Composition comprising a chromophore of azo or tri(hetero)arymethane type

0001The subject of the present invention is a dye composition comprising one or more mixed dyes comprising at least one azo type or tri- (hetero) aryl methane type chromophore, as well as a process for dyeing keratin fibers, in particular human fibers, play said composition. It likewise relates to mixed dyes as such.

0002It is known to dye keratinous fibers and in particular human hair with dye compositions containing direct dyes. These compounds are colored molecules and dyes having an affinity for the fibers. It is known, for example, to use direct dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines, dyes of the azo, xanthene, acridine, azine or triarylmethane type.

0003Usually, these dyes are applied to the fibers, optionally in the presence of an oxidizing agent, if it is desired to obtain a simultaneous effect of lightening the fibers. Once the exposure time has elapsed, the fibers are rinsed, optionally washed and dried.

0004The colorings that result from the use of direct dyes are temporary or semi-permanent dyes because the nature of the interactions that bind the direct dyes to the keratin fiber, and their desorption of the surface and / or the core of the fiber are responsible their low dyeing power and their relative poor resistance to washes or perspiration.

0005There is also an additional difficulty, because in order to obtain a particular color, it is necessary in most cases, if not all, to mix several dyes. However, each dye does not have the same affinity for the fiber, which results in either heterogeneous coloring or color bends over time, for example after one or more washes of the fibers, exposure to the sun, etc.

0006The object of the present invention is to provide direct dyes not having the disadvantages of existing direct dyes.

0007In particular, one of the aims of the present invention is to provide direct dyes which make it possible to obtain various shades without problem of turning the color over time.

0008These and other objects are achieved by the present invention which relates to a dye composition comprising in a medium suitable for dyeing keratinous fibers, especially human, at least one mixed dye comprising at least two different chromophores; at least one of the chromophores being selected from chromophores of the family of azo compounds or from chromophores of the tri- (hetero) aryl methane family; the chromophores being linked to one another via at least one linking arm which stops the delocalization of the electrons of each of the chromophores; mixed dyes whose chromophores are all of the azo type not forming part of the present invention.

0009It also relates to a process for dyeing keratinous fibers, in particular human fibers, in which the above-mentioned dyeing composition is applied, optionally in the presence of at least one oxidizing agent, it is left for a sufficient time to obtain the desired coloration, the fibers are optionally rinsed, optionally washed and rinsed, then dried or allowed to dry.

0010It also relates to mixed dyes comprising at least two different chromophores; at least one of the chromophores being selected from chromophores of the family of azo compounds or from chromophores of the tri- (hetero) aryl methane family; the chromophores being linked to one another via at least one linking arm which stops the delocalization of the electrons of each of the chromophores; mixed dyes whose chromophores are all of the azo type not forming part of the present invention, and except for the following compounds:<chemistry id="chem0001" num="0001"><img file="EP1574205A2_D0001.tif" /></chemistry><chemistry id="chem0002" num="0002"><img file="EP1574205A2_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP1574205A2_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP1574205A2_D0004.tif" /></chemistry>

0011It has been found that the dyeing composition according to the invention makes it possible to obtain powerful colors which are stable to light, resistant to bad weather, washing and transpiration, and tenacious over time.

0012But other features and advantages of the present invention will emerge more clearly from the description and examples which will be presented.

0013In the following, and unless otherwise indicated, substituted, substituted aryl (or aromatic) or substituted heteroaryl (or heteroaromatic) radical is understood to mean an alkyl, aryl or heteroaryl radical carrying one or more radicals selected from a radical hydroxyl; a halogen atom, and preferably chlorine, fluorine; a C-alkoxy radical₁-C₈ linear or branched, substituted or unsubstituted, preferably C₁-C₄ ; a monohydroxy alkoxy radical whose alkyl part is in C₁-C₈preferably in C₁-C₄linear or branched, substituted or unsubstituted; a polyhydroxyalkoxy radical, in C₂-C₈preferably in C₂-C₄linear or branched, substituted or unsubstituted; an amino radical which may or may not be substituted by one or more identical or different alkyl radicals in C₁-C₈preferably in C₁-C₆, linear or branched, substituted or unsubstituted and / or with one or more aryl radicals, preferably C₆optionally substituted; a thiol radical; a C-alkylthio radical₁-C₈preferably in C₁-C₄linear or branched, substituted or unsubstituted; a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted); an alkoxycarbonyl radical whose alkyl part is in C₁-C₈preferably in C₁-C₄linear or branched, substituted or unsubstituted; an alkylamide radical whose alkyl part is in C₁-C₈preferably in C₁-C₄linear or branched, substituted or unsubstituted; an alkylcarbamyl radical whose alkyl part is in C₁-C₈preferably in C₁-C₄linear or branched, substituted or unsubstituted; a nitro radical; a sulfonyl radical; a C-alkylsulfonyl radical₁-C₈preferably in C₁-C₄, linear or branched substituted or not; a sulfonylamino radical; an alkylsulphonylamido radical whose alkyl part is in C₁-C₈preferably in C₁-C₄, linear or branched, substituted or unsubstituted.

0014Recall that a heteroaromatic radical, or heteroaryl, corresponds to an aromatic radical in which at least one of the carbon atoms is replaced by a heteroatom, and more particularly, nitrogen, oxygen or sulfur.

0015In addition, when it is stated that the alkyl or aryl radical or the alkyl or aryl part of a radical which is substituted for another radical is itself substituted, it is understood that it comprises one or more substituents chosen from hydroxyl groups. ; amino; amino substituted with one or more identical or non-linear, linear or branched C₁-C₄optionally carrying at least one hydroxyl group; alkoxy radicals, linear or branched in C₁-C₄optionally carrying at least one or more hydroxyl groups.

0016When mention is made of amino radicals carrying two substituents chosen from optionally substituted alkyl radicals, it is understood that said alkyl radicals may also form, with the nitrogen atom to which they are bonded, a 5- or 6-membered ring of which at least one of the carbon atoms may be replaced by one or more nitrogen, oxygen or sulfur atoms.

0017In addition, unless otherwise indicated, the bounds defining the range of a range of values ​​are within this range of values.

0018In addition, the mixed dyes according to the invention being cationic, their counterion (s) are chosen from cosmetically acceptable anions, of mineral or organic nature. As examples of anions of a mineral nature, mention may be made in particular of halides, such as chlorides or bromides; hydroxides; sulphates; hydrogen sulphates; carbonates, hydrogenocarbonates.

0019As examples of anions of organic nature, anions such as acetate are suitable; citrate; tartrate; the alkyl sulphates for which the linear or branched alkyl part is C₁-C₆such as methosulphate ion, ethosulphate; the alkylsulphonates for which the linear or branched alkyl part is in C₁-C₆ ; arylsulphonates for which the aryl part, preferably phenyl, is optionally substituted by one or more C 1 -alkyl radicals₁-C₄.

0020The mixed dyes present in the composition according to the invention will firstly be described.

0021As indicated above, the mixed dyes comprise at least two different chromophores; at least one of the chromophores is selected from chromophores of the family of azo compounds or from chromophores of the tri- (hetero) aryl methane family; the chromophores being linked to each other via at least one linking arm which stops the delocalization of the electrons of each of the chromophores. Finally, mixed dyes whose chromophores are all of the azo type do not form part of the present invention.

0022Preferably at least one of the chromophores of the mixed dye carries one or more cationic charges.

0023By chromophore is meant a radical derived from a dye, that is to say a radical of a molecule absorbing in the visible range between 400 and 800 nm. It should be noted further that this absorbance of the dye does not require any prior oxidation thereof, or association with other (s) species (s) chemical (s).

0024When it is specified that the chromophores are different, it means that at least two of them, preferably all, differ in their chemical structure. Such chromophores may be chromophores from different families or from the same family provided that they have different chemical structures. For example, the chromophores can be chosen from the same family of dyes but differ by the chemical structure of the radicals constituting them.

0025According to a particular embodiment of the invention, the mixed dye comprises two to four chromophores, advantageously two to three chromophores.

0026It should be noted that when the dye comprises more than two chromophores, at least one of these chromophores is different from the other or the others.

0027According to a preferred embodiment of the invention, the mixed dye comprises two chromophores.

0028According to a particular variant of the invention, the cationic chromophore or chromophores are chromophores comprising at least one quaternized nitrogen atom.

0029In addition, the cationic charge (s) may or may not be engaged in a cycle.

0030Moreover, as indicated above, at least one of the chromophores of the mixed dye has at least one cationic charge, and more particularly a single cationic charge.

0031Preferably, according to this variant, each of the chromophores comprises at least one cationic charge, and very advantageously, a single cationic charge.

0032According to a particular embodiment of the invention, the mixed dye has an overall cationic charge, under the conditions of use of this mixed dye.

0033The mixed dye present in the composition according to the invention therefore comprises at least one chromophore of the family of azo compounds or at least one chromophore of the family of tri- (hetero) aryl methanes.

0034The chromophores of the family of azo (or azo) compounds are chosen from compounds comprising at least one -N = N- sequence whose two nitrogen atoms are not simultaneously engaged in a ring. However, it is not excluded that one of the two nitrogen atoms of the sequence -N = N- is engaged in a cycle.

0035According to one variant, the mixed dye comprises at least one cationic azo chromophore.

0036Such chromophores are described for example in EP 850 636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850637, EP 918053, WO 9744004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423. , FR 1567219, FR 1516943, FR 1221122, DE 4220388, DE 4137005, WO 0166646, US 5708151, WO 9501772, WO 9515144, GB 1195386, US 3524842, US 5879413, EP 1062940, EP 1133976, GB 738585, DE 2527638, 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; Chim. 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; Lihua 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.

0037As particularly advantageous examples, the chromophore or chromophores of the family of azos compounds correspond to the following formula (I), as well as its tautomeric forms:<maths id="math0001" num="(I)"><math display="block"><mrow><msub><mrow><mtext>AT</mtext></mrow><mrow><mtext>1</mtext></mrow></msub><msub><mrow><mtext> - [N = N - (A</mtext></mrow><mrow><mtext>3</mtext></mrow></msub><msub><mrow><mtext>)</mtext></mrow><mrow><mtext>there</mtext></mrow></msub><msub><mrow><mtext>]</mtext></mrow><mrow><mtext>x</mtext></mrow></msub><msub><mrow><mtext> - AT</mtext></mrow><mrow><mtext>2</mtext></mrow></msub></mrow></math><img file="EP1574205A2_D0005.tif" /></maths> Formula in which:<ul id="ul0001" list-style="dash" compact="compact"><li>x is an integer from 1 to 3;</li><li>y is 0 or 1;</li></ul>

0038Preferably, if y is zero, then x is 1.<ul id="ul0002" list-style="dash" compact="compact"><li>AT₁, AT₂, identical or not, represent an aromatic radical in C₆-C₃₀ or a 5- to 30-membered heteroaromatic radical, comprising at least one heteroatom selected from nitrogen, oxygen and / or sulfur; at least one of the A groups₁, AT₂ being substituted;</li><li>AT₁ or A₂ being bonded to the linking arm of the mixed dye;</li><li>AT₃ represents a mono- or poly-aromatic divalent radical in C₆-C₃₀optionally substituted, preferably with one or more groups, which may be identical or different, chosen from a linear or branched C 1 -C alkyl radical;₁-C₆ ; alkoxy, linear or branched, in C₁-C₆ ; hydroxyl; amino; amino substituted by one or more alkyl radicals, identical or not, linear or branched, in C₁-C₆optionally carrying at least one hydroxyl radical; nitro; by one or more halogen atoms, C-alkylsulphonamido₁-C₁₂ (Alkyl-SO₂-NH-), C-alkylsulfamoyl₁-C₁₂ (Alkyl-NH-SO₂-), acyloxy whose alkyl part is in C₁-C₁₂ ; alkoxycarbonyl whose alkyl part is in C₁-C₁₂ ; carboxyl.</li></ul>

0039Preferably, A₁, AT₂, identical or not, represent an aromatic radical in C₆-C₃₀ or a heteroaromatic radical comprising from 5 to 30 members, comprising at least one heteroatom selected from nitrogen, oxygen and / or sulfur; said radicals being optionally substituted by at least one linear or branched alkyl radical, in C₁-C₈substituted or unsubstituted; at least one (hetero) aromatic radical in C₅ or C₆, substituted or not by one or more linear or branched alkoxy radicals, in C₁-C₆ ; amino; amino substituted by one or more alkyl radicals, identical or different, linear or branched in C₁-C₆optionally carrying at least one hydroxyl group; amido; hydroxyl; halogen atom; nitro; cyano.

0040Preferably, at least one of the groups A₁ or A₂ is cationic.

0041According to a particularly advantageous embodiment, the chromophore or chromophores of the family of azos compounds correspond to the formula (I) in which x is equal to 1 and y is 0.

0042According to an even more particular embodiment of the invention, the chromophore or chromophores of the family of azos compounds correspond to the formula (I) with x = 1 and y = 0, as well as its tautomeric forms, in which:<ul id="ul0003" list-style="none" compact="compact"><li>AT₁ represent<chemistry id="chem0005" num="0005"><img file="EP1574205A2_D0006.tif" /></chemistry> the link a being connected to the azo group either via the ring or via N¹, Z₁, Z₂, Z₃, Z₄, R₁, R₂, R₃ ;</li><li>Z₁ represents an oxygen atom, sulfur, a radical NR₄ or a radical CR₅,</li><li>Z₂ represents a nitrogen atom or a radical CR₆,</li><li>Z₃ represents a nitrogen atom or a radical CR₇,</li><li>Z₄ represents a nitrogen atom or a radical CR₈,</li><li>R₁ and R₆ can together form an aromatic cycle,</li><li>An represents a cosmetically acceptable anion,</li></ul>

0043AT₂ represents an aromatic group in C₆-C₃₀ or heteroaromatic 5 to 30-membered, optionally substituted, optionally cationic, linked to the azo group either through said ring, or through one of its substituents.

0044Preferably, A₂ represents a carbon or pyridine aromatic group of formula:<chemistry id="chem0006" num="0006"><img file="EP1574205A2_D0007.tif" /></chemistry> Formulas in which:<ul id="ul0004" list-style="none" compact="compact"><li>The bond b is connected to the azo group through the ring;</li><li>Z₅ represents a nitrogen atom or a radical CR₁₀ ;</li><li>R₁, R₂, R₃, R₅, R₆, R₇, R₈, R₉, and R₁₀, identical or different, represent a hydrogen atom; an alkyl radical, linear or branched, in C₁-C₈optionally substituted; a 5- or 6-membered (hetero) aryl radical, optionally substituted; a halogen atom; a hydroxyl group; a linear or branched alkoxy radical in C₁-C₈optionally substituted; an amino radical; an amino radical substituted with one or more alkyl radicals, which may be identical or different, linear or branched in C₁-C₆optionally carrying at least one hydroxyl group; a nitro group; a cyano group; C-alkylsulfonamido₁-C₁₂ (Alkyl-SO₂-NH-); C-alkylsulfamoyl₁-C₁₂ (Alkyl-NH-SO₂-); acyloxy whose alkyl part is in C₁-C₁₂ ; alkoxycarbonyl whose alkyl part is in C₁-C₁₂ ; a carboxy group;</li><li>R₄ represents an alkyl radical, linear or branched, in C₁-C₈optionally substituted;</li><li>R₁ with R₅, and R₆ with R₇ can form an aromatic ring;</li><li>The coefficient b 'is equal to 4;</li><li>An represents a cosmetically acceptable anion of organic or mineral nature.</li></ul>

0045Preferably R₁, R₂, R₃, R₅, R₆, R₇, R₈, R₉ and R₁₀, identical or not, represent a hydrogen atom or a C 1 -C 4 alkyl radical₁-C₄, linear or branched, optionally substituted with at least one halogen atom, a nitro group, a cyano group, an amido group (-CONH₂), a C-alkoxy group₁-C₄ ; a hydroxyl group; a linear or branched alkoxy radical in C₁-C₈ ; an amino radical; an amino radical substituted with one or more identical or non-linear, linear or branched alkyl radicals, in C₁-C₄optionally carrying a hydroxyl group.

0046Preferably R₄ represents an alkyl radical, linear or branched, in C₁-C₄optionally substituted.

0047According to a first advantageous embodiment of the invention, Z₁ represents a radical NR₄. Moreover, according to this embodiment, Z₂ represents more preferably CR₆.

0048According to another advantageous embodiment of the invention, Z₁ represents a group NR₄ and Z₂ represents a CR group₆.

0049According to these two embodiments of the invention, the azo group is linked to the group of formula (II) via the ring.

0050According to another advantageous variant of the invention, the group A₁ corresponds to one of the formulas (III) or (IV) and the azo group is linked via the ring or Z₃ with Z₃ preferably representing a CR group₇.

0051In addition, the chromophore is connected to the link arm via the group A₁ or group A₂.

0052That the chromophore and the connecting arm are bound by group A₁ or by group A₂the bond may be carried out either via one of the ring links of the groups of formulas (II) to (IV) or the (hetero) aromatic group A₂and preferably of the group of formula (V), or via one of the substituents carried by the links of the aforementioned cycles.

0053More preferably, if the chromophore and the linking arm are connected by the group A1, the bond can be obtained advantageously via the nitrogen atom N¹, radicals R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈. Advantageously, the bonding takes place via the nitrogen atom N¹.

0054In the case where the chromophore and the connecting arm are not connected via the nitrogen atom N¹, then the nitrogen atom N¹ possibly carries a radical, identical or different from one of the radicals R₁ at R₁₀, and preferably by an alkyl radical, linear or branched, in C₁-C₄optionally substituted.

0055According to a first embodiment of the invention, when the chromophore and the linker are linked by group A₂, and more especially by a group A₂ of formula (V), then the chromophore and the linker may be linked via one of the radicals R₉, R₁₀ or by the cycle, preferably in the latter case, the presence of an oxygen or nitrogen atom directly linked to the aromatic ring. According to a preferred variant of the invention, the chromophore and the linker are linked via a radical R₉ More particularly, R₉ is linked to the ring via a nitrogen or oxygen atom.

0056According to a second embodiment of the invention, the chromophore and the linker are connected via group A₁ and more precisely via the nitrogen atom N¹.

0057According to a third embodiment of the invention, the chromophore and the connecting arm are connected via group A₁ and more specifically via the Z group₁, advantageously representing CR₅preferably directly by this carbon atom. According to this embodiment, R₁ and R₆ can together form a 6-membered aromatic ring.

0058In the case where the chromophore is connected to the link arm by group A₂at least one of the nitrogen atoms of the formulas (II) to (IV) optionally bears a C 1 -C 4 alkyl radical₁-C₁₂, linear, branched or cyclic, optionally substituted with at least one hydroxyl group, C alkoxy₁-C₈amino, amino substituted with one or more identical or non-linear C-linear or branched alkyl radicals₁-C₈ optionally carrying at least one hydroxyl group.

0059With regard to the family of tri- (hetero) aryl methanes, the latter more particularly correspond to the following formulas (VI) to (VIII):<chemistry id="chem0007" num="0007"><img file="EP1574205A2_D0008.tif" /></chemistry>    in which :<ul id="ul0005" list-style="dash" compact="compact"><li>Ar, identical or not, represent an aryl radical, such as phenyl or naphthyl, optionally substituted; a heterocycle, optionally substituted;</li><li>AT₄ represents O, NR₁₅, NOT⁺(R₁₆)₂ in which R₁₅, R₁₆, independently of each other, represent a hydrogen atom, an alkyl radical, linear or branched, in C₁-C₈ optionally substituted, preferably with at least one hydroxyl; an amido group (-CONH₂), a C-alkoxy group₁-C₄ ; an amino radical; an amino radical substituted with one or more identical or non-linear, linear or branched alkyl radicals, in C₁-C₄optionally carrying a hydroxyl group.</li><li>R₁₄, identical or not, represent a hydrogen atom; a halogen atom, preferably chlorine, fluorine; a sulfonylamino group; a hydroxyl; an alkyl radical, linear or branched, in C₁-C₈ optionally substituted; an alkoxy radical, linear or branched, in C₁-C₈optionally substituted; an alkylthio radical, linear or branched, in C₁-C₈ optionally substituted; an amino radical; an amino radical substituted with one or more identical or non-linear, linear or branched C₁-C₈optionally carrying at least one hydroxyl group; a heterocyclic radical; a nitro group; a cyano group; an aryl radical, preferably C₆optionally substituted; an acyl group; a linear or branched alkoxycarbonyl radical in C₁-C₈ a carboxamido group; -CO₂H; -SO₃H; -PO₃H₂ ; -PO₄H₂ ;</li><li>v is 4; v 'is equal to 2.</li></ul>

0060Preferably, when Ar represents a heterocycle, the latter can be chosen from heterocycles, substituted or not, of thiophene type, benzothiophene, furan, benzofuran, indole, indoline carbazole pyridine déhydroquinoléine, chromone julodinine, thiadiazole triazole, isoxazole, oxazole thiazole, isothiazole imidazole pyrazole triazine thiazine pyrazine pyridazine pyrimidine pyridine diazepine oxazepine, benzotriazole, benzoxazole benzimidazole benzothiazole morpholine piperidine piperonyl, piperazine, azetidine pyrrolidine aziridine.

0061In addition, the radicals Ar may be substituted more particularly by one or more halogen atoms, preferably chlorine or fluorine; a sulfonylamino group; a hydroxyl; an alkyl radical, linear or branched, in C₁-C₈ optionally substituted; an alkoxy radical, linear or branched, in C₁-C₈optionally substituted; an alkylthio radical, linear or branched, in C₁-C₈ optionally substituted; an amino radical; an amino radical substituted with one or more identical or non-linear, linear or branched C₁-C₈optionally carrying at least one hydroxyl group; a heterocyclic radical; a nitro group; a cyano group; an aryl radical, preferably C₆optionally substituted; an acyl group; a linear or branched alkoxycarbonyl radical in C₁-C₈ ; a carboxamido group; -CO₂H; -SO₃H; -PO₃H₂ ; -PO₄H₂.

0062It should be noted that the chromophore can be connected to the link arm via one of the groups A₄, R₁₄, R₁₅, R₁₆, Ar, or by one through a cycle. In this case, the radical carried by the ring represents a single bond between the chromophore and the linker.

0063The mixed dye according to the present invention may likewise comprise at least one chromophore of the methine family.

0064The latter are more particularly compounds comprising at least one sequence chosen from> C = C <and -N = C <whose two atoms are not simultaneously engaged in a ring. It is however specified that one of the nitrogen or carbon atoms of the chains can be engaged in a cycle.

0065More particularly, the chromophores of this family are derived from chromophores of methine, azomethine, mono- and di-arylmethane, indamines (or diphenylamines), indophenols, indoanilines, carbocyanines, azacabocyanines and their isomers, diazacarbocyanines and their isomers, tetraazacarbocyanines, hemicyanines .

0066More particularly, among the chromophores of the family of methines, mention may be made of the chromophores corresponding to the following formula (IX) as well as its tautomeric forms:<chemistry id="chem0008" num="0008"><img file="EP1574205A2_D0009.tif" /></chemistry> Formula (IX) in which:<ul id="ul0006" list-style="dash" compact="compact"><li>R₁₇, R₁₈, identical or not, represent a hydrogen atom; an aryl radical in C₆-C₃₀ an alkyl radical (C₁-C₈aryl, the aryl part being optionally substituted with one or more groups, which may be identical or different, chosen preferably from hydroxyl, alkoxy, linear or branched, substituted or unsubstituted C groups;₁-C₄, amino, amino substituted by one or more alkyl radicals, identical or not, linear or branched, in C₁-C₄ optionally bearing at least one hydroxyl group, the halogen atoms, preferably chlorine; a heterocyclic radical, chosen in particular from thiophene, furan, piperonyl, indole, indoline, pyridine, carbazole, dehydroquinoline and chromone heterocycles;</li><li>R₁₇, R₁₈can not simultaneously represent either an aromatic radical or a heteroaromatic radical;</li><li>R₁₉, identical or different, represent a hydrogen atom; an alkyl radical, linear or branched, in C₁-C₈ optionally substituted; an aryl radical in C₆-C₃₀optionally substituted; an amino radical; an amino radical substituted by one or more linear or branched C 1 -C alkyl radicals₁-C₄optionally carrying at least one hydroxyl group; a hydroxyl group; an alkoxy radical, linear or branched, in C₁-C₈optionally carrying at least one hydroxyl group, C alkoxy₁-C₄ ; a halogen atom and preferably chlorine;</li><li>X represents a nitrogen atom, a carbon atom;</li><li>the coefficient n represents 0 when X is a nitrogen atom, and 1 when X is a carbon atom;</li><li>the coefficient n 'is equal to 4;</li><li>AT₅ represents an amino group; an amino group substituted with one or more C-alkyl radicals₁-C₈, identical or not, linear or branched, optionally bearing at least one hydroxyl group, an ammonium group N⁺(R₂₀)₂ ; R₂₀, identical or not, represent an alkyl radical in C₁-C₈ optionally substituted; an aryl radical in C₆ optionally substituted, preferably with one or more hydroxyl, halogen atoms, preferably chlorine, fluorine, nitro groups, cyano groups, alkoxy groups, linear or branched C groups,₁-C₄, monohydroxy alkoxy in C₁-C₄, linear or branched, polyhydroxyalkoxy, C₂-C₄linear or branched, amino substituted or unsubstituted by one or more identical or different C 1 -C 4 alkyl or hydroxyalkyl radicals₁-C₄, linear or branched.</li></ul>

0067In addition, the chromophore is connected to the link arm via the group A₅ or one of the R radicals₁₇, R₁₈, R₁₉ and R₂₀ or directly on the (hetero) aromatic ring (s). In the latter case, the radical R₁₉ concerned then represents a simple bond between the chromophore and the connecting arm.

0068Preferably, when R₁₇ or R₁₈ represents a C-aryl radical₆the latter may optionally be substituted, preferably by at least one hydroxyl group, with at least one amino group; at least one amino group substituted with one or more C-alkyl radicals₁-C₈, identical or not, optionally bearing at least one hydroxyl group; one or more halogen atoms; at least one C-alkylsulphonamido radical₁-C₁₂ (Alkyl-SO₂-NH-); at least one alkylsulfamoyl radical in C₁-C₁₂ (Alkyl-NH-SO₂-); at least one acyloxy radical whose alkyl part is in C₁-C₁₂ ; alkoxycarbonyl, the alkyl part of which is C₁-C₁₂ ; at least one carboxyl radical.

0069Chromophores of the following formula (X) are also suitable:<chemistry id="chem0009" num="0009"><img file="EP1574205A2_D0010.tif" /></chemistry> and where appropriate their tautomeric forms; formula in which<ul id="ul0007" list-style="none" compact="compact"><li>B, D, E and F, identical or different, representing a nitrogen atom or a CR group₂₂, R₂₂, identical or not, represent a hydrogen atom or a C 1 -C 4 alkyl radical₁-C₈ optionally substituted, preferably with at least one hydroxyl; an alkoxy radical, linear or branched, in C₁-C₄ ; an amino radical; an amino radical substituted with one or more identical or non-linear, linear or branched C₁-C₄optionally carrying at least one hydroxyl group; an aryl radical in C₆ optionally substituted, a 5 to 12-membered heteroaryl radical, optionally substituted;</li><li>n = 0 or 1;</li><li>G representing a Cycle 4, or the remains:<chemistry id="chem0010" num="0010"><img file="EP1574205A2_D0011.tif" /></chemistry></li></ul> formulas in which:<ul id="ul0008" list-style="none" compact="compact"><li>R₂₁ and R₂₄ represent, independently of one another, a linear or branched C₁-C₈ optionally substituted; an optionally substituted benzyl radical;</li><li>R₂₃ represents a hydrogen atom, an alkyl radical in C₁-C₈ optionally substituted, preferably by at least one hydroxyl, a linear or branched C₁-C₄, an amino radical, an amino radical substituted with one or more identical or non-linear, linear or branched alkyl radicals, in C₁-C₄optionally carrying at least one hydroxyl group; an aryl radical in C₆ optionally substituted; a heteroaryl radical in C₂-C₁₂ optionally substituted;</li><li><b>J</b> represents a nitrogen atom or a CR group₂₅ ; with R₂₅ having the same meaning as R₂₂ ;</li><li><b>Cycle 1</b> being chosen from 5 to 12-membered heteroaromatic radicals bearing at least one cationic charge on a nitrogen atom and optionally comprising at least one other heteroatom selected from nitrogen, oxygen and / or sulfur; said radicals being optionally substituted with at least one linear or branched C₁-C₈ substituted or not; at least one alkoxy radical, linear or branched, in C₁-C₈ substituted or not; at least one amino radical; at least one amino radical substituted with one or more linear or branched, identical or non-linear alkyl groups, in C₁-C₈optionally carrying at least one hydroxyl group; at least one aromatic radical in C₅-C₆ ; at least one hydroxyl group; alkoxycarbonyl; nitro; cyano; C-alkylsulfonamido₁-C₁₂ (Alkyl-SO₂-NH-); C-alkylsulfamoyl₁-C₁₂ (Alkyl-NH-SO₂-);</li><li><b>Cycle 2</b> being selected from aromatic C radicals₆-C₁₂ ; heteroaromatic 5 to 12-membered radicals comprising at least one heteroatom selected from nitrogen, oxygen and / or sulfur; said radicals being optionally substituted with at least one linear or branched C₁-C₈ ; at least one alkoxy radical, linear or branched, in C₁-C₈ ; at least one amino radical; at least one amino radical substituted with one or more linear or branched, identical or non-linear alkyl groups, in C₁-C₈optionally carrying at least one hydroxyl group; at least one (hetero) aromatic radical preferably comprising 5 to 6 members; at least one hydroxyl group. Preferably, Cycle 2 represents an aromatic C radical₆-C₃₀optionally substituted as indicated above;</li><li><b>Cycle 3</b> being selected from 5- or 6-membered heteroaromatic radicals comprising at least one heteroatom selected from nitrogen, oxygen and / or sulfur; said radicals being optionally substituted with at least one linear or branched C₁-C₈ ; at least one alkoxy radical, linear or branched, in C₁-C₈ ; at least one amino radical; at least one amino radical substituted with one or more linear or branched, identical or non-linear alkyl groups, in C₁-C₈optionally carrying at least one hydroxyl group; at least one aromatic radical in C₅-C₆ ; at least one hydroxyl group; alkoxycarbonyl; nitro; cyano; C-alkylsulfonamido₁-C₁₂ (Alkyl-SO₂-NH-); C-alkylsulfamoyl₁-C₁₂ (Alkyl-NH-SO₂-);</li><li><b>Cycle 4</b> being selected from aromatic C radicals₆-C₁₂ ; heteroaromatic 5 to 12-membered radicals comprising at least one heteroatom selected from nitrogen, oxygen and / or sulfur; said radicals being optionally substituted with at least one linear or branched C₁-C₈ ; at least one alkoxy radical, linear or branched, in C₁-C₈ ; at least one amino radical; at least one amino radical substituted with one or more linear or branched, identical or non-linear alkyl groups, in C₁-C₈optionally carrying at least one hydroxyl group; at least one (hetero) aromatic radical preferably comprising 5 to 6 members; at least one hydroxyl group;</li></ul> with the proviso that when n is 1 and G is a ring, then B, D, E and F can not simultaneously represent a nitrogen atom; and that when n is 0 and G is a ring, then B and D do not simultaneously represent a nitrogen atom.

0070Moreover, the chromophore is connected to the linker via one of the radicals R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ or cycles. In this case, the radical carried by the ring represents a single bond between the chromophore and the linker.

0071The formula (X) comprises the position isomers corresponding to the different possibilities of implantation of the binding of B on ring 1 with respect to the quaternized nitrogen atom).

0072According to a particularly advantageous embodiment of the invention, the chromophore of the family of methines is chosen from the compounds of the following formulas, as well as their tautomeric forms:<tables id="tabl0001" num="0001"><img file="EP1574205A2_D0012.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP1574205A2_D0013.tif" /></tables> Formulas in which:<ul id="ul0009" list-style="none" compact="compact"><li><b>R</b>_<b>26</b> identical or different, represent a hydrogen atom or a C₁-C₈ optionally substituted; an aryl radical in C₆ optionally substituted, preferably with one or more hydroxyl, halogen atoms, preferably chlorine, fluorine, nitro groups, cyano groups, alkoxy groups, linear or branched C groups,₁-C₄, monohydroxy alkoxy in C₁-C₄, linear or branched, polyhydroxyalkoxy, C₂-C₄linear or branched, amino substituted or unsubstituted by one or more identical or different C 1 -C 4 alkyl or hydroxyalkyl radicals₁-C₄linear or branched;</li><li>Groups and radicals R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, Cycle₁, Cycle₂, Cycle₃ and Cycle₄ being defined as before.</li><li>Preferably, the grouping Cycle₁ represents an imidazolium, pyridinium or indolinium ring, optionally substituted as indicated previously.</li><li>Preferably, the grouping Cycle₃ represents an imidazole, pyridine or indoline ring, optionally substituted as indicated previously.</li><li>Preferably, the grouping Cycle₂ represents an aromatic radical in C₆ optionally substituted as indicated before.</li><li>Preferably, the grouping Cycle₄ represents an aromatic radical in C₆ optionally substituted as indicated before.</li></ul>

0073Note that the chromophore can be connected to the link arm via one of the R groups₁₉, R₂₀, R₂₁, R₂₂, R₂₃, R₂₄ and R₂₅ or via an aromatic or heteroaromatic cycle. In the case of attachment via a ring, the radical carried on said ring represents a single bond between the chromophore and the linker.

0074According to a particular embodiment of the invention, the chromophore is chosen from compounds of formula (X) and preferably from diazacarbocynaines and their isomers, hemicyanins. More particularly, R₂₂, identical or not, represent a hydrogen atom or a C 1 -C 4 alkyl radical₁-C₈ optionally substituted, preferably with at least one hydroxyl; an aryl radical in C₆ optionally substituted; n = 0; G representing a Cycle4, or -N (R₂₃) -Cycle2 with R₂₃ representing a hydrogen atom, an alkyl radical in C₁-C₈ optionally substituted, preferably with at least one hydroxyl; cycle2 and cycle4, identical or different, representing an aromatic radical in C₆, optionally substituted.

0075According to this particular embodiment of the invention, the chromophore and the linker are connected via the radical R₂₁.

0076It should be noted that the chromophores described above can be prepared according to the teaching of the following patents and patent applications GB 822846; DE 1254118; GB 1047796; US 3652556; US 3423427; BE 702239; GB 702240; US 3995088; US 4054718; US 4670385; US 5094688; US 5097034.

0077The mixed dye may likewise comprise at least one chromophore of the carbonyl family.

0078Among the chromophores of this type, mention may be made, for example, of the chromophores originating from the dyes chosen from acridone, benzoquinone anthraquinone naphthoquinone benzanthrone anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone idanthrone, flavone (Iso) violanthrone, isoindolinone, benzimidazolone isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigo, thioindigo naphthalimide, anthrapyrimidine diketopyrrolopyrrole, coumarin.

0079More particularly, the chromophore of the carbonyl family is represented by the following formula (XI):<chemistry id="chem0011" num="0011"><img file="EP1574205A2_D0014.tif" /></chemistry> Formula wherein the ring represents a 5- or 6-membered ring, optionally at least one of which is replaced by a heteroatom selected from oxygen, nitrogen, sulfur, or an additional carbonyl function; said ring being optionally substituted by one or more radicals selected from linear or branched C 1 -C 4 alkyl radicals;₁-C₈optionally substituted; by one or more hydroxyl radicals; halogen atoms such as chlorine; nitro, cyano, amino, alkylamino groups; said cycle being optionally condensed with one or more C aromatic rings₆this or these rings which can themselves be condensed with one or more aromatic rings of which at least one of the carbon atoms is replaced by one or more heteroatoms chosen from oxygen, nitrogen or sulfur.

0080On the other hand, the chromophore is connected to the linker via one of the substituent groups, the rings or via a ring. In the latter case, the radical carried by the ring represents a single bond between the chromophore and the linker.

0081According to a preferred embodiment of the invention, the chromophore of the carbonyl family is represented by one of the following formulas, as well as the tautomeric formulas:<tables id="tabl0003" num="0003"><img file="EP1574205A2_D0015.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP1574205A2_D0016.tif" /></tables> Formulas in which:<ul id="ul0010" list-style="none" compact="compact"><li>R₂₇, R₂₈, R₃₀, R₃₁, identical or not, represent a hydrogen atom; an alkyl radical, linear or branched, in C₁-C₈optionally substituted; a hydroxyl group; an alkoxy radical, linear or branched, in C₁-C₈ ; an amino radical; an amino radical substituted with one or more identical or non-linear, linear or branched C₁-C₈optionally carrying at least one hydroxyl group; a halogen atom and preferably chlorine or fluorine; a nitro group; a cyano group;</li><li>R₂₉ represents a hydrogen atom, an alkyl radical, linear or branched, in C₁-C₈ ; optionally substituted;</li><li>R₃₁, identical or not, represent a C-aryl radical₆optionally substituted, preferably by at least one hydroxyl, at least one amino, at least one amino substituted by one or more identical or different linear or branched C-linked alkyl radicals₁-C₈ optionally carrying at least one hydroxyl, at least one alkoxy group, linear or branched, in C₁-C₈ optionally carrying at least one hydroxyl, at least one halogen atom, preferably chlorine, fluorine, at least one nitro group, at least one cyano group;</li><li>p is 4; q is 3; r is 5; s is 2.</li></ul>

0082The chromophore can be connected to the connecting arm via one of the radicals R₂₇, R₂₈, R₂₉, R₃₀, R₃₁ or via one of the aromatic or heteroaromatic rings. In this case, the radical carried by the ring represents a single bond between the chromophore and the linker.

0083The mixed dye of the present invention may further comprise at least one chromophore of the family of cyclic azines.

0084More particularly, the chromophore of the family of cyclic azines is chosen from the radicals derived from the dyes chosen from azine, xanthene, thioxanthene, fluorindine, acridine, (di) oxazine, (di) thiazine, and pyronine.

0085Among the chromophores of the family of cyclic azines, mention may be made of the compounds of the following formula (XII) as well as its tautomeric forms:<chemistry id="chem0012" num="0012"><img file="EP1574205A2_D0017.tif" /></chemistry> formula in which:<ul id="ul0011" list-style="none" compact="compact"><li>L represents a heteroatom preferably selected from oxygen, sulfur; an NH group; a group NR₃₄,</li><li>M represents a heteroatom preferably selected from oxygen, sulfur, nitrogen; a group N⁺-R₃₄ ; a CH group; a CR group₃₅ ;</li><li>Q, K, identical or different, represent a hydroxyl group; an amino radical; an amino radical substituted with one or more identical or non-linear, linear or branched C₁-C₈optionally carrying at least one hydroxyl group, an optionally substituted aryl radical, an alkyl radical (C₁-C₈optionally substituted aryl; an ammonium group of type N + (R₃₆)_t with t equal to 2 for K and 3 for Q, R₃₆, identical or not, represent a hydrogen atom; an alkyl radical, linear or branched, in C₁-C₈optionally carrying at least one hydroxyl group; an optionally substituted aryl radical, an alkyl radical (C₁-C₈aryl, the aryl part being optionally substituted; a linear or branched C 1 -C 8 alkyl radical, optionally substituted, a linear or branched C 1 -C 8 alkoxy radical;₁-C₈optionally substituted;</li><li>Provided that Q and K do not represent both an N-type ammonium group⁺(R₃₆)_t ;</li><li>R₃₂, R₃₃, identical or not, represent a hydrogen atom; an alkyl radical, linear or branched, in C₁-C₈ optionally substituted; an amino radical; an amino radical which may or may not be substituted by one or more radicals, which may be identical or different, chosen from linear or branched C 1 -C 4 alkyl radicals;₁-C₈ optionally substituted, optionally substituted phenyl radicals; a halogen atom, preferably chlorine, fluorine;</li><li>In the case where Q represents a substituted or unsubstituted amino radical, or a hydroxyl group, R₃₂ can represent an alkylamino or alkoxy radical forming with the nitrogen or oxygen atom of the radical <b>J</b>a 6-membered ring, optionally fused with an aromatic radical, said aromatic radical being optionally substituted with at least one amino or amino group optionally substituted with one or more identical or different radicals chosen from linear or branched alkyl radicals, in C₁-C₈ optionally substituted, optionally substituted phenyl radicals;</li><li>R₃₄, R₃₅, identical or different, represent a linear or branched C 1 -alkyl radical₁-C₈ optionally substituted, preferably with at least one hydroxyl; at least one alkoxy radical, linear or branched in C₁-C₈ ; at least one amino radical; at least one amino radical substituted with one or more identical or non-linear, linear or branched alkyl radicals in C₁-C₈optionally carrying at least one hydroxyl radical.</li><li>R₃₄, R₃₅, identical or not, may also represent an aryl radical, preferably C₆optionally substituted, preferably with at least one linear or branched C₁-C₈ ; by at least one hydroxyl group; by at least one alkoxy radical, linear or branched, in C₁-C₈ ; by at least one amino radical; by at least one amino radical substituted with one or more identical or non-linear, linear or branched alkyl radicals, in C₁-C₈optionally carrying at least one hydroxyl group; a halogen atom and preferably chlorine or fluorine; by at least one nitro group; by at least one cyano group. Preferably R₃₄ and R₃₅, identical or not, represent a linear C alkyl radical₁-C₄an optionally substituted aryl radical;</li></ul>

0086Moreover, the chromophore is more particularly connected to the linker via one of the radicals R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, or through a cycle. In this case, the radical carried by the ring represents a single bond between the chromophore and the linker.

0087According to a preferred embodiment, the chromophore of the family of cyclic azines is represented by the formulas below, as well as, where appropriate, their tautomeric forms:<tables id="tabl0005" num="0005"><img file="EP1574205A2_D0018.tif" /></tables><tables id="tabl0006" num="0006"><img file="EP1574205A2_D0019.tif" /></tables> Formulas in which the radicals and the coefficients u and w have been defined previously.

0088The chromophore is further connected to the linker via one of the radicals R₃₃, R₃₄, R₃₅, R₃₆ or through a cycle. In this case, the radical carried by the ring represents a single bond between the chromophore and the linker.

0089As a possible chromophore, the mixed dye may comprise at least one chromophore of the family of nitro (hetero) aromatic compounds.

0090More particularly, there may be mentioned, for example, the compounds corresponding to formulas (XIII) and (XIV) below, as well as their tautomeric forms:<tables id="tabl0007" num="0007"><img file="EP1574205A2_D0020.tif" /></tables> Formulas in which<ul id="ul0012" list-style="none" compact="compact"><li>R₃₇, identical or not, represent a hydrogen atom; an alkyl radical, linear or branched, in C₁-C₈optionally carrying at least one hydroxyl group; an optionally substituted aryl radical, an alkyl radical (C₁-C₈aryl, the aryl part being optionally substituted; a linear or branched C 1 -C 8 alkyl radical, optionally substituted, a linear or branched C 1 -C 8 alkoxy radical;₁-C₈optionally substituted;</li><li>R₃₈, identical or different, represent a hydrogen atom; linear or branched C-alkyl₁-C₄optionally substituted; a linear or branched alkoxy radical in C₁-C₈optionally substituted; an aryl radical in C₆ optionally substituted; an amino radical; an amino radical substituted with one or more radicals chosen from linear or branched, identical or non-linear alkyl radicals, in C₁-C₈preferably in C₁-C₄optionally substituted, preferably by at least one hydroxyl, alkoxy, linear or branched C group₁-C₄linear or branched C-thioalkyl₁-C₄linear or branched C-alkylsulfonamido₁-C₄, among the aryl radicals in C₆ optionally substituted and from optionally substituted 5- to 6-membered heteroaryl radicals; a hydroxyl group; a nitro group; a cyano group;</li><li>The coefficient z being equal to 4 and the coefficient z 'being equal to 3.</li></ul>

0091In addition, the chromophore is connected to the linker via R₃₇, R₃₈, or through the cycle. In this case, the radical carried by the ring represents a single bond between the chromophore and the linker.

0092Thus, by way of examples of mixed dyes comprising two chromophores, mention may be made, for example, of the following mixed dyes:<ul id="ul0013" list-style="none" compact="compact"><li>Azo - linker - azine</li><li>Azo - linker - methine</li><li>Azo - linker - carbonyl</li><li>Azo - link arm - nitrated</li><li>Azo - linker - tri- (hetero) aryl methane</li><li>tri- (hetero) aryl methane - linker - azine</li><li>tri- (hetero) aryl methane - linker - methine</li><li>tri- (hetero) aryl methane - linker - carbonyl</li><li>tri- (hetero) aryl methane - linker - nitro</li><li>tri- (hetero) aryl methane - linker - tri (hetero) aryl methane</li></ul>

0093As indicated above, the chromophores of the mixed dye are connected to each other by means of at least one linking arm which stops the delocalization of the electrons of each of the chromophores.

0094Thus, the linker includes an atom or group of atoms that isolates each of the chromophores of the mixed dye.

0095Preferably, the bond between the radical and the linking arm is carried out via a nitrogen or oxygen atom.

0096It should be noted, moreover, that the linker may be cationic or non-cationic.

0097In addition, the linker may be divalent, trivalent or tetravalent.

0098According to an advantageous embodiment of the invention, the linker is chosen from a C-hydrocarbon chain.₁-C₂₀preferably in C₁-C₁₂, linear or branched, preferably an alkyl chain, one or more of the carbon atoms of said chain may each be replaced by a heteroatom such as sulfur, nitrogen, oxygen, provided that the chain does not include two adjacent hetero atoms; by a heterocycle comprising 5 or 6 members, saturated or not, preferably comprising at least two nitrogen atoms; said hydrocarbon chain being unsaturated or containing an arylene radical; from an arylene radical; from a divalent terephthalamide radical; among a divalent or trivalent radical, for example triazine type.

0099Preferably, the linking arm corresponds to a C-alkyl chain₁-C₂₀preferably in C₁-C₁₂, linear or branched, of which at least one of the carbon atoms may be replaced by a 5- or 6-membered heterocycle, saturated or unsaturated, preferably comprising at least two nitrogen atoms.

0100The mixed dyes of the invention may be prepared according to known chemical reactions, from functionalized chromophores capable of reacting with the chosen linker.

0101For example, when the linker is a triazine group, then the chromophore comprises an amino, OH or SH reactive group, and the synthesis is carried out, for example, according to the diagrams below:<chemistry id="chem0013" num="0013"><img file="EP1574205A2_D0021.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP1574205A2_D0022.tif" /></chemistry><chemistry id="chem0015" num="0015"><img file="EP1574205A2_D0023.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP1574205A2_D0024.tif" /></chemistry>

0102In a first step, a first chromophore is mixed with the compound capable of forming the linker, for example trichlorotriazine. When this reaction is complete, a second chromophore is added to the reaction medium. This sequence can be repeated as many times as there are reactive groups on the compound capable of forming the linker.

0103For the preparation of a col1-link-Col 2 mixed dye, the molar ratio of the linker to dye 1 is generally from 10: 1 to 0.5: 1, preferably 1: 1. This ratio can be changed when more than one linker or multiple chromophores are used.

0104The reaction temperature is generally from -100 ° C to + 130 ° C, preferably from -5 ° C to 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.

0105Advantageously, the pH of the reaction mixture is between 2 and 12.

0106The reaction may further be conducted in water and / or in one or more organic solvents.

0107Several publications describe the chemical association reaction between two identical chromophores. Examples include ISBN 0901956759, WO 0278596, DE19845640, US 5708151.

0108In addition, reactions or reactions of a linker with two different compounds, dyes or not, have been described in the literature, for example in WO03 / 029359, DE3335956, WO03 / 30909, WO0318021, Journal of medicinal chemistry 43 (9), 2000, 1892-97; Chemiker Zeitung 117 (7-8), 1987, 241-5.

0109According to another possibility, the mixed dye can be obtained by following the following reaction scheme:<chemistry id="chem0017" num="0017"><img file="EP1574205A2_D0025.tif" /></chemistry>

0110In a first step, a first chromophore is mixed with the compound capable of forming the connecting arm, for example dibromopropane. When this reaction is complete, a second chromophore is added to the reaction medium. This sequence can be repeated as many times as there are reactive groups on the compound capable of forming the linker.

0111For the preparation of a mixed dye Col1-linker-Col 2, the molar ratio of the linker to dye 1 is generally between 10: 1 and 0.1: 1, preferably 0.5 1. This ratio can be changed when more than one linker or multiple chromophores are used.

0112The reaction temperature is in general between -100 ° 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 24 hours, preferably between 30 minutes and 4 hours.

0113The reaction can be carried out in water and / or in one or more organic solvents.

0114Advantageously, the pH of the reaction mixture is between 2 and 12.

0115The composition according to the invention usually comprises a mixed dye content ranging from 0.001 to 20% by weight, more particularly from 0.005 to 10% by weight, and preferably from 0.01 to 5% by weight, relative to total po ids of the composition.

0116Preferably, the dye composition according to the invention does not comprise a mixed dye chosen from the following compounds:<chemistry id="chem0018" num="0018"><img file="EP1574205A2_D0026.tif" /></chemistry><chemistry id="chem0019" num="0019"><img file="EP1574205A2_D0027.tif" /></chemistry><chemistry id="chem0020" num="0020"><img file="EP1574205A2_D0028.tif" /></chemistry><chemistry id="chem0021" num="0021"><img file="EP1574205A2_D0029.tif" /></chemistry>

0117The dyeing composition according to the invention may contain one or more additional direct dyes different from the mixed dye described previously.

0118The direct dyes conventionally used in the field of dyeing keratin fibers, and especially human keratin fibers, may be used.

0119As such, mention may be made of nitro dyes of the benzene series, azo direct additional dyes, methine direct dyes. These direct dyes may be nonionic, anionic or cationic in nature. Preferably these additional direct dyes are cationic in nature.

0120According to a particular embodiment of the invention, the dye composition comprises a content in each of the direct dyes ranging from 0.001 to 10% by weight relative to the total weight of the dye composition.

0121The dye composition of the invention may also contain one or more oxidation bases and / or one or more couplers, conventionally used for dyeing keratinous fibers, and in particular human keratin fibers.

0122Among the oxidation bases that may be mentioned are para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

0123The oxidation base (s) present in the composition of the invention are in general each used in an amount ranging from 0.001 to 10% by weight relative to the total weight of the dyeing composition, preferably ranging from 0.005 to 6% by weight. .

0124Among the couplers that may be used, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.

0125In the composition of the present invention, the coupler or couplers are each generally present in an amount ranging from 0.001 to 10% by weight relative to the total weight of the dyeing composition, preferably ranging from 0.005 to 6% by weight.

0126In a general way, the addition salts, in particular oxidation bases and couplers that can be used in the context of the invention, are for example chosen from acid addition salts such as hydrochlorides, the hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as sodium hydroxide, potash, ammonia, amines or alkanolamines.

0127The medium suitable for dyeing, also called dyeing medium, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent to solubilize compounds that are not sufficiently soluble in water. the water.

0128As an organic solvent, for example monoalcohols may be mentioned, linear or branched, preferably saturated, comprising 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol; aromatic alcohols such as benzyl alcohol, phenylethyl alcohol; polyols or polyol ethers such as, for example, monomethyl ethers, monoethyl and monobutyl ethylene glycol, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol, hexylene glycol (2-methyl 2,4-pentanediol), neopentyl glycol and 3-methyl-1,5-pentanediol; as well as diethylene glycol alkyl ethers, especially in C₁-C₄, for example, diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.

0129The solvents are preferably present in proportions ranging from 1 to 40% by weight approximately relative to the total weight of the dye composition, and even more preferably from 5 to 30% by weight approximately.

0130The dyeing composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing keratin fibers, especially human and especially the hair, such as anionic surfactants, cationic, nonionic, amphoteric zwitterionic or mixtures thereof; anionic polymers, cationic, nonionic, amphoteric zwitterionic or mixtures thereof; inorganic or organic thickeners, and in particular anionic polymeric associative thickeners, cationic, nonionic and amphoteric; antioxidants; penetrants; sequestering agents; perfumes ; buffers; dispersants; conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified; film-forming agents; ceramides or pseudo-ceramides; preservatives; opacifying agents, etc.

0131The adjuvants above are generally present in an amount varying, for each of them, from 0.01 to 20% by weight relative to the weight of the composition.

0132The composition of the invention may further contain at least one oxidizing agent.

0133The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers, especially human, are for example hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, persalts such as perborates and persulphates of alkali or alkaline earth metals, like sodium, potassium, magnesium, alone or in mixtures, peracids and oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

0134The composition of the invention may further comprise at least one alkaline agent which may be chosen from those conventionally used in the cosmetics field.

0135Among these alkaline agents, mention may be made, for example, of ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and compounds of formula (A) below:<chemistry id="chem0022" num="0022"><img file="EP1574205A2_D0030.tif" /></chemistry> in which W is a propylene residue optionally substituted with a hydroxyl group or a C-alkyl radical₁-C₄ ; R_at, R_b, R_c and R_d, which may be identical or different, represent a hydrogen atom or a C 1 -alkyl radical₁-C₄ or hydroxyalkyl in C₁-C₄.

0136The pH of the dyeing composition of the invention is preferably between 8 and 11.

0137Of 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 composition according to the invention are not, or not substantially, impaired by the addition or additions envisaged .

0138The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, especially human fibers, and more particularly hair .

0139The 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, dry or otherwise.

0140According to a first variant, the composition applied to the keratinous fibers does not comprise an oxidizing agent. This variant is particularly suitable when the dye composition comprises at least one mixed dye according to the invention and optionally at least one additional direct dye.

0141According to a second variant of the invention, the process is carried out with at least one oxidizing agent. This second variant is appropriate regardless of the nature of the dyes present (mixed dye, additional direct dye, oxidation bases and / or couplers). Such a method makes it possible to obtain a lightening of the treated fiber.

0142According to this second variant, the oxidizing agent may be added to the dyeing composition at the time of use or it may also be used from an oxidizing composition comprising it, applied simultaneously or sequentially to the dyeing composition comprising the mixed dye. In the latter case, the oxidizing agent is present in a composition different from that comprising the mixed dye.

0143According to a particular embodiment, the composition comprising the mixed dye 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 an amount sufficient to obtain the desired lightening.

0144The mixture obtained is then applied to the keratinous fibers.

0145After a sufficient exposure time to obtain the desired coloration, usually ranging from about 3 to 50 minutes, preferably from 5 to about 30 minutes, the keratinous fibers are preferably rinsed, then washed with shampoo, rinsed again and then dried or allowed to dry. .

0146Furthermore, conventionally the composition is applied and left to act at a temperature ranging from 15 to 80 ° C, preferably from 15 to 40 ° C.

0147The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing keratinous fibers, in particular human fibers, and as defined above.

0148The 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 (ie in other words the ready-to-use composition) varies from preferably from 7 to about 12, and even more preferably from 8 to 11. It can be adjusted to the desired value by means of acidifying agent (s) or basifying agent (s).

0149Acidifying agents include, for example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, acetic acid.

0150As regards the alkalinizing compounds, reference may be made to the list previously indicated.

0151The ready-to-use composition, ie in other words the composition which is finally applied to the keratinous fibers, may be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratinous fibers, especially human keratinous fibers, such as the hair.

0152The invention also relates to a multi-compartment device in which at least a first compartment comprises a dye composition comprising at least one mixed dye as described above, and optionally at least one direct dye different from the mixed dye, optionally at least one oxidation base, optionally at least one coupler, and another compartment comprises an oxidizing agent.

0153It should be noted that the mixed dye (s), optionally the additional direct dye, the oxidation base (s), or the coupler (s) may be in the same compartment or in several compartments; the same compartment may comprise a single type of dye (mixed, additional direct, oxidation) or a combination of several of them.

0154This device may be equipped with means for delivering the desired mixture to the fibers to be treated, such as the devices described in patent FR 2 586 913.

0155A final subject of the invention consists of mixed dyes as just described, as well as their addition salts, with the exception of the following compounds:<chemistry id="chem0023" num="0023"><img file="EP1574205A2_D0031.tif" /></chemistry><chemistry id="chem0024" num="0024"><img file="EP1574205A2_D0032.tif" /></chemistry><chemistry id="chem0025" num="0025"><img file="EP1574205A2_D0033.tif" /></chemistry><chemistry id="chem0026" num="0026"><img file="EP1574205A2_D0034.tif" /></chemistry>

0156The invention relates more particularly to mixed dyes comprising two chromophores. Preferably at least one of the two chromophores carries at least one cationic charge, preferably both chromophores carry at least one cationic charge. Moreover, at least one of the chromophores is selected from the family of azo dyes, and the other is selected from the family of diazacarbocyanine dyes or its isomers, hemicyanine, nitro (hetero) aromatic. In addition and advantageously, the linker corresponds to a C-alkyl chain₁-C₂₀preferably in C₁-C₁₂, linear or branched, of which at least one of the carbon atoms may be replaced by a 5- or 6-membered heterocycle, saturated or unsaturated, preferably comprising at least two nitrogen atoms. The linker may optionally carry at least one cationic charge.

0157Examples of such mixed dyes include, for example, those corresponding to the following formulas:<chemistry id="chem0027" num="0027"><img file="EP1574205A2_D0035.tif" /></chemistry><chemistry id="chem0028" num="0028"><img file="EP1574205A2_D0036.tif" /></chemistry><chemistry id="chem0029" num="0029"><img file="EP1574205A2_D0037.tif" /></chemistry><chemistry id="chem0030" num="0030"><img file="EP1574205A2_D0038.tif" /></chemistry><chemistry id="chem0031" num="0031"><img file="EP1574205A2_D0039.tif" /></chemistry><chemistry id="chem0032" num="0032"><img file="EP1574205A2_D0040.tif" /></chemistry><chemistry id="chem0033" num="0033"><img file="EP1574205A2_D0041.tif" /></chemistry><chemistry id="chem0034" num="0034"><img file="EP1574205A2_D0042.tif" /></chemistry><chemistry id="chem0035" num="0035"><img file="EP1574205A2_D0043.tif" /></chemistry><chemistry id="chem0036" num="0036"><img file="EP1574205A2_D0044.tif" /></chemistry><chemistry id="chem0037" num="0037"><img file="EP1574205A2_D0045.tif" /></chemistry><chemistry id="chem0038" num="0038"><img file="EP1574205A2_D0046.tif" /></chemistry><chemistry id="chem0039" num="0039"><img file="EP1574205A2_D0047.tif" /></chemistry><chemistry id="chem0040" num="0040"><img file="EP1574205A2_D0048.tif" /></chemistry><chemistry id="chem0041" num="0041"><img file="EP1574205A2_D0049.tif" /></chemistry><chemistry id="chem0042" num="0042"><img file="EP1574205A2_D0050.tif" /></chemistry><chemistry id="chem0043" num="0043"><img file="EP1574205A2_D0051.tif" /></chemistry><chemistry id="chem0044" num="0044"><img file="EP1574205A2_D0052.tif" /></chemistry><chemistry id="chem0045" num="0045"><img file="EP1574205A2_D0053.tif" /></chemistry><chemistry id="chem0046" num="0046"><img file="EP1574205A2_D0054.tif" /></chemistry><chemistry id="chem0047" num="0047"><img file="EP1574205A2_D0055.tif" /></chemistry><chemistry id="chem0048" num="0048"><img file="EP1574205A2_D0056.tif" /></chemistry><chemistry id="chem0049" num="0049"><img file="EP1574205A2_D0057.tif" /></chemistry>

0158Concrete but non-limiting examples of the present invention will now be presented

<b>EXAMPLE 1 Synthesis of the mixed dye</b>

0159<chemistry id="chem0050" num="0050"><img file="EP1574205A2_D0058.tif" /></chemistry><chemistry id="chem0051" num="0051"><img file="EP1574205A2_D0059.tif" /></chemistry>

Process

:

0160In a tricolor, 1.06 equivalents of the hydrazone dye (3 g) and about 100 mg of KI are introduced into 2 ml of DMF with stirring and heated to 95 ° C.

01611 equivalent of the azo dye (1.49 g) dissolved in 5 ml of DMF is then added and allowed to react for 24 hours.

0162The product is recovered by precipitation in ethyl acetate (50 ml), filtered and the product which is in the form of a black powder is dried.

0163The product is purified by solubilization in dichloromethane and then precipitated in a mixture containing an isopropanol / ethyl acetate mixture (1/4) and then filtered.

0164The 13 C and 1 H NMR spectrum are in agreement with the structure of the expected product.

<b>Example 2: Coloring Applications</b>

<b>1 / Lightening and non-lightening coloring</b>

0165The mixed dye obtained in the preceding example is formulated at 4.7 × 10^-4 mol% in the following coloring compositions A: <tables id="tabl0008" num="0008"><table frame="all"><tgroup cols="2" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="center"><b>Composition A</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Alkyl (C₈/ C₁₀ 50/50) polyglucoside in 60% buffered aqueous solution</entry><entry namest="col2" nameend="col2" align="left">10 g</entry></row><row><entry namest="col1" nameend="col1" align="left">Benzyl alcohol</entry><entry namest="col2" nameend="col2" align="left">10 g</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyethylene glycol 400 with 8 ethylene oxide units</entry><entry namest="col2" nameend="col2" align="left">12 g</entry></row><row><entry namest="col1" nameend="col1" align="left">Mixed dye</entry><entry namest="col2" nameend="col2" align="left">4,7x10^-4 mol.</entry></row><row><entry namest="col1" nameend="col1" align="left">Ammonia at 20.5%</entry><entry namest="col2" nameend="col2" align="left">13 g</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Demineralized Water</entry><entry namest="col2" nameend="col2" align="left">qsp 100 g</entry></row></tbody></tgroup></table></tables>

0166At the time of use, the composition A is mixed either with hydrogen peroxide 40V (weight for weight, pH = 3.5) or with acidified water (pH = 3.5).

0167The pH of the dyeing compositions after mixing is between 9.5 and 10.

0168The mixture is then applied to hair strands at 90% natural white (BN) or permed (BP).

0169The wicking time is 20 minutes at room temperature.

0170The locks are then washed with shampoo.

0171In both cases we obtain colored locks.

<b>2 / Shampoo resistance</b>

0172A dyeing composition according to the invention was prepared from the mixed dye (4.7 × 10^-4 mol%) and dye support A.

0173Furthermore, a comparative dyeing composition was prepared under the same experimental conditions, except that the mixed dye is replaced by an equimolar mixture of the two monazo monoazo direct dyes constituting said mixed dye.<chemistry id="chem0052" num="0052"><img file="EP1574205A2_D0060.tif" /></chemistry><chemistry id="chem0053" num="0053"><img file="EP1574205A2_D0061.tif" /></chemistry>

0174At the time of use, the above compositions are mixed with 40% hydrogen peroxide (weight for weight, pH = 3.5).

0175The pH of the dyeing compositions after mixing is between 9.5 and 10.

0176The blends are then applied to strands of hair 90% white permed (BP).

0177The wicking time is 20 minutes at room temperature.

0178The colored locks then undergo six shampoos, with an intermediate drying between two shampoos.

0179The color after the six shampoos is compared to the initial color of the colored wick, visually and by colorimetric measurement.

0180The resistance to shampooing is measured on colored permed hair according to the formula of ΔE below from the values ​​of L * a * b * measured on each type of wick before L₀*at₀* b₀* and after the six shampoos L₁*at₁* b₁* (CM2002 Minolta colorimeter, illuminant D65-10 ° CSI)).<maths id="math0002" num=""><math display="block"><mrow><mtext>ΔE = </mtext><msqrt><msub><mrow><mtext>(L</mtext></mrow><mrow><mtext>1</mtext></mrow></msub><msub><mrow><mtext>* -L</mtext></mrow><mrow><mtext>0</mtext></mrow></msub><msup><mrow><mtext>*)</mtext></mrow><mrow><mtext>2</mtext></mrow></msup><msub><mrow><mtext> + (a</mtext></mrow><mrow><mtext>1</mtext></mrow></msub><msub><mrow><mtext>*-at</mtext></mrow><mrow><mtext>0</mtext></mrow></msub><msup><mrow><mtext>*)</mtext></mrow><mrow><mtext>2</mtext></mrow></msup><msub><mrow><mtext> + (b</mtext></mrow><mrow><mtext>1</mtext></mrow></msub><msub><mrow><mtext>* -b</mtext></mrow><mrow><mtext>0</mtext></mrow></msub><msup><mrow><mtext>*)</mtext></mrow><mrow><mtext>2</mtext></mrow></msup></msqrt></mrow></math><img file="EP1574205A2_D0062.tif" /></maths>

0181The colorimetric results are summarized in Table 2. <tables id="tabl0009" num="0009"><table frame="all"><title>Table 2</title><tgroup cols="5" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col5" align="left"><u><b>Composition according to the invention</b></u></entry></row><row><entry namest="col1" nameend="col1" align="center"><b>Hair type</b></entry><entry namest="col2" nameend="col2" align="center"><b>L *</b></entry><entry namest="col3" nameend="col3" align="center"><b>at*</b></entry><entry namest="col4" nameend="col4" align="center"><b>b *</b></entry><entry namest="col5" nameend="col5" align="center"><b>Degradation</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">BP / before shampoos</entry><entry namest="col2" nameend="col2" align="char" char=",">22.9</entry><entry namest="col3" nameend="col3" align="char" char=",">15.0</entry><entry namest="col4" nameend="col4" align="char" char=",">3.9</entry><entry namest="col5" nameend="col5" morerows="1" align="char" char=",">2.1</entry></row><row><entry namest="col1" nameend="col1" align="center">BP / after shampoos</entry><entry namest="col2" nameend="col2" align="char" char=",">24.7</entry><entry namest="col3" nameend="col3" align="char" char=",">16.1</entry><entry namest="col4" nameend="col4" align="char" char=",">3.9</entry></row></tbody></tgroup><tgroup cols="5" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col5" align="left"><u><b>Comparative composition:</b></u></entry></row><row><entry namest="col1" nameend="col1" align="center"><b>Hair type</b></entry><entry namest="col2" nameend="col2" align="center"><b>L *</b></entry><entry namest="col3" nameend="col3" align="center"><b>at*</b></entry><entry namest="col4" nameend="col4" align="center"><b>b *</b></entry><entry namest="col5" nameend="col5" align="center"><b>Degradation</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">BP / before shampoos</entry><entry namest="col2" nameend="col2" align="char" char=",">24.5</entry><entry namest="col3" nameend="col3" align="char" char=",">18.2</entry><entry namest="col4" nameend="col4" align="char" char=",">6.4</entry><entry namest="col5" nameend="col5" morerows="1" align="char" char=",">4.8</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">BP / after shampoos</entry><entry namest="col2" nameend="col2" align="char" char=",">28.6</entry><entry namest="col3" nameend="col3" align="char" char=",">20.6</entry><entry namest="col4" nameend="col4" align="char" char=",">6.7</entry></row></tbody></tgroup></table></tables>

0182These results show that the composition of the invention has good resistance to shampoos.

0183In addition, its toughness is greater than that of the mixture of dyes.

<b>EXAMPLE 2</b>

0184<chemistry id="chem0054" num="0054"><img file="EP1574205A2_D0063.tif" /></chemistry><chemistry id="chem0055" num="0055"><img file="EP1574205A2_D0064.tif" /></chemistry><chemistry id="chem0056" num="0056"><img file="EP1574205A2_D0065.tif" /></chemistry>

Process

:

0185In a tricolor, the azo compound (5 g), 100 ml of DMF and the hydrazone compound (2 g) are introduced. Allowed to react for 4 hours at 100 ° C. The product is recovered by precipitation in diisopropyl oxide (250 ml). The product, which is in the form of a black powder (2 g), is filtered off and dried.

0186The NMR and mass spectra are in agreement with the structure of the expected product.

0187The use of a dye composition of the same type as those described in Example 1 but comprising the dye obtained in this example makes it possible to obtain colored locks.

<b>EXAMPLE 3</b>

0188<chemistry id="chem0057" num="0057"><img file="EP1574205A2_D0066.tif" /></chemistry><chemistry id="chem0058" num="0058"><img file="EP1574205A2_D0067.tif" /></chemistry>

Process

:

0189In a tricolor are introduced the hydrazone compound (98 mg), 10 ml of DMF and the azo compound (200 mg). Allowed to react for 4 hours at 100 ° C. The product is recovered by precipitation in ethyl acetate (100 ml). The product, which is in the form of a black powder (200 mg), is filtered off and dried.

0190The NMR and mass spectra are in agreement with the structure of the expected product.

0191The use of a dye composition of the same type as those described in Example 1 but comprising the dye obtained in this example makes it possible to obtain colored locks.

EXAMPLE 4

0192<chemistry id="chem0059" num="0059"><img file="EP1574205A2_D0068.tif" /></chemistry><chemistry id="chem0060" num="0060"><img file="EP1574205A2_D0069.tif" /></chemistry>

Process

0193In a tricolor are introduced the nitrated compound (3.33 g), 100 ml of DMF and the azo compound (6.16 g). Allowed to react for 4 hours at 100 ° C. Evaporate to dryness.

0194The product is taken up in diisopropyl ether. Filtered and dried under vacuum.

0195A black powder (6 g) is obtained.

0196The NMR and mass spectra are in agreement with the structure of the expected product.

0197The use of a dye composition of the same type as those described in Example 1 but comprising the dye obtained in this example makes it possible to obtain colored locks.

EXAMPLE 5

0198<chemistry id="chem0061" num="0061"><img file="EP1574205A2_D0070.tif" /></chemistry><chemistry id="chem0062" num="0062"><img file="EP1574205A2_D0071.tif" /></chemistry>

Process

0199The azo compound (1.628 g) and the hydrazone compound (2.53 g) are suspended in 10 ml of dry acetonitrile, 10 mg of potassium iodide and a drop of DMF are added.

0200The reaction mixture is heated at 60 ° C. for three hours and then an acetonitrile fraction is removed by distillation.

0201The reaction mixture is again maintained at 60 ° C for 14h.

0202After cooling, the product (0.5 g) is isolated by precipitation in acetone.

0203The NMR and mass spectra are in agreement with the structure of the expected product.

0204The use of a dye composition of the same type as those described in Example 1 but comprising the dye obtained in this example makes it possible to obtain colored locks.

EXAMPLE 6

0205<chemistry id="chem0063" num="0063"><img file="EP1574205A2_D0072.tif" /></chemistry><chemistry id="chem0064" num="0064"><img file="EP1574205A2_D0073.tif" /></chemistry>

Process

0206200 mg of compound obtained in Example 5 are dissolved in 2 ml of methanol and then 1 ml of methanol solution containing 17 mg of ethanolamine is added.

0207The reaction mixture is heated at 60 ° C for one hour, cooled and diluted with acetone.

0208A precipitate forms. After filtration, 110 mg of compliant product is collected.

0209The NMR and mass spectra are in agreement with the structure of the expected product.

0210The use of a dye composition of the same type as those described in Example 1 but comprising the dye obtained in this example makes it possible to obtain colored locks.

EXAMPLE 7

0211<chemistry id="chem0065" num="0065"><img file="EP1574205A2_D0074.tif" /></chemistry><chemistry id="chem0066" num="0066"><img file="EP1574205A2_D0075.tif" /></chemistry>

Process

0212The azo compound (0.63 g) and the hydrazone compound (1.0 g) are suspended in 10 mL of dry DMF, 224 mg of potassium iodide are added and the reaction mixture is heated at 80 ° C. for 18 hours. .

0213The product (0.441 g) is isolated by precipitation in ethyl acetate

0214The NMR and mass spectra are in agreement with the structure of the expected product.

0215The use of a dye composition of the same type as those described in Example 1 but comprising the dye obtained in this example makes it possible to obtain colored locks.

EXAMPLE 8

0216<chemistry id="chem0067" num="0067"><img file="EP1574205A2_D0076.tif" /></chemistry><chemistry id="chem0068" num="0068"><img file="EP1574205A2_D0077.tif" /></chemistry><chemistry id="chem0069" num="0069"><img file="EP1574205A2_D0078.tif" /></chemistry>

Process

0217In a tricolor are introduced the azo compound (1.0 g), picoline (2 molar equivalents) and 30 ml of propan-2-ol.

0218It is allowed to react with stirring for 24 hours at 85 ° C. and then for 3 days at 92 ° C. Evaporate to dryness.

0219The product is taken up in water and washed with dichloromethane.

0220The aqueous phase is evaporated to dryness. The powder is taken up in ethyl acetate. Filtered and dried under vacuum.

0221A black powder (0.566 g) is obtained.

0222The NMR and mass spectra are in agreement with the structure of the intermediate.

0223In a tricolor, the intermediate obtained (0.25 g), N, N dimethyl-4-benzaldehyde (0.112 g), pyrrolidine (0.043 ml) and methanol (7 ml) are introduced.

0224It is left to react with stirring for 3 days at room temperature.

0225Evaporate to dryness. Wash with diisopropyl ether and then with ethyl acetate.

0226It is solubilized in dichloromethane (10 ml) and the product is precipitated by addition in a solution of ethyl acetate (90 ml) and propan-2-ol (10 ml).

0227Filtered and dried under vacuum.

0228A black powder (0.17 g) is obtained.

0229The NMR and mass spectra are in agreement with the structure of the product.

0230The use of a dye composition of the same type as those described in Example 1 but comprising the dye obtained in this example makes it possible to obtain colored locks.

EXAMPLE 9

0231<chemistry id="chem0070" num="0070"><img file="EP1574205A2_D0079.tif" /></chemistry><chemistry id="chem0071" num="0071"><img file="EP1574205A2_D0080.tif" /></chemistry>

Process

0232In a vial, the azo compound (1.0 g), 7 ml of pentanol and the nitro compound (0.6 g) are introduced.

0233It is left stirring for 18 hours at 85 ° C.

0234The product is precipitated by the addition of ethyl acetate. Filtered and dried under vacuum.

0235A black powder (1.3 g) is obtained.

0236The NMR and mass spectra are in agreement with the structure of the expected product.

0237The use of a dye composition of the same type as those described in Example 1 but comprising the dye obtained in this example makes it possible to obtain colored locks.

EXAMPLE 10

0238<chemistry id="chem0072" num="0072"><img file="EP1574205A2_D0081.tif" /></chemistry><chemistry id="chem0073" num="0073"><img file="EP1574205A2_D0082.tif" /></chemistry>

Process

0239In a vial, the azo compound (1.0 g), 7 ml of pentanol and the nitro compound (0.85 g) are introduced. It is left stirring for 18 hours at 85 ° C.

0240The nitrated compound (0.42 g) is then added and allowed to react with stirring for 3 hours at 90 ° C. Finally, the nitrated compound (0.85 g) is added.

0241It is left to react with stirring for 2 days at 90 ° C.

0242The product is precipitated by the addition of ethyl acetate. Filtered and washed with ethyl acetate and dried under vacuum.

0243A black powder (0.84 g) is obtained.

0244The NMR and mass spectra are in agreement with the structure of the expected product.

0245The use of a dye composition of the same type as those described in Example 1 but comprising the dye obtained in this example makes it possible to obtain colored locks.

EXAMPLE 11

0246<chemistry id="chem0074" num="0074"><img file="EP1574205A2_D0083.tif" /></chemistry><chemistry id="chem0075" num="0075"><img file="EP1574205A2_D0084.tif" /></chemistry>

Process

:

0247In a tricolor are introduced the azo compound (1 g), KI (100 mg) and 5 ml of dimethylformamide (DMF).

0248Stir and heat for 5 minutes at 90 ° C.

0249The hydrazone compound (1.79 g) solubilized in 5 ml of DMF is added. Allowed to react with stirring for 16 hours at 90 ° C.

0250The product is precipitated in ethyl acetate (250 ml).

0251Filtered and washed with ethyl acetate and dried under vacuum.

0252A black powder (2.0 g) is obtained.

0253The NMR and mass spectra are in agreement with the structure of the expected product.

0254The use of a dye composition of the same type as those described in Example 1 but comprising the dye obtained in this example makes it possible to obtain colored locks.

0255Examples 12 to 23 are obtained according to the procedure described in Example 11 by adjusting the amounts and replacing the DMF with N-methylpyrrolidone (NMP) or DMPU.

EXAMPLE 12

0256<chemistry id="chem0076" num="0076"><img file="EP1574205A2_D0085.tif" /></chemistry><chemistry id="chem0077" num="0077"><img file="EP1574205A2_D0086.tif" /></chemistry><chemistry id="chem0078" num="0078"><img file="EP1574205A2_D0087.tif" /></chemistry>

0257The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 289

0258Maximum absorption wavelength: λ_max : 420 nm; 566 nm; 250 nm

EXAMPLE 13

0259<chemistry id="chem0079" num="0079"><img file="EP1574205A2_D0088.tif" /></chemistry><chemistry id="chem0080" num="0080"><img file="EP1574205A2_D0089.tif" /></chemistry>

0260The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 303

0261Maximum absorption wavelength: λ_max : 566 nm; 420 nm; 252 nm

EXAMPLE 14

0262<chemistry id="chem0081" num="0081"><img file="EP1574205A2_D0090.tif" /></chemistry><chemistry id="chem0082" num="0082"><img file="EP1574205A2_D0091.tif" /></chemistry><chemistry id="chem0083" num="0083"><img file="EP1574205A2_D0092.tif" /></chemistry>

0263The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 247

0264Maximum absorption wavelength: λ_max : 424 nm; 518 nm; 258 nm

EXAMPLE 15

0265<chemistry id="chem0084" num="0084"><img file="EP1574205A2_D0093.tif" /></chemistry><chemistry id="chem0085" num="0085"><img file="EP1574205A2_D0094.tif" /></chemistry>

0266The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 261

0267Maximum absorption wavelength: λ_max : 422 nm; 538 nm; 256 nm

EXAMPLE 16

0268<chemistry id="chem0086" num="0086"><img file="EP1574205A2_D0095.tif" /></chemistry><chemistry id="chem0087" num="0087"><img file="EP1574205A2_D0096.tif" /></chemistry><chemistry id="chem0088" num="0088"><img file="EP1574205A2_D0097.tif" /></chemistry>

0269The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 277

0270Maximum absorption wavelength: λ_max : 558nm; 416 nm; 254 nm

EXAMPLE 17

0271<chemistry id="chem0089" num="0089"><img file="EP1574205A2_D0098.tif" /></chemistry><chemistry id="chem0090" num="0090"><img file="EP1574205A2_D0099.tif" /></chemistry>

0272The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 275

0273Maximum absorption wavelength: λ_max : 418 nm; 552 nm; 256 nm

EXAMPLE 18

0274<chemistry id="chem0091" num="0091"><img file="EP1574205A2_D0100.tif" /></chemistry><chemistry id="chem0092" num="0092"><img file="EP1574205A2_D0101.tif" /></chemistry><chemistry id="chem0093" num="0093"><img file="EP1574205A2_D0102.tif" /></chemistry>

0275The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 313

0276Maximum absorption wavelength: λ_max : 418 nm; 568 nm; 256 nm

EXAMPLE 19

0277<chemistry id="chem0094" num="0094"><img file="EP1574205A2_D0103.tif" /></chemistry><chemistry id="chem0095" num="0095"><img file="EP1574205A2_D0104.tif" /></chemistry>

0278The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 268

0279Maximum absorption wavelength: λ_max : 574 nm; 420 nm; 256 nm

EXAMPLE 20

0280<chemistry id="chem0096" num="0096"><img file="EP1574205A2_D0105.tif" /></chemistry><chemistry id="chem0097" num="0097"><img file="EP1574205A2_D0106.tif" /></chemistry><chemistry id="chem0098" num="0098"><img file="EP1574205A2_D0107.tif" /></chemistry>

0281The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 290

0282Maximum absorption wavelength: λ_max : 556 nm; 420 nm; 254 nm

EXAMPLE 21

0283<chemistry id="chem0099" num="0099"><img file="EP1574205A2_D0108.tif" /></chemistry><chemistry id="chem0100" num="0100"><img file="EP1574205A2_D0109.tif" /></chemistry>

0284The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 275

0285Maximum absorption wavelength: λ_max : 426 nm; 562 nm; 256 nm

EXAMPLE 22

0286<chemistry id="chem0101" num="0101"><img file="EP1574205A2_D0110.tif" /></chemistry><chemistry id="chem0102" num="0102"><img file="EP1574205A2_D0111.tif" /></chemistry><chemistry id="chem0103" num="0103"><img file="EP1574205A2_D0112.tif" /></chemistry>

0287The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 298

0288Maximum absorption wavelength: λ_max : 424 nm; 572 nm; 256 nm

EXAMPLE 23

0289<chemistry id="chem0104" num="0104"><img file="EP1574205A2_D0113.tif" /></chemistry><chemistry id="chem0105" num="0105"><img file="EP1574205A2_D0114.tif" /></chemistry>

0290The structure of the product is confirmed by LCMS analysis: molecular peak m / z = 279

0291Maximum absorption wavelength: λ_max : 424 nm; 590 nm

0292The use of dyeing compositions of the same type as that described in Example 1 but each comprising dyes obtained in Examples 12 to 23 makes it possible to obtain colored locks.