obtained 7.1 g of a brown powder (compound v) (Yield = 82%, HPLC purity: 92%).

Mass (ESI +): m / z = 352

NMR (¹H, 400 MHz, MeOD): 3.86-3.87 ppm (br s, 4H), 4.05 ppm (s, 6H), 4.12 ppm

(S, 6H), 4.88 ppm (br s, 4H), 7.10-7.12 ppm (d, 2H), 7.28-7.26 ppm (d, 2H), 7.55 ppm (s, 2H), 7.69 ppm (s, 2H), 7.77-7.79 ppm (d, 2H), 7.97-7.95 ppm (d, 2H), 8.09-8.04 ppm (m, 4H).

The following compounds were synthesized by employing the step 2 using the reagents listed below

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EXAMPLES OF DYE

EXAMPLES INVENTION

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At the time of use, the composition above is mixed with hydrogen peroxide 40V (weight for weight). The mixture is then applied to locks of hair 90% natural white (BN) or permanent (BP). The locks on pause time is 20 min at room temperature. The locks are then washed with shampoo.

After drying, the color uptake is evaluated visually and by measuring the L * a * b * (CM2002 colorimeter, illuminant D65-10⁰ CSI).

The selectivity is measured by the difference between the level of coloration of a natural wick (BN) and a permanent-bit (BP) from the L * a * b * measured for each type of fuse according to the following formula :

Ei "/ 4_P = _Λ/ (Li * -Li "*)² + (A6 * - _to *)² + (B6 * -b6 *)²

Chromaticity C * is calculated from the following formula in which c * = (^at *) ² + (^b *) ²

The results are summarized in Table 1 below The colorful locks are then 12 shampoos, with intermediate drying between shampoos. Color after 12 shampoos is compared with the initial color of the colored lock visually and by colorimetric measurement. The shampoo fastness is measured on colored natural hair and colored hair standing in the words of .DELTA.E above from the values ​​of L * a * b * measured on each type of hair before and after 12 shampoos.

The colorimetric results are summarized in Table 1 below.

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The results in Table 1 show that the resulting color is powerful and little color (dark purple). They have more good resistance to shampooing as well on natural hair and on permanent hair. Furthermore, there is no observed color change.

COMPARATIVE EXAMPLES

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The orange dye is marketed under the name Basic Orange 31. The purple dye was synthesized by the method described in US 5 708 151. At the time of use, the composition is mixed with hydrogen peroxide 40V (weight for weight) . The mixture is then applied to a lock of hair at 90% white, natural (BN) or permanent (BP). The locks on pause time is 20 min at room temperature. The locks are then washed with shampoo. After drying, the color uptake is evaluated visually and by colorimetric L * a * b * as defined above (CM2002 colorimeter, illuminant D65-10 ° CSI).

The colorful locks are then 12 shampoos, with intermediate drying between shampoos. Color after 12 shampoos is compared with the initial color of the colored lock visually and by colorimetric measurement.

Selectivity and shampoo fastness are determined according to the method described above. The results are summarized in Table 2 below. TABLE 2

<img id="imgf000027_0002" he="51" wi="134" file="imgf000027_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" /> The results of the outcome coloration of the mixture of purple and orange dyes show that although the color obtained either little color, it varies depending on the nature of the hair that is colored. Indeed, comparing the values ​​of a *, the color obtained on natural hair is red while on permanent hair is black. In addition, a color change to purple is observed both on natural hair and on permanent hair.

Comparing the results in Table 1 and Table 2 show that the present invention provides uniform colorings whatever the nature of colored hair, without bend and exhibit good resistance to shampooing.