FR3044661A1 - NOVEL ANIONIC COLORANTS HETEROCYCLIC DISULFIDE PATTERN, DYE COMPOSITION COMPRISING SAME, AND METHOD FOR COLORING HUMAN KERATINIC MATERIALS FROM THESE DYES - Google Patents

Abstract

The invention relates to the dyeing of keratin materials using anionic direct dyes with a heterocyclic disulfide group. The subject of the invention is a dyeing composition comprising a fluorescent dye with a heterocyclic disulfide group, a process for dyeing keratin materials such as the hair, using said composition. It also relates to novel dyes heterocyclic disulfide group and their uses in the coloring of keratin materials. This composition makes it possible to obtain a particularly persistent and visible lightening effect on dark keratinous fibers. In addition, the process for dyeing keratin materials, the composition and the anionic dyes of the invention make it possible to obtain colors with said powerful, chromatic materials and with a good color increase.

Description

NOVEL ANIONIC COLORANTS HAVING A HETEROCYCLIC DISULFIDE PATTERN, DYE COMPOSITION COMPRISING SAME, AND METHOD FOR COLORING HUMAN KERATINIC MATERIALS THEREFROM

The invention relates to the dyeing of keratin materials using anionic dyes with a heterocyclic disulfide group of formulas (I).

It is known to dye keratinous fibers, especially human fibers, by direct dyeing. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and dyeing molecules having an affinity for the fibers, allowing them to diffuse and then rinsing the fibers.

The direct dyes which are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines, dyes of the azo, xanthene, acridine, azine or triarylmethane type.

The coloring of the keratinous fibers from these conventional direct dyes does not make it possible to significantly lighten the keratin fibers. The lightening of the color of dark keratin fibers to lighter shades, possibly modifying the shade of these, constitutes an important demand.

Conventionally, to obtain a lighter color, a chemical bleaching process is used. This method consists in treating the keratinous fibers, such as the hair, with a strong oxidizing system, generally consisting of hydrogen peroxide associated or not with persalts, most often in an alkaline medium. This bleaching system has the disadvantage of degrading the keratinous fibers, and altering their cosmetic properties. The fibers tend to become rough, more difficult to disentangle and more fragile. Finally, the lightening or the bleaching of keratinous fibers by oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in the straightening treatments.

Another lightening technique consists in applying fluorescent direct dyes to dark hair. This technique, described in particular in the documents WO 03/028685 and WO 2004/091473, makes it possible to respect the quality of the keratinous fiber during the treatment. However, these fluorescent direct dyes do not have a satisfactory tenacity vis-à-vis the external agents.

In order to improve the remanence, it is known to use fluorescent chromophore dyes interconnected by a "spacer" or "linker" which contains a disulfide function (see for example WO 2005/097051, EP 1647580, WO 2006/134043 , WO 2006/136617, WO 2007/110533, WO 2007/110534, WO 2007/110535, WO 2007/110537, WO 2007/110542). Nevertheless, for the fixing of these disulfide dyes to the surface of the keratin fibers to function, it is generally necessary to carry out at the same time, before or after the application of disulfide dyes, a treatment with a reducing agent. However, the use of reducing agents in a significant amount may have the disadvantage of releasing an unpleasant odor during the treatment of keratin fibers so that there is a real need to reduce the level of reducing agent. In addition, it is generally necessary to perform additional oxidative treatment using chemical oxidizing agent to fix the dyes on the keratinous fibers and thus improve the tenacity of the coloring.

On the other hand, carboxylic dyes comprising a heterocycle disulfide (A) and (B) (see formulas hereinafter) have been used and evaluated respectively as SERS (Surface Enhanced Raman Scanning) to detect specific DNA sequences (Tetrahedron, 68 ( 4), 1230-1240 (2012)) and as SAMs (Self Assembled Monolayers) on gold. These compounds have not been used for cosmetic purposes.

The object of the present invention is to provide novel systems for dyeing and / or lightening keratin materials, in particular human keratinous fibers, such as hair, that are powerful and durable.

In particular, it is an object of the invention to provide direct dyeing systems which make it possible to obtain colors and / or lightening effects which are stubborn in the face of successive washes, which do not degrade the keratin materials and which do not alter their properties. cosmetics. It is also sought to obtain a good rise in color after treatment of keratin materials.

Another object of the invention is to chromatically color, powerful and / or remanent vis-à-vis the external aggressions keratin materials. The invention also aims to provide compounds dyeing keratinous fibers such as hair with a low selectivity of coloration between the root and the tip, whether on natural or permed fibers.

These objects are achieved with the present invention which relates to a process for dyeing and / or lightening keratin materials, particularly dark keratinous fibers, in which a cosmetic composition comprising one or more anionic direct dyes is applied to said materials. with a heterocyclic disulfide group of the following formula (I): A- (X) p - Csat - (X ') p' - Het (I) their organic or inorganic acid salts, optical isomers, geometric isomers, and solvates such as than hydrates; formula (I) wherein:> A represents a radical containing at least one anionic chromophore; Het represents a monocyclic disulfide heterocyclic radical comprising from 4 to 10 members; X and X ', which are identical or different, represent: a linear or branched, saturated or unsaturated, linear or branched CrCi6 hydrocarbon chain, optionally interrupted and / or optionally terminated at one or both of its ends by one or more divalent groups or their combinations selected from: -N (R) -; -O-; -S-; -C (O) -; -S (O) 2 with R, which are identical or different, are chosen from a hydrogen atom, a C1-C4 alkyl radical and a C1-C4 hydroxyalkyl radical; an aromatic radical (hetero) cyclic or not, saturated or unsaturated, condensed or not, optionally comprising one or more identical or different heteroatoms, optionally substituted; a divalent group or the combination chosen from: -N (R) -; -O-; -S-; -CO)-; -S (0) 2- with R, as previously defined; preferentially the divalent group or groups or combinations thereof are chosen from -O-; -N (R) -; -C (O) - with R selected from a hydrogen atom, and a C 1 -C 4 alkyl radical; > p and p ', which are identical or different, represent an integer equal to 0 or 1; and> Csat represents a linear or branched, optionally substituted, saturated or unsaturated C 1 -C 6 hydrocarbon-based chain.

Another subject of the invention is a dyeing composition comprising, in a suitable cosmetic medium, at least one anionic direct dye with a heterocyclic disulfide group of formula (I) as defined above.

Another subject of the invention relates to the anionic direct dyes with a heterocyclic disulfide group of formula (I) as defined above, it being understood that the compound of formula (I) can not represent the carboxylate forms of compounds (A) or (B) ):

The method of the invention makes it possible to obtain a visible coloration of even dark keratin materials, in particular human keratinous fibers, in particular the hair, without degrading said material, which is persistent with regard to shampoos, of the common aggressions (sun, perspiration). ), and other hair treatments even in the absence of reducing agent. The process of the invention also makes it possible to obtain a lightening of keratin materials such as keratinous fibers, particularly dark keratinous fibers and more particularly dark hair. In addition, the dyes, the composition and the process of the invention make it possible to improve the color of the keratin materials, in particular in terms of intensity chromaticity and / or color increase.

The dyes of the invention are, moreover, stable with respect to the oxidants, and have a solubility in satisfactory cosmetic dyeing media. These dyes extend the color range to yellows and oranges. The dyes of formula (I) color after application on keratin fibers chromatically and remanent vis-à-vis the external aggressions keratin materials with a low selectivity of coloration between the root and the tip, and on different types of fibers.

In addition, it makes it possible to envisage the use of dye supports comprising, as an ingredient, anionic compounds such as anionic surfactants and anionic polymers, without altering the colon properties of the direct dyes.

For the purposes of the invention, the term "dark keratin material" is understood to mean that which has an enumerated luminescence L * in the CIE system L * a * b *, less than or equal to 45 and preferably less than or equal to 40, while also knowing that L * = 0 is equivalent to black and L * = 100 is white.

For the purposes of the invention, the term naturally or artificially dark hair, hair whose pitch is less than or equal to 6 (dark blonde) and preferably less than or equal to 4 (chestnut). The lightening of the hair is evaluated by the variation of "pitch" before and after application of the compound of formula (I). The notion "tone" is based on the classification of natural nuances, a tone separating each nuance from that which follows or immediately precedes it. This definition and the classification of natural shades is well known to hair professionals and published in the book "Science of hair treatments" Charles ZVIAK 1988, Ed Masson, p. 215 and 278.

Heights range from 1 (black) to 10 (very light blond), a unit corresponding to a tone; the higher the number, the clearer the nuance.

For the purposes of the invention, the term "hair discolored" means hair whose tone is greater than 4 (chestnut) and preferably greater than 6 (dark blonde).

One means for measuring the lightening effect provided to the hair after application of the fluorescent dyes of the invention is to use the hair reflectance phenomenon.

Preferably, the composition should, after application to dark hair bring to the results below. - We are interested in the reflectance performance of hair when irradiated with visible light in the wavelength range of 400 to 700 nanometers. The reflectance curves are then compared as a function of the wavelength, of the hair treated with the composition of the invention and of the untreated hair. - The curve corresponding to the treated hair must show a reflectance in the wavelength range from 500 to 700 nanometers higher than the curve corresponding to untreated hair. This means that, in the wavelength range of 500 to 700 nanometers, there is at least one range where the reflectance curve corresponding to the treated hair is greater than the reflectance curve corresponding to the untreated hair. The term "superior" means a difference of at least 0.05% reflectance, and preferably at least 0.1%. This does not prevent that there may exist in the wavelength range from 540 to 700 nanometers, at least one range where the reflectance curve corresponding to the treated hair is superimposable, or less than the reflectance curve corresponding to the untreated hair.

Preferably, the wavelength where the difference is greatest between the reflectance curve of the treated hair and that of the untreated hair is in the wavelength range of 500 to 650 nanometers, and preferably in the the wavelength range from 550 to 620 nanometers.

For the purposes of the present invention, and unless a different indication is given: - the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent borne by a carbon atom, chosen from: a C 1 -C 8 alkyl radical, optionally substituted by one or more radicals chosen from hydroxyl, C 1 -C 2 alkoxy, (C 2 -C 4) poly (hydroxy) alkoxy, acylamino, amino substituted by two identical or different C 1 -C 4 alkyl radicals, optionally carriers with at least one hydroxyl group or, the two radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered, preferably 5 or 6-membered, optionally substituted saturated or unsaturated heterocycle comprising optionally another heteroatom identical or different from the nitrogen; . a halogen atom such as chlorine, fluorine or bromine; . a hydroxyl group; . a C 1 -C 2 alkoxy radical; . a C2-C4 (poly) -hydroxyalkoxy radical; . an amino radical; . a 5- or 6-membered heterocycloalkyl radical; . a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (Cr C4) alkyl radical, preferably methyl; An amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: i) a hydroxyl group, ii) an amino group optionally substituted by one or two optionally substituted C 1 -C 3 alkyl radicals , said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom different from or different from nitrogen, an acylamino radical (-N (R) -C (O) R ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C1-C2 alkyl radical; . a carbamoyl radical ((R) 2 N-C (O) -) in which the radicals R, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; . a carboxylic acid or ester radical, (-OC (O) R ') or (-C (O) OR'), in which the radical R 'is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing a at least one hydroxyl group and the radical R 'is a C 1 -C 2 alkyl radical; . the carboxylic radical may be in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not); . an alkylsulphonylamino radical (R'S (O) 2-NR-) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C 1 -C 4 alkyl radical; a phenyl radical; . an aminosulphonyl radical ((R) 2 N -S (O) 2 -) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group, . a cyano group (CN); . a polyhaloalkyl group, preferentially trifluoromethyl (CF3); the cyclic or heterocyclic part of a non-aromatic radical may be substituted by at least one substituent carried by a carbon atom chosen from the groups: hydroxyl, C1-C4 alkoxy, (poly) hydroxyalkoxy C2-C4, alkylcarbonylamino ((RC (O) -NR'-) in which the radical R 'is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R is a C 1 -C 2 alkyl radical, amino substituted with two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered heterocycle, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or different from nitrogen; alkylcarbonyloxy ((RC (O) -O-) in which the radical R is a C 1 -C 4 alkyl radical, amino substituted with two identical or different alkyl groups C 1 -C 4 optionally carrying at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, optionally substituted urea or unsaturated optionally comprising at least one other heteroatom different or different from nitrogen; . alkcoxycarbonyl ((RO-C (O) -) in which the radical R is a C 1 -C 4 alkyl radical, amino substituted with two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other non-nitrogen heteroatom or a heterocyclic ring radical, or a part thereof; a non-aromatic radical of an aryl or heteroaryl radical may also be substituted by one or more oxo groups; a hydrocarbon chain is unsaturated when it comprises one or more double bonds and / or one or more triple bonds; Represents a mono or polycyclic group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; erentially the aryl radical is phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl; a "heteroaryl radical" represents a mono- or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium; , and of which at least one cycle is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl; a "cyclic radical" is a non-aromatic, mono or polycyclic cycloalkyl radical, condensed or not, containing from 5 to 22 carbon atoms, which may contain from 1 to several unsaturations; a "heterocyclic radical" is a non-aromatic mono or polycyclic radical, condensed or not, containing from 5 to 22 members, containing from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium morpholinyl, thiomoropholinye, piperidinyl, piperazinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothophenyl, azepanyl, thioazepanyl; preferentially pirrolidinyl and morpholino; a "heterocyclic disulfide radical" is a heterocyclic radical comprising in its cycle a disulfide chain SS between two carbon atoms, directly, said heterocycle being able to be substituted; an "alkyl radical" is a linear or branched C 1 -C 16 hydrocarbon radical, preferably a C 1 -C 8 hydrocarbon radical; the expression "optionally substituted" ascribed to the alkyl radical implies that said alkyl radical may be substituted with one or more radicals chosen from the radicals i) hydroxyl, ii) optionally substituted C 1 -C 4 alkoxy, iii) acylamino, iv) amino by one or two identical or different C 1 -C 4 alkyl radicals, said alkyl radicals being capable of forming, with the nitrogen atom carrying them, a 5- to 7-membered heterocyl, optionally comprising another heteroatom different from or different from nitrogen; v) C (O) M with M representing a hydrogen atom or a cationic counterion such as alkali metal, alkaline earth metal or ammonium; an "alkoxy radical" is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in C1-C16, preferentially in C1-C8; when the alkoxy group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above

The compounds of formula (I) according to the invention may be anionic, cationic or neutral; the chromophore A is anionic, or it comprises one or more counterions or a mixture of counterions to ensure electroneutrality, or one or more groups in the compound makes it possible to ensure electroneutrality. For example, if the remainder of the compound is anionic with -O ', -C (O) O', S (O) 2-O ', -P (O) (OH) 2-O'groups; either in the molecule is one or more -N + (R) 2-, or phosphonium groups, to ensure electroneutrality, or they are in the form -O ', M +, -C (0) 0', M +, S (O) 2 -O 'M +, with M + representing a cationic counterion, preferentially chosen from alkaline or alkaline earth cations such as Na, Mg, K and Ca, and organic cations such as ammonium NH4 + or ( di / tri) (CrC6) alkylammonium; an "organic or inorganic acid salt" is more particularly chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 SO 4, iv) alkyl sulphonic acids: Alk-S (O) 20H such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 20H such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-O-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3PO4; xiii) acetic acid CH3COOH; xiv) triflic acid CF3SO3H and xv) tetrafluoroboric acid HBF4.

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

According to the present invention, the term "anionic chromophore" means a radical derived from an anionic direct dye. An anionic direct dye is a compound that is capable of absorbing in the visible and possibly in the ultraviolet ie at a wavelength λabs of between 250 and 800 nm.

The chromophore can be further fluorescent ie it is able to absorb in the visible and possibly in the ultraviolet and is also able to re-emit light absorbed in the visible range to a length of emission wave greater than the absorption wavelength ie Xem between 400 and 800 nm. Preferably, the fluorescent chromophore is derived from a fluorescent dye capable of absorbing in the visible range between 400 and 800 nm and reemitting in the visible Xem between 400 and 800 nm. More preferably, the fluorescent chromophore is derived from a dye capable of absorbing at an Aabs of between 420 nm and 550 nm and of reemitting in the visible at an Xem of between 470 and 600 nm. /. Formula dyes (!)

The dye (s) of formula (I) are anionic, ie the radical A of formula (I) contains one or more chromophores, which are identical or different, anionic being understood that when A comprises several chromophores, it comprises more anionic chromophores than cationic chromophores. Preferably all the chromophores of A are anionic.

/. 1. Anionic Chromophore A

The dyes of the invention of formula (I) are anionic direct dyes. The anionic chromophore (s) of the invention are derived from anionic direct dyes called "acid dyes" or "acid dyes" for their affinity with alkaline substances (see for example "Industrial Dyes, Chemistry, Properties, Application", Klaus Hunger Ed Wiley-VCH Verlag GmbH & CoKGaA, Weinheim 2003). Acidic or anionic dyes are known in the literature (see for example "Ullman's Encyclopedia of Industrial Chemistry", Azo Dyes, 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a03 245, Section 3.2;

Textile Auxiliaries, 2002 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a26 227 and "Ashford's Dictionary of Industrial Chemicals, Second Edition, p. 14-p. 39, 2001).

By "anionic direct dyes" is meant any direct dye comprising in its structure at least one sulphonate group SO 3 'and / or at least one carboxylate group C (O) O' and optionally one or more additional anionic groups G "with G ', identical or different, representing an anionic group chosen from alcoholate O ', thiolate S', carboxylate and thiocarboxylate: -C (Y) -Y "with Y and Y 'identical or different representing an oxygen or sulfur atom, preferably G 'represents a carboxylate ie Y and Y' represents an oxygen atom.

More particularly, A represents a chromophore A1:

A1

With:

Col (_) m representing the anionic portion of the chromophore derived from anionic direct dye or acid dye having in its structure at least one sulphonate group and / or at least one carboxylate group and comprising m anionic charge (s): m and n, identical or different, represent an integer inclusive between 1 and 10; Q +, identical or different, represents a cationic, organic or inorganic counterion, cosmetically acceptable, preferably selected from alkali or alkaline earth metal cations such as Na + or K +, or ammonium, (di) (tri) (Cr C6) alkylammonium, cationic heteroaryl such as pyridinium, imidazolium; it being understood that - when n is greater than or equal to 2, then Q may be identical or different from each other; m and n are such that the electroneutrality of the dyes of the invention (I) is ensured. Preferably -Col () m comprises in its structure: at least one sulphonate group and at least one (hetero) aryl group, it being understood that at least one sulphonate group is linked directly to a (hetero) aryl preferentially aryl group such that phenyl or benzo; and o optionally one or more anionic groups G 'as defined above.

According to another preferred embodiment of the invention -Col () m comprises in its structure:

at least one carboxylate group and at least one (hetero) aryl group, it being understood that at least one carboxylate group is directly linked to a (hetero) aryl group, preferentially aryl such as phenyl or benzo; and o optionally one or more anionic groups G 'as defined above.

According to yet another preferred embodiment of the invention -Col (, m comprises in its structure: o at least one carboxylate group and at least one (hetero) aryl group, it being understood that at least one sulphonate or carboxylate group is directly connected to a group (hetero) aryl preferably aryl such as phenyl or benzo, and o optionally one or more anionic groups G 'as defined above.

According to yet another preferred embodiment of the invention, -C has, in its structure: at least one carboxylate group, at least one sulphonate group and at least one (hetero) aryl group, it being understood that at least one a sulphonate or carboxylate group is directly linked to a (hetero) aryl group, preferably an aryl group such as phenyl or benzo, and optionally one or more anionic groups G "as defined above.

According to a particular embodiment of the invention, the dyes of formula (I) are such that A represents A1 with m equal to n. An advantageous variant of the invention relates to the dyestuffs of formula (I) for which m and n are 1, 2 or 3.

According to a particular embodiment, the preferred dye (s) of formula (I) of the invention are chosen from those for which A is derived from acid nitro dyes, acid azo dyes such as diaryls or pyrrazolones, and azine dyes. acids, acidic triarylmethane dyes, acidic indoamine dyes, acid xanthenes, acid anthraquinone dyes, acidic quinolines, indigoids and acidic natural dyes; each of these dyes having at least one cationic counterionic sulphonate or carboxylate group as defined above, more particularly between 1 and 5 sulphonate or carboxylate groups, preferably between 1 and 3 sulphonate or carboxylate groups;

Preferably, the preferred dye (s) of formula (I) of the invention are chosen from those for which A is derived from direct dyes chosen from diaryl anionic azo dyes; anionic azo dyes pyrrazolone; anionic anthraquinone dyes; anionic nitro dyes; anionic triarylmethane dyes; dyes derived from indoles or anionic indigoids; and anionic quinoline dyes; each of these dyes having at least one cationic counterionic sulphonate or carboxylate group as defined above, more particularly between 1 and 5 sulphonate or carboxylate groups, preferably between 1 and 3 sulphonate or carboxylate groups; More preferably A is derived from diaryl anionic azo dyes. By way of examples of dyes of the formula of diaryl anionic azo dyes, mention may be made of: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33 , Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Red Acid 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2; Acid Red 111, Acid Red 134, and Acid yellow 38;

According to a particular embodiment A is an anionic fluorescent chromophore derived from anionic direct fluorescent dyes. The following direct dyes may be mentioned: anionic triarylmethanes; anionic xanthenes and anionic quinoline dyes; each of these dyes having at least one cationic counterionic sulfonate or carboxylate group as defined above. Preferably A is derived from fluorescent dye that absorbs in the range of yellow, orange, and red. 1.2. Ct:

As indicated previously, in the formula (I), Csat represents a divalent hydrocarbon chain C1-C16, linear or branched, optionally substituted. As a substituent, mention may be made of amino, (CrC 4) alkylamino, (C 4 -C 4) dialkylamino groups, or the group Ra-Za-C (Zb) - (in which Za, Zb, which may be identical or different, represent an atom of oxygen, sulfur, or a group NRa ', and Ra, represents an alkali metal, a hydrogen atom, or a group CrC4 alkyl and Ra' represents a hydrogen atom or a group CrC4 alkyl) present preferably on the carbon in the beta or gamma position of the atoms of the disulfide -SS- chain of the heterocycle Het.

In particular, in the case of formulas (I), Csat represents a divalent, saturated or unsaturated, preferably saturated, linear or branched, preferably linear, hydrocarbon-based chain comprising from 1 to 14 carbon atoms, preferably from 2 to 10 carbon atoms. more preferably between 3 and 6 carbon atoms such as 4 carbon atoms. 1.3. X and X ':

According to a particular embodiment of the invention, in formula (I), mentioned above, when p or p 'is equal to 1, X and X', which are identical or different, represent the following sequence: (T) t- (Z) z- (T ') t- said sequence being connected in formulas (I), as follows: - Csat- (T') t '- (Z) z- (T) t- (A or Het) ; a sequence in which:> T and T ', which may be identical or different, represent one or more radicals or their combinations chosen from: -S (O) 2-; -O-; -S-; -N (R) -; -C (O) -; with R, representing a hydrogen atom, a C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or aryl (C 1 -C 4) alkyl radical; and a heterocycloalkyl or heteroaryl radical, cationic or non-cationic, preferentially monocyclic, preferably containing two heteroatoms (more preferably two nitrogen atoms) and preferably comprising from 5 to 7 members, more preferably piperazinyl or piperidinyl; preferentially T and T 'represent one or more radicals or their combinations chosen from -O-, -N (R) -, -C (O) -, with R chosen from a hydrogen atom, and a C 1 -C 4 alkyl radical; > the indices t and t ', identical or different, are 0 or 1; Z represents: - (CRiR 2) m - with m integer between 1 and 8 and R 2, which may be identical or different, represent a hydrogen atom or a CrC 4 alkyl, CrCl 2 alkoxy, hydroxy, cyano, carboxy, amino or CrC 4 group; alkylamino, Cr C4 dialkylamino, said alkyl radicals being able to form with the nitrogen atom which carries them a heterocyle comprising from 5 to 7 members, optionally comprising another heteroatom different or different from nitrogen; - (CH2CH2O) q- or - (OCH2CH2) q- in which q is an integer between 1 and 15, or an aryl, alkylaryl or arylalkyl radical in which the alkyl radical is C 1 -C 4 and the aryl radical is preferably C 6, being optionally substituted by at least one SO 3 M group with M representing a hydrogen atom, an alkali metal or an ammonium ammonium group substituted with one or more identical or non-linear, linear or branched, optionally substituted C 1 -C 6 alkyl radicals; at least one hydroxyl> z is 0 or 1.

Moreover, according to one particular embodiment of the invention, Z represents:

With q as defined above and r representing an integer inclusively between 0 and 4, M representing an anionic counterion as defined above. 1.4. Het:

As indicated previously, in the formula (I), Het represents a monocyclic disulfide heterocyclic radical comprising from 4 to 10 members.

According to a particular embodiment, Het is of formula (II) linked to the remainder of the molecule by one of the substituents R5, R6, R7, R8, R6 or R10, or else said radical is connected to the remainder of the molecule directly by one of the atoms of carbon of the heterocycle radical in position alpha, beta of the disulfide chain or when q is 2 or 3 in the gamma position in which case one of the substituents R5, R6, R7, Rs, R9 or R10, is absent: formula (II) in which :

R5, R6, R9 and R10, which may be identical or different, represent a hydrogen atom, or a group chosen from: i) (CrC8) alkyl, iii) hydroxy, iv) (di) (CrC8) (alkyl) amino, v ) (CrC8) alkoxy, especially R5, R6, R9 and R10 represent a hydrogen atom or a (CrC4) alkyl group such as methyl, preferably R5, R6, R9 and R10 represent a hydrogen atom; R7 and R8, identical or different, represent a hydrogen atom, or

a group selected from: i) (CrC8) alkyl, iii) hydroxy, iv) (di) (Cr C8) (alkyl) amino, v) (CrC8) alkoxy; in particular R 7 and R 8 are chosen from a hydrogen atom and a (CrC 4) alkyl group such as methyl, preferably R 7 and R 8 represent a hydrogen atom; or two radicals carried by the same carbon atom R5 and R6, R7 and R8, and / or Rg and R10 together with the carbon atom carrying them a carbonyl group; q represents an integer inclusive of between 1 and 3, particularly between 1 and 2; it being understood that when q is 2 or 3 then the groups R7 and R8 may be identical or different from each other; preferably q is 1; and more particularly all the substituents R5 to R10 represent a hydrogen atom. 1.4. Dyes of formula (fl) or EL ·

Another subject of the invention relates to the anionic direct dyes with heterocyclic disulfide group of formula (I) as defined with the understanding that the compounds of formula (I) can not represent the carboxylate forms of compounds (A) or (B) :

According to a particular embodiment of the invention, the anionic direct dyes of the invention are chosen from the following dyes of formula (a) to (g):

As well as their salts of organic or mineral acid, optical isomers, geometrical isomers, their tautomers and solvates such as hydrates;

Formulas (a) to (g) in which: A is as defined above, in particular A is derived from acid nitrated direct dyes, acid azo dyes such as diaryl or pyrrazolone, acidic azine dyes, acid triarylmethane dyes, acidic indoamine dyes, acid xanthenes,

acid anthraquinone dyes, acidic quinolines, indigoids and acidic natural dyes; each of these dyes having at least one cationic counterionic sulphonate or carboxylate group as defined above, more particularly between 1 and 5 sulphonate or carboxylate groups, preferably between 1 and 3 sulphonate or carboxylate groups; more preferentially A is derived from diaryl anionic azo dyes comprising from 1 to 5 sulphonate or carboxylate groups, preferably from 1 to 3 sulphonate groups; X and X 'are as defined above, in particular X and X' represent a divalent group or the combination chosen from: -N (R) -, -O-, -S-, -C (O) - and - S (O) 2- with R, as previously defined; preferably the divalent group or groups or combinations thereof are chosen from -O-, -N (R) - and -C (O) - with R chosen from a hydrogen atom, and a C 1 -C 4 alkyl radical; more preferably X and X 'represents a divalent amide group -N (R) -C (O) - or -C (O) -N (R) - with R representing a hydrogen atom, or a C 1 -C 4 alkyl radical; • p and p ', identical or different, represent an integer equal to 0 or 1; preferably p is 1 and p 'is 0; and Csat is as defined above, preferably represents a linear or branched C 1 -C 10 alkylene chain, unsubstituted, more preferably C 2 -C 8, better C 3 -C 5 than C 4; R5, R6, R9 and R10, as defined above, especially represent a hydrogen atom or a (CrC4) alkyl group such as methyl, preferably R5, R6, R9 and R10 represent a hydrogen atom; R 7 and R 8 as defined above, especially represent a hydrogen atom and a (CrC 4) alkyl group such as methyl, preferably R 7 and R 8 represent a hydrogen atom; preferably all the substituents R5 to R10 represent a hydrogen atom.

Preferably, the compounds of formula (I) of the invention are chosen from compounds (a) and (b), more preferably (a).

According to one particular embodiment, the anionic dyes of formula (I) of the invention are chosen from the following compounds (1 "a) and (1" b):

As well as their salts of organic or mineral acid, optical isomers, geometrical isomers, their tautomers and solvates such as hydrates; formula (I) in which: X, X ', p, p', Csat, R5, R6, R7, Re, R9 and R10 are as defined above for compounds of formulas (a) to (l) g), q is 1 or 2 with the proviso that when q is 2 then the groups R7 and R8 may be the same or different from each other, preferably q is 1; preferably p is 1 and p 'is 0, R5 to R10 are hydrogen, X is a divalent amide group -N (R) -C (O) - or -C (O) -N (R) - with R representing a hydrogen atom, or a C 1 -C 4 alkyl radical; and Csat represents a C1-C10 alkylene chain, linear or branched, unsubstituted, more preferably linear; R 1 and R 2, which are identical or different, represent a group chosen from: i) hydroxy, ii) thiol, iii) nitro, iv) (CrC 6) alkyl optionally substituted, in particular (CrC 4) alkyl such as methyl or ethyl, v) (CrC6) alkoxy in particular (CrC4) alkoxy such as ethoxy or methoxy, vi) (CrC6) alkylthio, vii) halogen and viii) amino-NRaRb with Ra and Rb, identical or different, representing: o a hydrogen atom, a (CrC6) alkyl group, particularly (CrC4) alkyl such as methyl, or ethyl, said alkyl group being optionally substituted by one or more hydroxyl groups, or where Ra and Rb form with the nitrogen atom which carry them a saturated or unsaturated 5- to 8-membered heterocyclic ring, preferably 5 or 6-membered heterocycle, said heterocycle being able to:

a) contain one or more heteroatoms or groups selected from oxygen, sulfur, and N (RC), with Rc representing a hydrogen atom or a (CrC4) alkyl group optionally substituted by one or more hydroxyl groups, such as methyl, ethyl or hydroxyethyl, and / or b) be substituted with one or more identical or different groups selected from hydroxy, (C1-C4) alkyl optionally substituted with one or more hydroxy, (C1-C4) alkyloxy groups such as ethoxy or methoxy, (di ) (CrC4) (alkyl) amino, (di) hydroxy (CrC4) alkylamino; Z and Z ', which are identical or different, represent a carboxylate group -C (O) O', M + or sulfonate -S (O) 2 -O 'M +, with M + representing a cationic counterion, cosmetically acceptable, preferably chosen from alkaline or alkaline earth cations such as Na, Mg, K and Ca, and organic cations such as ammonium NH4 +, (di / tri) (CrC6) alkylammonium, cationic heteroaryl such as pyridinium; preferentially Z and Z 'represent a group -S (O) 2-0' M +; • t and t ', identical or different, represent an integer inclusive between 0 and 5, it being understood that z + z' is an integer greater than or equal to 1; in particular z + z 'is an integer inclusive of between 1 and 3; • x is an integer inclusive between 0 and 5; • x 'is an integer inclusive between 0 and 4; • present or absent, represents a benzo ring, preferably the cycle is absent; it being understood that when x, x ', t and t' are greater than or equal to 2, then Ri respectively are identical or different from each other, R2 are identical to or different from each other, Z are identical or different from each other, and Z 'are identical or different from each other.

Preferably, the anionic dyes of formula (I) according to the invention are chosen from those of formula (I "b).

According to a particular embodiment of the invention, the dyes are chosen from those of formula (I "'b):

As well as their salts of organic or mineral acid, optical isomers, geometrical isomers, their tautomers and solvates such as hydrates; formula (I "'b) wherein X, p, Z', t ', q, Csat, R1, x, R2, x', are as previously defined for compounds of formula (I"b); preferentially: • x represents an integer between 0 and 4 inclusive, particularly between 1 and 3, preferably equal to 0 or 1; X 'represents an integer between 0 and 3, especially between 1 and 2, preferably equal to 1; X represents a divalent amide group -N (R) -C (O) - or -C (O) -N (R) -, preferably -N (R) -C (O) - with R representing a hydrogen atom or a C 1 -C 4 alkyl radical; P is 1; • represents an integer inclusive between 1 and 3, such as 2; R 1, which is identical or different, represents a group chosen from: i) hydroxy, ii) nitro, iv) (CrC 6) alkyl, in particular (CrC 4) alkyl such as methyl or ethyl, v) (CrC 6) alkoxy in particular (CrC 4) alkoxy such as ethoxy or methoxy, vi) (Cr C6) alkylthio particular (CrC4) alkylthio such as ethylthio or methylthio, and vii) amino -NRaRb with Ra and Rb, identical or different, representing: o a hydrogen atom, o a (CrC6) alkyl group, particularly (CrC4) alkyl such as methyl, or ethyl, said alkyl group being optionally substituted with one or more hydroxy groups such as hydroxyethyl, or where Ra and Rb form with the nitrogen atom which they carry a saturated 5- or 6-membered heterocycle, said heterocycle being able to furthermore: a) contain one or more heteroatoms or groups chosen from oxygen, sulfur, and N (RC), with Rc representing a hydrogen atom or a group ( CrC4) alkyl optionally substituted with one or more groups hydroxy, such as methyl, ethyl or hydroxyethyl, and / or b) be substituted with one or more hydroxy groups; R 2, identical or different, represents a group chosen from: i) hydroxy, ii) thiol, iv) (CrC 6) alkyl, in particular (CrC 4) alkyl such as methyl or ethyl, v) (Cr C 6) alkoxy in particular ( CrC4) alkoxy such as ethoxy or methoxy, vi) (Cr C6) alkylthio, especially (CrC4) alkylthio, such as ethylthio or methylthio, and vii) amino -NRaRb with Ra and Rb, identical or different, representing a hydrogen atom or a (CrC6) alkyl group, particularly (CrC4) alkyl such as methyl, or ethyl; preferably R2 represents a hydroxy or thiol group, more preferably a thiol; • Z ', identical or different, represents a group -S (O) 2-0' M + with M + representing a cationic counterion, preferentially chosen from alkaline or alkaline earth cations such as Na, Mg, K and Ca, and organic cations such as ammonium NH4 + or (di / tri) (CrC4) alkylammonium; Csat represents a linear or branched, preferably linear, (C -C 8) alkylene group, such as - (CH 2) m - with m representing an integer between 2 and 8, in particular between 3 and 6, such that m is 4; particularly R 1 is on the phenyl ring in the 2 ', 4' and / or 6 'position, preferably in the 4'position; particularly R2 is on the naphthyl ring in position 1, 4, 5 and / or 8, preferably in the 8 position; particularly the group X is connected to the naphthyl ring in position 1, 4, 5 and / or 8, preferably in position 1; it being understood that X can not be positioned at a position where a group R2 is located; in particular, Z 'is on the naphthyl ring in position 2, 3, 6, and / or 7, preferably in position 3 and 6; and particularly the azo group -N = N- is connected to the naphthyl ring in the 2, 3, 6, and / or 7 position, preferably in the 2 or 7 position, more preferably 7; it being understood that -N = N- can not be positioned on a position where there is a group Z '.

According to one particular embodiment of the invention, the dyes are chosen from those of formula (I "" b):

As well as their salts of organic or mineral acid, optical isomers, geometrical isomers, their tautomers and solvates such as hydrates; formula (I "" b) in which Csat, M +, R, R4, x, R2, and x 'are as defined above,

preferably x 'is 0, 1 or 2, more particularly x' is 0; R represents a hydrogen atom or a (CrC4) alkyl group, more preferably; R represents a hydrogen atom; and R2 is positioned at position 2 or 5 on the naphthyl ring.

Preferably, the anionic dyes of formula (I) are of formula (I "'b) with x' = 0; x = 0 or 1; R represents a hydrogen atom or a (CrC4) alkyl group, more preferably; R represents a hydrogen atom;

R 1 represents a group chosen from i) hydroxy, ii) nitro, iii) C 1 -C 4 alkylthio such as methylthio, iv) C 1 -C 4 alkoxy, more preferably C 1 -C 2 such as methoxy or ethoxy, v) NRaRb amino with:

Ra and Rb, identical or different, representing a hydrogen atom, a C 1 -C 4 alkyl group such as methyl, or ethyl or a C 1 -C 4 hydroxyalkyl group, preferably C 1 -C 2 such as hydroxethyl; or

Ra and Rb, together with the nitrogen atom carrying them, form a saturated 5- or 6-membered heterocycle, said heterocycle may furthermore comprise one or more heteroatoms or groups chosen from the oxygen atom or group - N (RC) -, with Rc representing a hydrogen atom or a C 1 -C 4 alkyl group such as methyl, and / or o being substituted by one or more identical or different groups selected from hydroxy, C 1 -C 4 alkyl, hydroalkyl groups; CrC 4, C 1 -C 4 alkoxy, (di) (C 1 -C 4) (alkyl) amino, (di) hydroxy (C 1 -C 4) alkylamino; and Csat denotes a saturated divalent hydrocarbon chain (or alkylene) containing from 2 to 8 carbon atoms, preferably from 3 to 6 carbon atoms.

More particularly, the anionic dyes of formula (I) are of formula (I "'b) with: - x' = 0; x = 0 or 1 R represents a hydrogen atom; and R 1 represents a group selected from: i) hydroxy, nitro (NO 2), iii) C 1 -C 4 alkylthio such as methylthio, C 1 -C 4 alkoxy such as methoxy, or ethoxy, iv) amino NRaRb with R a and R b independently representing a hydrogen atom a C 1 -C 4 alkyl group such as methyl, or ethyl; a C 1 -C 4 hydroxyalkyl group, more preferably C 1 -C 2 such as hydroxethyl or else R a and Rb form, with the nitrogen atom carrying them, a saturated 5- or 6-membered heterocycle, chosen from the pyrrolidine, piperidine, piperazine and heterocycle rings; may also be substituted by one or more identical or different groups selected from hydroxy, C 1 -C 4 alkyl such as methyl, C 1 -C 4 hydroalkyl such as hydroxyethyl;

Csat represents a (C3-C6) alkylene group such as butylene - (CH2) 4-.

More preferably, the anionic dyes of formula (I) are chosen from:

With M + a cationic counterion as defined above, preferably alkaline such as Na, K, ammonium, or pyridinium; compounds 1 to 15 as well as their optical, geometric, tautomeric and solvated isomers such as hydrates;

Thus the compounds of formula (I) can be obtained by reaction of the acid chloride (b) on the derivative (c) in an aprotic solvent in the presence of a base such as for example in THF in the presence of pyridine.

When necessary, the acid chloride (b) can be prepared by conventional methods known to those skilled in the art, for example by reaction of the acid

corresponding carboxylic acid with thionyl chloride in an anhydrous aprotic solvent.

The compounds (I) can be synthesized by a reaction between a compound (a1) and a compound (a1). This reaction is exemplified in the diagram below:

with A, X, p, q, Csat and R5 to R10, are as previously defined; Nude representing a nucleophilic group; <e representing an electrophilic group; and Tb the bond generated after nucleophilic attack on the electrophile.

These nucleophilic substitution reactions are known to those skilled in the art. For example, reference may be made to the book Advanced Organic Chemistry (ISBN 0-471-60180-2). By way of example, the covalent bonds Tb that can be generated are listed in Table A below from condensation of electrophiles with nucleophiles:

Table A

* / es activated esters of general formula -CO-Part with Part representing a leaving group such as oxysuccinimidyl, oxybenzotriazolyl, optionally substituted aryloxy; ** Acyl azides can rearrange to give isocyanates.

These reactions are known to those skilled in the art and are described in the literature. Reference can be made to Advanced Organic Chemistry (ISBN 0-471-60180-2).

An alternative to this method is to use a fluorescent chromophore having an electrophilic acrylate function (-O-C (O) -C = C-) on which an addition reaction is carried out which will generate a Tb bond.

In some cases it is necessary to protect the nucleophilic and electrophilic groups of reagents that are not desired to react with each other before the condensation reaction. Then it is necessary to deprotect said nucleophilic and electrophilic groups. Protective groups of amines, hydroxy, thiols, by

Examples are well known to those skilled in the art including the reaction conditions necessary for the protection and deprotection step. Reference can be made to Protecting groups in Organic Chemistry (ISBN 0-471-05764-9) for protection and deprotection conditions.

Compounds (a2) are known to those skilled in the art and their synthesis is described in Comprehensive Heterocyclic Chemistry III, 2008, Chapter 4.11, Pages 893-954 and Comprehensive Heterocyclic Chemistry III, 2008, Chapter 13.10, Pages 299-319. . Compounds are commercially available.

Alternatively the compounds (h) can be synthesized by a reaction between a compound (a3) and a compound (a4). This reaction is exemplified in the diagram below:

The compounds (I) can be synthesized by a reaction between a compound (a1) and a compound (a1). This reaction is exemplified in the diagram below:

with A, X, p, q, Csat, Rs to R10, and Tb are as previously defined; representing a nucleophilic group; <E representing an electrophilic group.

Alternatively, the compounds (12) can be synthesized by a reaction between a compound (a5) and a compound (a6). This reaction is exemplified in the diagram below:

with A, X, p, q, Csat, Rs to R10, are as previously defined; Nude representing a nucleophilic group; Έ representing an electrophilic group; and Ta the bond generated after nucleophilic attack on the electrophile. For example, links

Covalent Ta that can be generated are listed in Table B from condensation of electrophiles with nucleophiles:

Table B:

* activated esters of general formula -CO-Part with Part representing a leaving group such as oxysuccinimidyl, oxybenzotriazolyl, optionally substituted aryloxy; ** Acyl azides can rearrange to give isocyanates.

These reactions are known to those skilled in the art and are described in the literature. Reference can be made to Advanced Organic Chemistry (ISBN 0-471-60180-2).

Another variation of the synthesis is to react a compound (a7) with a heterocyclic compound (a8). This reaction is exemplified in the diagram below:

with A, X ', p', q, Csat, R5 to R10, and Ta are as previously defined; Nude representing a nucleophilic group; £ representing an electrophilic group;

Compounds (a8) are known to those skilled in the art and their synthesis is described in Comprehensive Heterocyclic Chemistry III, 2008, Chapter 4.11, Pages 893-954 and Chapter 13.10, Pages 299-319. Compounds are also commercially available.

The reagent (a10) can react with an anionic chromophore (a7) to yield an anionic dye (13) according to the invention. Compounds (A9) and (a10) are known to those skilled in the art and are described in the literature. Some of them are commercially available.

with A, q, Csat, Rs to R10, Ta and Tb are as previously defined; Nude representing a nucleophilic group; Έ representing an electrophilic group;

Compounds (a4) and (a9) are known to those skilled in the art and some are commercially available.

The reagent (a12) can react with an anionic chromophore (a2) to yield an anionic dye (13) according to the invention. Compounds (a11) and (12) are known to those skilled in the art and are described in the literature. Some of them are commercially available.

with A, q, Csat, R5-R10, Ta, Tb, and (13) are as previously defined; Nude representing a nucleophilic group; <e representing an electrophilic group; II. Composition comprising the dye of formulas (I)

Another subject of the invention is a cosmetic composition comprising at least one anionic dye with a heterocyclic disulfide group of formula (I) as defined above. Preferentially in said composition, the compound of formula (I) can not represent the carboxylate forms of compounds (A) or (B):

In addition to the presence of at least one dye of formula (I), the composition of the invention may also contain a reducing agent.

Preferably, the composition does not contain a reducing agent

The dye composition useful in the invention generally contains an amount of dye of formula (I) of between 0.001 and 50% relative to the total weight of the composition. Preferably, this amount is between 0.005 and 20% by weight and even more preferably between 0.01 and 5% by weight relative to the total weight of the composition.

The composition according to the invention may also contain additional direct dyes different from the dyes of formula (I). These direct dyes are, for example, chosen from neutral, acidic or cationic nitro-benzene direct dyes, neutral azo, acid or cationic direct dyes, tetraazapentamethine dyes, neutral or acidic or cationic quinone dyes, in particular neutral anthraquinone dyes and direct azine dyes. , triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the natural direct dyes that may be mentioned are lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna.

The composition according to the invention may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratinous fibers.

Among 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. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. The coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.

The oxidation base (s) present in the dyeing composition are in general each present in an amount of between 0.001% and 10% by weight relative to the total weight of the dyeing composition, preferably between 0.005% and 6% by weight. In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

Preferably, the process of the invention does not use oxidation dye, and the composition comprising the anionic dye (s) of formula (I) preferably does not contain any oxidation dye. According to a particular embodiment, the dyeing method of the invention does not use an oxidizing agent. The composition comprising the anionic dye (s) of formula (I) of the invention preferably does not comprise an oxidizing agent.

The composition according to the invention is cosmetic ie it is in a medium which is suitable for dyeing keratin materials, also known as a dyeing support, a cosmetic generally consisting of water or a mixture of water and at least one organic solvent. As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvents when they are present are preferably present in proportions preferably of between 1 and 99% by weight approximately relative to the total weight of the dyeing composition, and even more preferably between 5 and 95% by weight approximately.

The composition according to the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic polymers, amphoteric, zwitterionic or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or otherwise, such as aminosilicones, film-forming agents, ceramides, preserving agents, opacifying agents, conductive polymers.

The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition.

Of course, one 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 dyeing composition according to the invention are not, or not substantially, impaired by the or the additions envisaged.

The pH of the composition according to the invention is generally between 3 and 14 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems.

Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (y):

formula (γ) in which:

Wa is a propylene residue optionally substituted by a hydroxy group or a C 1 -C 4 alkyl radical;

Ra1, Ra2, Ra3 and Ra4, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl or a C1-C4 hydroxyalkyl radical.

The composition according to the invention may be in various forms, such as in the form of liquid, cream, gel, or in any other form suitable for dyeing keratinous fibers, and in particular hair. III. Process for coloring and / or lightening from the anionic dyes of formula (I) of the invention

Another subject of the invention is a process for coloring and / or lightening keratinous substances, in particular human keratin fibers such as the hair, comprising applying to said materials a composition comprising at least one anionic dye of formula ( I) as defined above.

According to a particular embodiment of the invention, the method for dyeing and brightening dark keratin materials, in particular human keratinous fibers such as the hair, comprising applying to said materials a composition comprising at least one anionic dye of formula (I) fluorescent and preferably absorbs in the range of yellow, orange and red.

In particular, the anionic dyes of formula (I) comprising a chromophore A which is anionic and derived from anionic fluorescent dyes. Mention may be made of anionic triarylmethane fluorescent direct dyes; anionic xanthenes and anionic quinoline dyes; each of these dyes having at least one cationic counterionic sulfonate or carboxylate group as defined above. Preferably A is derived from fluorescent dye that absorbs in the range of yellow, orange, and red.

According to a particular embodiment in the method of the invention a reducing agent is applied before, at the same time or after the application of the composition containing at least one anionic dye of formula (I) as defined above.

Preferably, the reducing agent is used in the process according to the invention before the application of the anionic dye (s) of formula (I).

According to another method of the invention, the reducing agent is used at the same time as the anionic dye (s) of formula (I). For example, the anionic dye (s) of formula (I) are found in a cosmetic composition, a composition according to the invention, which further comprises the reducing agent. This composition is then applied to the keratin materials.

According to a variant, once the composition containing at least one anionic dye of formula (I) is applied to the keratin materials, the composition is left for a certain time then, the keratin materials are rinsed, and / or dewatered and / or undergo thermal treatment, in particular steam (steampod) and / or exposed to ultraviolet (UV) light.

The duration of the treatment after application of the composition containing at least one anionic dye of formula (I) may be short, for example from 0.1 second to 1 hour, particularly between 5 minutes and 50 minutes, more particularly between 10 and 45 and preferentially the break time is 30 minutes.

The duration of the post heat treatment can be short, for example from 0.1 to 30 minutes. The temperature is between 40 ° C and 250 ° C. More particularly between 50 ° C and 200 ° C. Preferably from 80 ° C to 180 ° C. According to a particular embodiment, the heat treatment of the keratinous fibers is carried out using a straightening iron for the keratinous fibers or by means of a hairdressing helmet, a hair dryer or a dispenser of rays. infrared

According to a preferred variant of the invention, the dyeing and / or lightening process according to the invention consists in applying to the keratin materials the composition according to the invention and then wringing them out and / or subjecting them to a heat treatment. particularly at a temperature between 50 and 200 ° C, more preferably between 80 and 180 ° C with for example a smoothing iron. Optionally in this process variant, the heat treatment is followed by rinsing.

The duration of the post-UV treatment is between 1 second and 2 hours. Preferably 30 minutes.

A particular embodiment of the invention relates to a method in which the anionic direct dye of formula (I) can be applied directly to hair without reducing agents, free from pre or post-treatment reducers.

A treatment with an oxidizing agent may optionally be associated. Any type of conventional oxidizing agent may be used in the art. Thus, it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, as well as the enzymes among which may be mentioned peroxidases, oxides, 2-electron reductases such as uricases and 4-electron oxygenases such as laccases. The use of hydrogen peroxide is particularly preferred.

This oxidizing agent may be applied to the fibers before or after the application of the composition containing at least one anionic direct dye of formula (I) as defined above. The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains a dye composition comprising at least one compound of formula (I) and a second compartment contains an oxidizing agent. One of these compartments may further contain one or more other dyes of direct dye type or oxidation dye. The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains a dye composition comprising at least one compound of formula (I) and a second compartment contains a reducing agent. One of these compartments may further contain one or more other dyes of direct dye type or oxidation dye.

Each of the devices mentioned above can be equipped with a means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2 586 913.

The examples which follow serve to illustrate the invention without, however, being limiting in nature. The thiol fluorescent dyes of the examples below have been fully characterized by conventional spectroscopic and spectrometric methods.

I- EXAMPLES OF SYNTHESIS

General procedure:

The anionic dyes of formula (I) as defined above can be obtained according to the following scheme:

Thus, the compounds of formula (I) and in particular those of formula (I "'b) can be obtained by reaction of acid halide, preferably acid chloride (b), on derivative (c) in a solvent. aprotic preferably polar in the presence of a base, such as in THF in the presence of pyridine.

When necessary, the acid halide, in particular the acid chloride (b), may be prepared by conventional methods known to those skilled in the art, for example by reaction of the corresponding carboxylic acid with the thionyl in an anhydrous aprotic solvent.

Synthesis of the following compounds:

with M + representing K +, or pyridinium

Example 1 Synthesis of 5 - {[5- (1,2-dithiolan-3-yl) pentanoyl] amino} -4-oxo-3- (2-phenylhydrazinylidene) -3,4-dihydronaphthalene-2,7-disulfonate dipotassium

1

Step 1 :

The pentanoyl 5- (1,2-dithiolan-3-yl) chloride used in the subsequent step is prepared according to the following procedure: 0.5 mol of lipoic acid are dissolved in 1 liter of dichloromethane and then 1 , 1 equivalent of thionyl chloride drip under cooling at zero degrees using an ice bath.

Once the addition is complete, the medium is stirred for 2 hours in an ice bath, then stirring is continued at room temperature for 2 hours before removing the solvent by evaporation. The product obtained (5- (1,2-dithiolan-3-yl) pentanoyl chloride) is dissolved again in anhydrous dichloromethane and used as such.

Step 2: Synthesis of 5 - {[5- (1,2-dithiolan-3-yl) pentanoyl] amino} -4-oxo-3- (2-phenylhydrazinylidene) -3,4-dihydronaphthalene-2,7 dipotassium disulfonate:

In a tricoi of 1000 ml, equipped with a magnetic stirrer, a condenser, a thermometer and a dropping funnel, 450 ml of anhydrous THF, 2 ml of pyridine and 4.25 g (9 ml) are added. , 09 mmol) of disodium 5-amino-4-hydroxy-3- (phenylazo) -naphthalene-2,7-disulfonate, then 70 ml of a 5% solution were added dropwise at room temperature. (1,2-dithiolane-3-yl) pentanoyl chloride in anhydrous dichloromethane (0.78 molar). After about 80 hours, the reaction is complete and the crude product is collected by centrifugation of the reaction medium. The solid obtained is washed 3 times with anhydrous THF and then dried to yield 7.8 g of red solid.

The crude product is taken up with potassium hydroxide (1.0M solution in EtOH) with stirring for 1 hour. The salt formed is then filtered, washed with ethanol and dried under vacuum to yield 2 g of compound 1 as a red solid.

The analysis by proton NMR spectroscopy and mass spectrometry confirms the structure of the expected product 1.

EXAMPLE OF COLORING The dye evaluation is carried out according to different modes in one or two stages, with or without pretreatment of the keratinous fiber.

The color of the locks was evaluated before staining / after successive staining. The color of the wicks is measured with the Minolta CM2600d spectrophotometer (specular components included, angle 10 °, illuminant D65) in the CIEL * a * b * system. In this system, L * represents the intensity of the color, a * indicates the green / red color axis and b * the blue / yellow color axis.

The lower the value of L, the darker or more intense the color. The higher the value of a * the higher the shade is red and the higher the value of b * the hue is yellow.

Rise of color:

The variation of the coloration of the locks before and after coloration is measured by (ΔΕ) which corresponds to the rise of the color according to the following equation:

In this equation, L *, a * and b * represent the values measured after staining and L0 *, a0 * and b0 * represent the values measured before staining.

The higher the value of ΔΕ, the greater the difference in color of the wick before and after staining, which shows a good rise in color.

Chromaticity:

The greater the value of C *, the more the color of the treated locks is chromatic.

I) First evaluation mode with reductive pretreatment of the fiber and post-oxidative treatment:

A lock of 1 g of 90% natural white hair (90 BN) is treated in two stages with i) 10 ml of solution from 9 ml of water and then ii) 1 ml of 10% thioglycolic acid solution ( w / w) containing 50 mg of the compound of Example 1 is applied to the hair and left for 20 minutes on the hair. Then the wick is treated with 8 volumes of hydrogen peroxide solution for 10 minutes.

Following this application, the wick is washed with water and shampoo is finally dried with hair dry.

The color obtained is pink red aesthetic, chromatic and tenacious. In addition the rise of the color is very good.

Comparative:

dye C

With respect to the coloration obtained with the comparative dye C (under the same operating conditions as in Example 1), the color is significantly more intense, more tenacious and more chromatic to the eye, with the compound of the invention. vs. the comparative. Moreover it appears that the rise is much higher than with the comparative. These visual observations have been corroborated with the spectrocolorimetric results below:

II) Second mode of evaluation without reducing pretreatment or oxidative post-treatment:

A wick of 1 g of 90% natural white hair is treated with 50 mg of Example 1 solubilized in 10 ml of water.

This solution is applied to the lock of hair with a heating time of 30 minutes on a hot plate at a temperature of 37 ° C.

After removing the excess of formula, the lock is washed with water, then with shampoo and finally dried with hair dry. The color obtained is red pink

Compared to the coloring obtained with the comparative dye C, the same tendency as with the previous process was observed for the process of the invention. This has been corroborated with the spectrocolorimetric results below:

The color of the hair is measured with colorimeter_

Claims (18)

A method for dyeing keratin materials, wherein a cosmetic composition comprising one or more anionic direct dyes of the following formula (I) is applied to said materials: A- (X) p - Csat - (X'V - Het ( I) their organic or inorganic acid salts, optical isomers, geometric isomers, and solvates such as hydrates, formula (I) in which:> A represents a radical containing at least one anionic chromophore;> Het represents a monocyclic heterocyclic radical; 4 to 10-membered disulphide; X and X ', which may be identical or different, represent: a linear or branched, saturated or unsaturated, C1-C16 hydrocarbon-based chain, optionally interrupted and / or optionally terminated at one or two its ends by one or more divalent groups or combinations thereof selected from: -N (R) -; -O-; -S-; -C (O) -; -S (O) 2- with R, same or different , are chosen from a hy a C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl radical; an aromatic radical (hetero) cyclic or not, saturated or unsaturated, condensed or not, optionally comprising one or more identical or different heteroatoms, optionally substituted; a divalent group or the combination chosen from: -N (R) -; -O-; -S-; -CO)-; -S (0) 2- with R, as previously defined; preferentially the divalent group or groups or combinations thereof are chosen from -O-; -N (R) -; -C (O) - with R selected from a hydrogen atom, and a C 1 -C 4 alkyl radical; > p and p ', which are identical or different, represent an integer equal to 0 or 1; and Csat represents a linear or branched, optionally substituted, saturated or unsaturated C 1 -C 16 hydrocarbon-based chain. 2. The method of dyeing according to any preceding claim wherein the dye of formula (I) is such that p or p 'is equal to 1, X and X', identical or different, represent the following sequence: (T) t - (Z) z- (T ') t- said sequence being connected in formulas (I), as follows: - Csat- (T') t '- (Z) z- (T) t- (A or Het ); a sequence in which:> T and T ', which may be identical or different, represent one or more radicals or their combinations chosen from: -S (O) 2-; -O-; -S-; -N (R) -; -C (O) -; with R, representing a hydrogen atom, a C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or aryl (C 1 -C 4) alkyl radical; and a heterocycloalkyl or heteroaryl radical, cationic or non-cationic, preferentially monocyclic, preferably containing two heteroatoms (more preferably two nitrogen atoms) and preferably comprising from 5 to 7 members, more preferably piperazinyl or piperidinyl; preferentially T and T 'represent one or more radicals or their combinations chosen from -O-, -N (R) -, -C (O) -, with R chosen from a hydrogen atom, and a C 1 -C 4 alkyl radical; > the indices t and t ', identical or different, are 0 or 1; Z represents: - (CRiR 2) m - with m integer between 1 and 8 and R 2, which may be identical or different, represent a hydrogen atom or a CrC 4 alkyl, CrCl 2 alkoxy, hydroxy, cyano, carboxy, amino or CrC 4 group; alkylamino, Cr C4 dialkylamino, said alkyl radicals being able to form with the nitrogen atom which carries them a heterocyle comprising from 5 to 7 members, optionally comprising another heteroatom different or different from nitrogen; - (CH2CH2O) q- or - (OCH2CH2) q- in which q is an integer between 1 and 15, or an aryl, alkylaryl or arylalkyl radical in which the alkyl radical is C 1 -C 4 and the aryl radical is preferably C 6, being optionally substituted by at least one SO 3 M group with M representing a hydrogen atom, an alkali metal or an ammonium ammonium group substituted with one or more identical or non-linear, linear or branched, optionally substituted C 1 -C 6 alkyl radicals; minus one hydroxyl; > or Z represents: With q as defined above and r representing an integer inclusive between 0 and 4, M representing an anionic counterion; > z is 0 or 1. 3. Staining process according to any one of the preceding claims wherein the dye of formula (I) is such that A is derived from acid nitro dyes, acidic azo dyes such as diaryls or pyrrazolones, acidic dyes, dyes acid triarylmethanes, acidic indoamine dyes, acid xanthenes, acid anthraquinone dyes, acidic quinolines, indigoids and acidic natural dyes; each of these dyes having at least one cosmetically acceptable cationic, organic or inorganic cationic counterion or carboxylate group, preferably chosen from alkali or alkaline earth metal cations such as Na + or K +, or ammonium, (di) (tri) (CrC6) alkylammonium, cationic heteroaryl such as pyridinium, imidazolium; more particularly each of these dyes having between 1 and 5 sulphonate or carboxylate groups, preferably between 1 and 3 sulphonate or carboxylate groups; more preferably A is derived from diaryl anionic azo dyes. 4. Coloring process according to any one of the preceding claims, in which the dye of formula (I) is such that Csat represents a divalent, saturated or unsaturated, preferably saturated, linear or branched, preferably linear, hydrocarbon-based chain comprising from 1 to 14 carbon atoms, preferably between 2 and 10, more preferably between 3 and 6 carbon atoms such as 4 carbon atoms. 5. Staining process according to any one of the preceding claims wherein the dye of formula (I) is such that Hét is of formula (II) connected to the remainder of the molecule by one of substituents R5, R6, R7, R8, R9 or R10 or else said radical is connected to the rest of the molecule directly by one of the carbon atoms of the heterocycle radical in the alpha, beta position of the disulfide bond or when q is 2 or 3 in the gamma position, in which case one of the substituents R5, R6 , R7, Rs, R9 or R10, is absent: formula (II) in which: R5, R6, R9 and R10, identical or different, represent a hydrogen atom, or a group chosen from: i) (CrC8) alkyl, iii) hydroxy, iv) (di) (CrC8 ) (alkyl) amino, v) (CrC8) alkoxy, especially R5, R6, R9 and R10 represent a hydrogen atom or a (CrC4) alkyl group such as methyl, preferably R5, R6, R9 and R10 represent an atom hydrogen; R7 and R8, which may be identical or different, represent a hydrogen atom or a group chosen from: i) (CrC8) alkyl, iii) hydroxy, iv) (di) (Cr C8) (alkyl) amino, v) (CrC8 ) alkoxy; in particular R 7 and R 8 are chosen from a hydrogen atom and a (CrC 4) alkyl group such as methyl, preferably R 7 and R 8 represent a hydrogen atom; or two radicals carried by the same carbon atom R5 and R6, R7 and R8, and / or Rg and R10 together with the carbon atom carrying them a carbonyl group; q represents an integer inclusive of between 1 and 3, particularly between 1 and 2; it being understood that when q is 2 or 3 then the groups R7 and R8 may be identical or different from each other; preferably q is 1; and more particularly all the substituents R5 to R10 represent a hydrogen atom. 6. Coloring process according to any one of the preceding claims, in which the dye of formula (I) is chosen from the following dyes of formula (a) to (g): As well as their salts of organic or mineral acid, optical isomers, geometrical isomers, their tautomers and solvates such as hydrates; Formulas (a) to (g) in which: A is as defined in claim 1 or 3, in particular A is derived from acid nitro dyes, acidic azo dyes such as diaryl or pyrrazolone, acidic azine dyes, acid triarylmethane dyes, acidic indoamine dyes, acid xanthenes dyes, acidic anthraquinone dyes, acidic quinolines, indigoids and acidic natural dyes; each of these dyes having at least one cationic counterionic sulphonate or carboxylate group as defined above, more particularly between 1 and 5 sulphonate or carboxylate groups, preferably between 1 and 3 sulphonate or carboxylate groups; more preferentially A is derived from diaryl anionic azo dyes comprising from 1 to 5 sulphonate or carboxylate groups, preferably from 1 to 3 sulphonate groups; X and X 'are as defined in claim 1 or 2, in particular X and X' represent a divalent group or the combination chosen from: -N (R) -, -O-, -S-, -C ( O) - and -S (O) 2- with R, as previously defined; preferably the divalent group or groups or combinations thereof are chosen from -O-, -N (R) - and -C (O) - with R chosen from a hydrogen atom, and a C 1 -C 4 alkyl radical; more preferably X and X 'represents a divalent amide group -N (R) -C (O) - or -C (O) -N (R) - with R representing a hydrogen atom, or a C 1 -C 4 alkyl radical; • p and p ', identical or different, represent an integer equal to 0 or 1; preferably p is 1 and p 'is 0; and Csat is as defined in claim 1 or 4, preferably represents a linear or branched, unsubstituted C1-C10 alkylene chain, more preferably C2-C8, more preferably C3-C5, such as C4; R5, R6, R9 and R10 as defined in claim 5, especially represent a hydrogen atom or a (CrC4) alkyl group such as methyl, preferably R5, R6, R9 and R10 represent a hydrogen atom; ; R 7 and R 8, as defined in claim 5, especially represent a hydrogen atom and a (CrC 4) alkyl group such as methyl, preferably R 7 and R 8 represent a hydrogen atom; preferably all the substituents R5 to R10 represent a hydrogen atom. 7. Coloring process according to any one of the preceding claims, in which the dye of formula (I) is chosen from the following dyes of formula (I "a) and (1" b): As well as their salts of organic or mineral acid, optical isomers, geometrical isomers, their tautomers and solvates such as hydrates; formula (I) in which: X, X ', p, p', Csat, R5, Re, R7, Re, R9 and R10 are as defined in the preceding claim, q is 1 or 2 with the proviso that when q is 2 then the groups R7 and R8 may be the same or different from each other, preferably q is 1, p is 1 and p 'is 0, R5 to R10 are hydrogen, X is a divalent amide group -N (R) -C (O) - or -C (O) -N (R) - with R representing a hydrogen atom, or a C 1 -C 4 alkyl radical; and Csat represents a C1-C10 alkylene chain, linear or branched, unsubstituted, more preferably linear; R 1 and R 2, which are identical or different, represent a group chosen from: i) hydroxy, ii) thiol, iii) nitro, iv) (CrC 6) alkyl optionally substituted, in particular (CrC 4) alkyl such as methyl or ethyl, v) (CrC6) alkoxy in particular (CrC4) alkoxy such as ethoxy or methoxy, vi) (CrC6) alkylthio, vii) halogen and viii) amino-NRaRb with Ra and Rb, identical or different, representing: o a hydrogen atom, a (CrC6) alkyl group, particularly (CrC4) alkyl such as methyl, or ethyl, said alkyl group being optionally substituted by one or more hydroxyl groups, or where Ra and Rb form with the nitrogen atom which carry them a saturated or unsaturated 5- to 8-membered heterocyclic ring, preferably 5 or 6-membered, said heterocycle may furthermore contain: a) contain one or more heteroatoms or groups selected from oxygen, sulfur, and N (RC), with Rc representing a hydrogen atom or a (CrC4) alkyl group substituted with one or more hydroxy groups, such as methyl, ethyl or hydroxyethyl, and / or b) be substituted by one or more identical or different groups selected from hydroxy, (CrC4) alkyl optionally substituted by one or more hydroxy groups, ( CrC4) alkyloxy such as ethoxy or methoxy, (di) (CrC4) (alkyl) amino, (di) hydroxy (CrC4) alkylamino; Z and Z ', which are identical or different, represent a carboxylate group -C (O) O', M + or sulfonate -S (O) 2 -O 'M +, with M + representing a cationic counterion, cosmetically acceptable, preferably chosen from alkaline or alkaline earth cations such as Na, Mg, K and Ca, and organic cations such as ammonium NH4 +, (di / tri) (CrC6) alkylammonium, cationic heteroaryl such as pyridinium; preferentially Z and Z 'represent a group -S (O) 2-0' M +; • t and t ', identical or different, represent an integer inclusive between 0 and 5, it being understood that z + z' is an integer greater than or equal to 1; in particular z + z 'is an integer inclusive of between 1 and 3; • x is an integer inclusive between 0 and 5; • x 'is an integer inclusive between 0 and 4; • present or absent, represents a benzo ring, preferably the ring is absent; it being understood that when x, x ', t and t' are greater than or equal to 2, then Ri respectively are identical or different from each other, R2 are identical to or different from each other, Z are identical or different from each other, and Z 'are identical or different from each other; preferably, the anionic dyes of formula (I) according to the invention are chosen from those of formula (I "b). 8. Staining process according to any one of the preceding claims wherein the dye of formula (I) is chosen from the following dyes of formula (I "'b): As well as their salts of organic or mineral acid, optical isomers, geometrical isomers, their tautomers and solvates such as hydrates; formula (I "'b) wherein X, p, Z', t ', q, Csat, R1, x, R2, x', are as defined in the preceding claim; preferentially: • x represents an integer between 0 and 4 inclusive, particularly between 1 and 3, preferably equal to 0 or 1; X 'represents an integer between 0 and 3, especially between 1 and 2, preferably equal to 1; X represents a divalent amide group -N (R) -C (O) - or -C (O) -N (R) -, preferably -N (R) -C (O) - with R representing a hydrogen atom or a C 1 -C 4 alkyl radical; P is 1; • represents an integer inclusive between 1 and 3, such as 2; R 1, which is identical or different, represents a group chosen from: i) hydroxy, ii) nitro, iv) (CrC 6) alkyl, in particular (CrC 4) alkyl such as methyl or ethyl, v) (CrC 6) alkoxy in particular (CrC 4) alkoxy such as ethoxy or methoxy, vi) (Cr C6) particular alkylthio (CrC4) alkylthio such as ethylthio or methylthio, and vii) amino -NRaRb with Ra and Rb, same or different, representing: o a hydrogen atom, o a (CrC6) alkyl group, particularly (CrC4) alkyl such as methyl, or ethyl, said alkyl group being optionally substituted with one or more hydroxy groups such as hydroxyethyl, or else Ra and Rb form, with the nitrogen atom which carries them, a saturated 5- or 6-membered heterocycle, said heterocycle may furthermore comprise: a) containing one or more heteroatoms or groups selected from oxygen, sulfur, and N (RC), with Rc representing a hydrogen atom or a (CrC4) alkyl group optionally substituted with one or more hydroxyl groups such as methyl, ethyl or hydroxyethyl, and / or b) be substituted with one or more hydroxy groups; R 2, identical or different, represents a group chosen from: i) hydroxy, ii) thiol, iv) (CrC 6) alkyl, in particular (CrC 4) alkyl such as methyl or ethyl, v) (Cr C 6) alkoxy in particular ( CrC4) alkoxy such as ethoxy or methoxy, vi) (Cr C6) alkylthio, especially (CrC4) alkylthio, such as ethylthio or methylthio, and vii) amino -NRaRb with Ra and Rb, identical or different, representing a hydrogen atom or a (CrC6) alkyl group, particularly (CrC4) alkyl such as methyl, or ethyl; preferably R2 represents a hydroxy or thiol group, more preferably a thiol; • Z ', identical or different, represents a group -S (O) 2-0' M + with M + representing a cationic counterion, preferentially chosen from alkaline or alkaline earth cations such as Na, Mg, K and Ca, and organic cations such as ammonium NH4 + or (di / tri) (Ci-C4) alkylammonium; Csat represents a linear or branched, preferably linear, (C -C 8) alkylene group, such as - (CH 2) m - with m representing an integer between 2 and 8, in particular between 3 and 6, such that m is 4; particularly R-1 is on the phenyl ring in the 2 ', 4' and / or 6 'position, preferably in the 4' position; particularly R2 is on the naphthyl ring in position 1, 4, 5 and / or 8, preferably in the 8 position; particularly the group X is connected to the naphthyl ring in position 1, 4, 5 and / or 8, preferably in position 1; it being understood that X can not be positioned at a position where a group R2 is located; in particular, Z 'is on the naphthyl ring in position 2, 3, 6, and / or 7, preferably in position 3 and 6; and particularly the azo group -N = N- is connected to the naphthyl ring in the 2, 3, 6, and / or 7 position, preferably in the 2 or 7 position, more preferably 7; it being understood that -N = N- can not be positioned on a position where there is a group Z '. 9. A dyeing process according to any preceding claim wherein the dye of formula (I) is selected from the following dyes of formula (I "" b): As well as their salts of organic or mineral acid, optical isomers, geometrical isomers, their tautomers and solvates such as hydrates; formula (I "" b) in which Csat, M +, R-1, x, R2, and x 'are as defined in the preceding claim, preferably x' is 0, 1 or 2, more particularly x 'is 0; R represents a hydrogen atom or a (CrC4) alkyl group, more preferably; R represents a hydrogen atom; and R2 is positioned at position 2 or 5 on the naphthyl ring. 10. The method of dyeing according to the preceding claim wherein the dye of formula (I) is chosen from dyes of formula (I "" b) with: - x '= 0; x = 0 or 1; R represents a hydrogen atom or a (CrC4) alkyl group, more preferably; R represents a hydrogen atom; R 1 represents a group chosen from i) hydroxy, ii) nitro, iii) C 1 -C 4 alkylthio such as methylthio, iv) C 1 -C 4 alkoxy, more preferably C 1 -C 2 such as methoxy or ethoxy, v) NRaRb amino with: Ra and Rb, identical or different, representing a hydrogen atom, a C 1 -C 4 alkyl group such as methyl, or ethyl or a C 1 -C 4 hydroxyalkyl group, preferably C 1 -C 2 such as hydroxethyl; or Ra and Rb, together with the nitrogen atom which carries them, form a saturated 5- or 6-membered heterocycle, said heterocycle may furthermore comprise one or more heteroatoms or groups chosen from the oxygen atom or -N (RC) - group, with Rc representing a hydrogen atom or a C 1 -C 4 alkyl group such as methyl, and / or o being substituted with one or more identical or different groups selected from hydroxy, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxy, (di) (C 1 -C 4) (alkyl) amino, (di) hydroxy (C 1 -C 4) alkylamino; and Csat denotes a saturated divalent hydrocarbon chain (or alkylene) containing from 2 to 8 carbon atoms, preferably from 3 to 6 carbon atoms; in particular, the anionic dyes of formula (I) are of formula (I "'b) with: - x' = 0; x = 0 or 1 R represents a hydrogen atom; and R 1 represents a group selected from: i) hydroxy, nitro (NO 2), iii) C 1 -C 4 alkylthio such as methylthio, C 1 -C 4 alkoxy such as methoxy, or ethoxy, iv) amino NRaRb with R a and R b independently representing a hydrogen atom a C 1 -C 4 alkyl group such as methyl, or ethyl; a C 1 -C 4 hydroxyalkyl group, more preferably C 1 -C 2 such as hydroxethyl or else R a and Rb form, with the nitrogen atom carrying them, a saturated 5- or 6-membered heterocycle, chosen from the pyrrolidine, piperidine, piperazine and heterocycle rings; may also be substituted by one or more identical or different groups selected from hydroxy, C 1 -C 4 alkyl such as methyl, C 1 -C 4 hydroalkyl such as hydroxyethyl; Csat represents a (C3-C6) alkylene group such as butylene - (CH2) 4-, 11. The method of dyeing according to any one of the preceding claims wherein the dye of formula (I) is chosen from the following dyes: With M + a cationic counterion as defined in the preceding claims, preferably alkaline such as Na, K, ammonium, or pyridinium; compounds 1 to 15 as well as their optical, geometric, tautomeric and solvated isomers such as hydrates; 12. A method of dyeing keratinous material according to any one of the preceding claims wherein the composition comprising the compound (s) of formula (I) is allowed to pause then, the keratin materials are rinsed, and / or dewatered and / or undergo a heat treatment. and / or exposed to ultraviolet light (UV). 13. A process for the dyeing and / or lightening of dark keratin materials, in particular human keratinous fibers such as the hair, comprising applying to said materials a composition comprising at least one anionic dye of formula (I) which is fluorescent and preferably which absorbs in the range of yellow, orange and red; in particular the anionic dyes of formula (I) comprising a chromophore A which is anionic and derived from fluorescent dyes anionic triarylmethanes; anionic xanthenes and anionic quinoline dyes; each of these dyes having at least one cationic counterionic sulfonate or carboxylate group as defined above. 14. A process for dyeing keratinous material according to any one of the preceding claims wherein a reducing agent is applied before, at the same time or after the application of the composition containing at least one anionic dye of formula (I) as defined in a any of the preceding claims, preferably the reducing agent is used in the process according to the invention before the application of the anionic dye (s) of formula (I). 15. Compound of formula (I) according to any one of claims 1 to 11 understood that the compound of formula (I) can not represent the carboxylate forms of compounds (A) or (B): 16. A composition comprising one or more dyes of formula (I) according to any one of claims 1 to 11 understood that the dye (s) of formula (I) can not represent the carboxylate forms of compounds (A) or (B) such that defined in the preceding claim. 17. Composition according to the preceding claim, wherein the dye (s) of formula (I) are present in an amount of between 0.001 and 50% by weight relative to the total weight of the composition. 18. Use of the dyes of formula (I) as defined in claims 1 to 11 for the dyeing and / or lightening of human keratin materials such as human keratin fibers such as hair.