Method of dyeing and lightening keratin materials in the presence of a reducing agent comprising a fluorescent disulphide dye

Translation of description of equivalent WO 2007110542 A2

DYE PROCESS AND CLARIFICATION OF CONTENTS

KERATINOUS IN THE PRESENCE OF A REDUCING AGENT HAVING

FLUORESCENT DYE DISULPHIDE

p0004The invention relates to a method for coloring and lightening keratin materials in the presence of a reducing agent.

p0005It is known to dye keratin fibers, particularly human, by direct dyeing. The process conventionally used in direct dyeing comprises applying to the keratin fibers direct dyes, which are colored and coloring molecules that have affinity for the fibers, allowing them to diffuse and then rinsing the fibers.

p0006The direct dyes which are conventionally used are for example dyes of the nitrobenzene type, anthraquinone dyes, nitropyridine dyes of the azo, xanthene, acridine, azine or triarylmethane.

p0007The colorations resulting from the use of direct dyes are temporary or semi-permanent colorings since the nature of the interactions that bind the direct dyes to the keratin fiber, and their desorption from the surface and / or the heart of the fiber are responsible their low dyeing power and their poor resistance to washing or perspiration.

p0008Furthermore, the dyeing of keratinous fibers from conventional direct dyes does not allow to significantly lighten keratin fibers.

p0009The lightening of the color of keratin fibers, especially dark to lighter shades, by optionally modifying the shade thereof, constitutes an important demand.

p0010Conventionally, to obtain a lighter coloring implements a chemical bleaching process. This method comprises treating keratin materials such as keratin fibers, in particular hair, with a strong oxidizing system, generally consisting of hydrogen peroxide associated or not with persalts, usually under alkaline conditions.

p0011This bleaching system has the disadvantage of degrading the fibers and of impairing their cosmetic properties. The fibers have a tendency to become rough, more difficult to disentangle and more brittle. Finally, the lightening or bleaching of keratin fibers from oxidizing agent is incompatible with the treatments for modifying the shape of said fibers, particularly in hair straightening treatments.

p0012Another lightening technique comprises applying to the hair dark fluorescent direct dyes. This technique, described in particular in FR 2830189 allows to respect the quality of the keratin fiber during the treatment but employees fluorescent dyes do not exhibit satisfactory resistance to shampoos. To increase the toughness of direct dyeing, it is known to fix direct dyes by covalent bonding to the hair. For example, it is known to react with reactive groups in dyes residues cystine or cysteine ​​in a large number of the keratin fibers. Are thus described certain dyes with Bunte salts functions and isothiuroniums or other protective groups of thiols. However, obtaining the reactive form of the dye, generally requires the use of strongly basic media. In addition, the thiol groups are generally generated in excess which makes necessary a post neutralization step following staining.

p0013Other disulphide dyes known for coloring keratin fibers are disulphide derivatives of aminothiophenol derivatives. Such dyes are described for example in FR 1 156407. These dyes may be used under relatively mild conditions in the presence of a slightly reducing medium or after a reducing pre-treatment of the hair. However, these dyes can cause colourshifts when applying. Finally, WO 2005/097051 describes the document disulfide dyes aza imidazoliums for the direct dyeing of keratin fibers.

p0014The object of the present invention is to provide novel systems for dyeing with lightening effect of keratin substances, in particular human keratin fibers, in particular hair, which do not present the drawbacks of the existing bleaching processes. In particular, an object of the present invention is to provide direct dyeing systems for obtaining lightening effects especially on naturally or artificially dark keratin fibers, stubborn face successive shampooing and do not damage the keratin fibers that do not alter their cosmetic properties.

p0015This object is achieved with the present invention which relates to a method for coloring dark keratin materials comprising applying to the keratin materials, a dye composition comprising, in a suitable cosmetic medium, at least one fluorescent disulphide dye chosen, for example the dyes of formulas (I) and (II):

p0016A- (X)_p - C_sat - SS - C'sat - (XV - A '(I)

p0017A- (X)_p - C_sat - SS - C '_hert - (X V - D (N) the organic or mineral acid salts, optical isomers, geometrical isomers, and solvates such as hydrates; in which formulas:

p0018• A and A ', identical or different, represent a radical containing at least one cationic fluorescent chromophore;

p0019• X and X ', identical or different, represent a hydrocarbon chain -C_thirtyLinear or branched, saturated or unsaturated, optionally interrupted and / or optionally terminated at one or both of its ends by one or more divalent groups or combinations thereof selected from: - N (R) -, -N⁺(R) (R ') -, -O-, -S-, -CO-, -SO₂- With R, R ', identical or different, are selected from hydrogen, alkyl C₁- C₄Hydroxyalkyl and aminoalkyl a (hetero) aromatic or non-cyclic, saturated or unsaturated, fused or non-optionally comprising one or more identical heteroatoms or unsaturated, optionally substituted;

p0020• the coefficient p, and p ', equal or different, represent an integer of O or 1;

p0021• C sat, C '_Sat the same or different represent an alkylene chain Ci-Ci₈Linear or branched, optionally substituted, optionally cyclic; • D corresponds to a radical chosen from hydroxyl, hydroxyalkyl, alkoxy, carboxy, carboxylate, amino, alkylamino, or dialkylamino, this application is conducted in the presence of a reducing agent.

p0022This reducing agent may be chosen from thiols such as cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulphite, sulphites, thioglycolic acid and its esters, in particular glycerol monothioglycolate, and thioglycerol.

p0023This reducing agent may also be selected from borohydrides and derivatives thereof, such as salts of borohydride, cyanoborohydride, triacetoxyborohydride of trimethoxyborohydride: sodium, lithium, potassium, calcium salts, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra-n butylammonium, benzyltriethylammonium); catecholborane.

p0024The method of the invention allows to obtain a lightening dark keratin materials. Including the method of the invention provides a lightening of keratin fibers such as hair, very tough to shampoos, to current aggressions (sun, sweating), and other hair treatments without degrading the keratin fiber.

p0025Within the meaning of the invention, the term dark keratin material which exhibits a lightness L^* measured in the CIE L system^*at^*b^*Less than or equal to 45 and preferably less than or equal to 40, given also that L^*= 0 is equivalent to black and L^*100 = white.

p0026Within the meaning of the invention, the term hair naturally or artificially dark hair whose tone height is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (chestnut).

p0027The lightening of hair is evaluated by the "tone height", which characterizes the degree or level of lightening. The notion of "tone" is based on the classification of natural shades, one tone separating each shade from the following or preceding immediately. This definition and classification of the natural shades are well known to hair styling professionals and published in the book "Science of hair treatment" by Charles Zviak 1988 Ed. Masson, p. 215 and 278.

p0028The tone heights range from 1 (black) to 10 (light light blond), one unit corresponding to one tone; the higher the number, the higher the grade is clear.

p0029An artificially colored hair is a hair whose color has been modified by for example a dyeing treatment, a dyeing with direct dyes or oxidation dyes.

p0030Preferably, the composition should, after application to the hair, for example chestnut, bring the results below.

p0031We are interested in hair reflectance performance when irradiated with visible light in the wavelength range from 400 to 700 nanometers. - It then compares the reflectance curves as a function of wavelength, of hair treated with the composition of the invention and the untreated hair. - The curve corresponding to the treated hair should show a reflectance in the range of wavelengths from 450 to 700 nanometers higher than the curve corresponding to the untreated hair. - This means that, in the wavelength range from 450 to 700 nanometers, there is at least a range where the reflectance curve corresponding to the treated hair is higher than the reflectance curve corresponding to the untreated hair. The term "higher" is a difference of at least 0.05% reflectance and preferably at least 0.1%. This does not exclude that there may be in the wavelength range from 450 to 700 nanometers, at least a range where the reflectance curve corresponding to the treated hair is superimposable on or lower than the reflectance curve corresponding to the untreated hair.

p0032Preferably, the wavelength at which the difference is between the maximum reflectance curve of the treated hair and of the untreated hair is in the wavelength range from 450 to 650 nanometers, and preferably in the wavelength range of 450-620 nanometers.

p0033Within the meaning of the present invention, and unless a different indication is given: - a fluorescent disulphide dye is a fluorescent compound having at least one fluorescent chromophore as defined below, and comprising one or more disulfide bonds between two SS carbon atoms, directly or indirectly connected to (x) chromophore (s) fluorescent (s) of the compound, preferably the binding is likely to be reduced in a cosmetically acceptable medium;

p0034- The radicals "aryl" or "heteroaryl" or the aryl or heteroaryl part of a radical may be substituted by at least one substituent on a carbon atom selected from:

p0035• an alkyl radical C₁-C₁₆, Preferably C₁-C₈Optionally substituted by one or more radicals chosen from hydroxyl, alkoxy, C₁-C₂,

p0036(Poly) hydroxyalkoxy C₂-C₄, Acylamino, amino substituted with two alkyl radicals, identical or different C₁-C₄ Optionally carrying at least one hydroxyl group, or the two radicals to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, preferably 5 or 6 membered saturated or unsaturated optionally substituted optionally comprising another heteroatom identical to or different from nitrogen;

p0037. a halogen atom such as chlorine, fluorine or bromine;

p0038• a hydroxyl group;

p0039. alkoxy C₁-C₂ ; a radical (poly) hydroxyalkoxy C₂-C₄ ; . an amino radical;

p0040• a heterocycloalkyl with 5 or 6 members;

p0041. a heteroaryl radical with 5 or 6 members optionally cationic, preferably imidazolium, optionally substituted with a (C₁-C₄) Alkyl, preferably methyl; • an amino radical substituted by one or two alkyl radicals, identical or different C₁-C₆ optionally bearing at least: i) a hydroxyl group, ii) an amino group optionally substituted by one or two alkyl radicals -C₃ optionally substituted, said alkyl radicals possibly forming with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated, optionally substituted and optionally comprises at least one other heteroatom or may not be nitrogen, iii ) a quaternary ammonium group -N R'R "R" ', M in which R', R ", R" ', identical or different, represent a hydrogen atom, or an alkyl group Ci-C₄; and M represents the against-ion of the organic acid, mineral acid or the corresponding halide, iv) or a heteroaryl radical with 5 or 6 members optionally cationic, preferably imidazolium, optionally substituted with a (C₁- C₄) Alkyl, preferably methyl;

p0042. acylamino (-NR-COR ') wherein the radical R is a hydrogen atom, an alkyl radical -C₄ optionally bearing at least one hydroxyl group and the radical R 'is an alkyl radical dC₂ ; a carbamoyl radical ((R)₂N-CO-) in which the radicals R, identical or different, represent a hydrogen atom, an alkyl radical dC₄ optionally bearing at least one hydroxyl group; an alkylsulfonylamino radical (R¹SO₂-NR-) In which the radical R represents a hydrogen atom, an alkyl radical C₁-C₄ optionally bearing at least one hydroxyl group and the radical R 'represents an alkyl radical -C₄A phenyl radical; an aminosulfonyl radical ((R)₂N-SO₂-) Wherein the radicals R, identical or different, represent a hydrogen atom, an alkyl radical -C₄ optionally bearing at least one hydroxyl group, • a carboxyl group in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted);

p0043• cyano (CN);

p0044. a polyhaloalkyl group, preferably trifluoromethyl (CF₃); - The cyclic or heterocyclic part of a non aromatic radical may be substituted by at least one substituent on a carbon atom selected from the groups:

p0045• hydroxyl,

p0046. alkoxy dC₄(Poly) hydroxyalkoxy, C₂-C₄, • alkylcarbonylamino ((RCO-NR'-) in which the radical R 'is a hydrogen atom, an alkyl radical dC₄ optionally bearing at least one hydroxyl group and the radical R is an alkyl radical C₁-C₂, Substituted amino with two alkyl groups are identical or different dC₄ optionally bearing at least one hydroxyl group, said alkyl radicals possibly forming with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated, optionally substituted and optionally comprises at least one other heteroatom or not nitrogen;

p0047. alkylcarbonyloxy ((RCO-O-) in which the radical R is an alkyl radical -C₄And amino substituted with two alkyl groups are identical or different Ci-C₄ optionally bearing at least one hydroxyl group, said alkyl radicals possibly forming with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated, optionally substituted and optionally comprises at least one other heteroatom or not nitrogen;

p0048. alkcoxycarbonyle ((RO-CO-) in which the radical R is an alkyl radical -C₄And amino substituted with two alkyl groups are identical or different Ci-C₄ optionally bearing at least one hydroxyl group, said alkyl radicals possibly forming with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated, optionally substituted and optionally comprises at least one other heteroatom or not nitrogen; - A cyclic radical, heterocyclic, or a non-aromatic part of an aryl or heteroaryl radical may also be substituted by one or more oxo groups;

p0049- A hydrocarbon chain is unsaturated when it comprises one or more double and / or one or more triple bonds bonds; - An "aryl" radical represents a monocyclic or polycyclic group, condensed or not, comprising from 6 to 22 carbon atoms, and at least one ring is aromatic; preferably the aryl is phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl;

p0050- A "heteroaryl radical" represents a monocyclic or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 members and from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium and of which at least one ring 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, phénooxazolyle, pyrazinyl, pyrazolyl, pyrilyle, pyrazoyltriazyle, pyridyl, pyridinoimidazolyle, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyle, thiopyrylyle, triazolyl, xanthylyle and its ammonium salt;

p0051- A "cyclic group" is a non-aromatic cycloalkyl, mono- or polycyclic, condensed or not, containing from 5 to 22 carbon atoms, which may contain 1 or more unsaturations;

p0052- A "heterocyclic group" is a non-aromatic radical mono- or polycyclic, condensed or not, containing from 5 to 22 members and having from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium ; - An "alkyl group" is a hydrocarbon radical C₁-C₁₆Linear or branched, preferably C₁-C₈,

p0053- The expression "optionally substituted" assigned to the alkyl radical implies that said alkyl radical may be substituted by one or more radicals chosen from the radicals: i) hydroxy, ii) alkoxy, C₁-C₄Iii) acylamino, iv) amino optionally substituted by one or two alkyl radicals, identical or different C₁-C₄, Said alkyl radicals possibly forming, with the nitrogen atom which bears them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom identical to or different from nitrogen; v) or a quaternary ammonium group -N R'R "R" ', M in which R', R ", R" ', identical or different, represent a hydrogen atom, or an alkyl group C₁-C₄Or else -N R'R "R" 'forms a heteroaryl such as imidazolium optionally substituted by a C₁-C₄ alkyl, and M represents the against-ion of the organic acid, mineral acid or the corresponding halide,

p0054- A "alkoxy" is an alkyl-oxy radical for which the alkyl is a hydrocarbon radical, linear or branched C₁-C₁₆ preferably C₁-C₈ ; where the alkoxy group is optionally substituted, this means that the alkyl group is optionally substituted as defined above.

p0055In addition, unless otherwise indicated, the limits delimiting the extent of a range of values ​​are included in this range of values. According to the present invention, the term "fluorescent chromophore" means a radical derived from a fluorescent compound. A fluorescent compound is a compound which is capable of absorbing in the UV or visible radiation at a wavelength λ_abs between 250 and 800 nm and capable of re-emitting in the visible range at a transmission wavelength λ_em between 400 and 800 nm. Preferably fluorescent compounds are dyes capable of absorbing in the visible λ_atbs between 400 and 800 nm and re-emit in the visible λ_em between 400 and 800 nm. More preferably dyes Fluorescent dyes are capable of absorbing at a λ_abs between 420 nm and 550 nm and re-emit in the visible range at a λ_em between 470 and 600 nm.

p0056/. Dyes of formulas (I) and (II) the radicals A and A 'of the formulas (I) and (II) may contain one or more fluorescent chromophores, which are identical or different. 1.1. chromophores

p0057Within the meaning of the present invention, the chromophores are said to be different when they differ in their chemical structure. Such chromophores may be chromophores from different families or one family on the condition that have different chemical structures. For example, the chromophore may be selected from the family of dyes (poly) methine but differ by the chemical structure of the constituting radicals or by the respective position of these radicals. By way of useful fluorescent chromophores in the present invention include the radicals derived from acridine dyes, acridone, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro {2 - [(2H-pyrrol-2 -ylidene-kN) methyl] -1 H-pyrrolato- kNJbores (BODIPY ®) dipyrrinones, diketopyrrolopyrroles, fluorindines, (poly) methine (including cyanine and styryl / hemicyanines) naphthalimides, naphthanilides, naphthylamine (like dansylated), oxadiazoles , oxazines, périlones, perinone, perylene, polyene / carotenoids, squaranes, stilbene, xanthenes.

p0058Also exemplary fluorescent dyes described in EP 1 133975, WO 03/029359, EP 860 636, WO 95/01772, WO 95/15144, EP 714954 and those listed in the encyclopedia "The chemistry of synthetic dye" of K. VENKATARAMAN, 1952 Academy press vol 1 to 7 in the encyclopedia "Kirk Othmer" "Chemical technology" chapter "dyes and Dye intermediate" 1993, Wiley and sons, and in various chapters of the encyclopedia "Ullmann's Encyclopedia of Industrial chemistry "7th edition, Wiley and sons, in the Handbook - A Guide to Fluorescent Probes and Labeling Technologies, 10th Ed Molecular Probes / Invitrogen - Oregon 2005 available on the Internet or in previous editions printed.

p0059Preferably, the chromophores are chosen from those derived from coumarin dyes, (poly) methine (including cyanine and styryl / hemicyanines) and naphthalimides. Alternatively, the radicals A and A 'of formulas (I) or (II) contain at least one cationic radical carried by or included in at least one of the chromophores. Preferably, the cationic group is a quaternary ammonium.

p0060These cationic groups are, for example a radical alkylammonium, acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium benzotriazolium, benzoxazolium, bi-pyridinium bis-tetrazolium dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium. <img id="imgf000011_0001" he="9" wi="32" file="imgf000011_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0061As indicated above, in the formulas (I) or (II), C_hert and C '_hert, independently of one another represent an alkylene chain CRCI₈Linear or branched, optionally substituted, optionally cyclic. As a substituent, there may be mentioned amino, (CrC₄) Alkylamino, (-C₄) Dialkylamino, or the R^at-Z^at-C (Z^b) - (Wherein Z^at, Z^b, Identical or different, represent an oxygen, sulfur, or NR^at'And R^atRepresents an alkali metal, a hydrogen atom, or a group Ci-C₄ alkyl and R^at'Represents a hydrogen atom or a group dC₄ alkyl) preferably present on the carbon in position beta or gamma sulfur atoms.

p0062Preferably, in the case of formulas (I) or (II), C_sat and C '_satRepresent a chain - (CH₂)_k- K is an integer, ranging from 1 to 8. <img id="imgf000011_0002" he="6" wi="25" file="imgf000011_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> any way to a particular embodiment of the invention, in formulas (I) or (II) above, when p is 1, X and X ', identical or different, represent the following sequence:

p0063- (T)₁- (Z)₂- (T¹), - Said sequence being linked in formulas (I) or (II) in a symmetrical manner as follows:

p0064- C_sat (Or C'sat) - (T) r (Z)_z- (A or A '); in which

p0065T and T, identical or different, represent one or more radicals or combinations thereof selected from: -SO₂-; -O-; -S-; -N (R) -; -NOT⁺(R) (R⁰) -; -CO-; with R, R °, identical or different, representing a hydrogen atom, an alkyl radical C_rC₄Hydroxyalkyl, C_rC₄ or aryl (dC₄) Alkyl; and a heterocycloalkyl or heteroaryl radical, cationic or noncationic, preferably monocyclic, containing preferably two heteroatoms (more preferably two nitrogen atoms) and preferably having from 5 to 7 members, more preferably imidazolium; t and t indices', identical or different, are O or 1; Z represents:

p0066- - (CH₂)_m- M is an integer between 1 and 8 - - (CH₂CH₂O)_q- Or - (OCH₂CH₂)_q- In which q is an integer between 1 and 15 aryl, alkylaryl or arylalkyl radical whose alkyl radical is C d-₄ and the aryl radical is preferably C₆, Being optionally substituted by at least one group SO₃M with M representing a hydrogen atom, an alkali metal ammonium or an ammonium group substituted by one or more alkyl radicals, identical or different, linear or branched CRCI₈ optionally bearing at least one hydroxyl z is O or 1. Moreover, according to a particular embodiment of the invention, Z represents:

p0067<img id="imgf000012_0001" he="15" wi="124" file="imgf000012_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p00681.4. disulfide fluorescent dyes:

p0069According to a preferred variant of the invention, the disulphide dye is a cationic fluorescent dye comprising at least one quaternary ammonium radical and such that, in the formula (I) with p equal to 1:

p0070A and A ', identical or different, more preferably identical, represent toilet (R^c) = C (R^d) -Ar- Or -WC (R^c) = C (R^d) -Ar, W represents a heterocycle or a heteroaryl comprising a quaternary ammonium; Ar represents a (hetero) aryl, 5- or 6-membered phenyl type or pyridinium, or a bicyclic (hetero) aromatic naphthyl type benzopyrydinium, indolinyl, or benzoindolinyle, optionally substituted by one or more halogen atoms, preferably chlorine, fluorine; by one or more alkyl, preferably C₁-C₄ ; by one or more hydroxyl groups; by one or more alkoxy groups, by one or more hydroxyalkyl groups, with one or more amino or (di) alkylamino, preferably with the alkyl part Ci-C₄, By one or more acylamino groups; by one or more heterocycloalkyl groups or 5- or 6-membered heterocycle preferably selected from pyrrolidinyl, piperazinyl, piperidinyl and imidazolinyl; R^c, R^d, Identical or different, represent a hydrogen atom or an alkyl group dC₄.

p0071According to a preferred variant p, p '= 1; z = 0; t '= 0 and t = 1 and T is -N (R) - , Preferably in the para position on Ar with respect to the olefin function -C (R^c) = C (R^d) -.

p0072According to another preferred embodiment p, p '= 1; z = 0; t, t '= 1; T represents - N (R) -, preferably in para-position on Ar with respect to the olefin function - C (R^c) = C (R^d) - And T is -N (R) -, -N⁺(R) (R⁰) - Or an imidazolium.

p0073Preferably, W is an imidazolium, pyridinium, benzopyridinium, benzimidazolium, quinolinium, and pyrazolium, optionally substituted by one or more alkyl radicals, identical or not, dC₄.

p0074According to another preferred embodiment, the disulphide dye is a cationic fluorescent dye comprising at least one quaternary ammonium radical and such that, in the formula (I) with p equal to 1:

p0075A representing a radical naphthalimidyle formula:

p0076<img id="imgf000013_0001" he="32" wi="68" file="imgf000013_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> --I-- representative with the association with the group X or X ', C_sat or C '_5AT wherein R^e, R^f, R⁹, And R^h, Identical or different, represent a hydrogen atom or an alkyl group -C₆ optionally substituted.

p0077More preferably, the disulphide dye is a fluorescent dye selected from:

p0078<img id="imgf000013_0002" he="26" wi="160" file="imgf000013_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0079<img id="imgf000014_0001" he="185" wi="150" file="imgf000014_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0080<img id="imgf000014_0002" he="26" wi="136" file="imgf000014_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000015_0001" he="160" wi="139" file="imgf000015_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0081in which

p0082• G and G ', same or different, represent a group -NR_cR_d, - NR '_cR '_dOr C₁-C₆ alkoxy optionally substituted, preferably unsubstituted; preferentially G and G 'represent a group NR_cR_d and -

p0083NR '_cR '_d respectively ;

p0084• R₃ and R '_at, Identical or different, an aryl (dC₄) Alkyl or a group -C₆ alkyl optionally substituted with a hydroxyl or amino group, -C₄ alkylamino, Ci-C₄ dialkylamino, said alkyl radicals possibly forming, with the nitrogen atom which bears them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom identical to or different from nitrogen; preferably R₃ and R 'a represent a C_rC₃ alkyl optionally substituted by hydroxy, or a benzyl group; • Rb, R'b, identical or different, represent a hydrogen atom, an aryl (dC₄) Alkyl or a C_rC₆ optionally substituted alkyl; preferably R_b, R'b represent a hydrogen atom or a C_rC₃ alkyl or benzyl;

p0085• R_c, R'c, R_d and R '_d, Identical or different, represent a hydrogen atom, an aryl group (-C₄) Alkyl, C₁-C₆ alkoxy or a C₁-C₆ optionally substituted alkyl; R_c, R '_c, R_d and R '_d preferably represent a hydrogen atom, a hydroxy group, C₁-C₃ alkoxy, amino, C₁-C₃ (Di) alkylamino, or a C₁-C₃ alkyl optionally substituted with i) hydroxy, ii) amino, iii) C₁-C₃ (Di) alkylamino, or iv) quaternary ammonium (R ") (R") (R " ') N⁺-; or when two adjacent R_c and R_d, R '_c and R '_d carried by the same nitrogen atom together form a heterocyclic or heteroaryl group; preferably the heterocycle or heteroaryl is monocyclic and has 5 to 7 members; more preferably the groups are selected from imidazolyl and pyrrolidinyl;

p0086• R_e and R '_e, Identical or different, represent a hydrocarbon chain C₁-C₆ alkylenyl divalent, linear or branched, optionally unsaturated;

p0087• R_f and R '_f, Identical or different, represent a quaternary ammonium group (R ") (R") (R " ') N⁺- Wherein R ", R '" and R "" are identical or different, represent a hydrogen atom or a C₁-C₄ alkyl or so

p0088(R ") (R") (R "") n - is a cationic group optionally substituted heteroaryl preferably an imidazolinium group optionally substituted by a C₁-C₃ alkyl;

p0089• R₉, R '_g, R "_g, R " 'g, R_h, R '_h, R "_hAnd R "_h, Identical or different, represent a hydrogen atom, a halogen atom, amino group, C₁-C₄ alkylamino, C₁-C₄ dialkylamino, cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, alkoxy, C₁-C₄(Poly) hydroxyalkoxy, C₂-C₄, Alkoxycarbonyl alkylcarbonyloxy, alkylcarbonylamino, acylamino, carbamoyl, alkylsulfonylamino, aminosulfonyl radical, or a radical C₁- C₁₆ alkyl optionally substituted by a group selected from C₁-C₁₂ alkoxy, hydroxy, cyano, carboxy, amino, C₁-C₄ alkylamino and C₁-C₄ dialkylamino, or else the two alkyl radicals borne by the nitrogen atom amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different than the nitrogen atom; preferably R₉, R '_g, R "_g, R "_g, R_h, R'H, R'V and R ' "_h represent a hydrogen atom, halogen or a group Ci-C₃ alkyl;

p0090• or else two groups R₉ and R '_g ; R "_g and R " '_g ; R_hAnd R '_h ; R "_h and R " '_h carried by two adjacent carbon atoms, together form a benzo, indeno, heterocycloalkyl fused or fused heteroaryl; the benzo, indeno, heterocycloalkyl or heteroaryl being optionally substituted by a halogen atom, amino group, C_rC₄ alkylamino,

p0091-C₄ dialkylamino, nitro, cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, alkoxy dC₄(Poly) hydroxyalkoxy, C₂-C₄, Alkoxycarbonyl alkylcarbonyloxy, alkylcarbonylamino, acylamino, carbamoyl, alkylsulfonylamino, amino-sulfonyl or a radical CRCI₆ alkyl optionally substituted by a group selected from CRCI₂ alkoxy, hydroxy, cyano, carboxy, amino, -C₄ alkylamino, C_rC₄ dialkylamino, or else the two alkyl radicals borne by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different than the nitrogen atom; preferably R_g and R '_g ; R "_g and R " '_g together form a benzo group;

p0092• or so when G represents -NR_cR_d and G 'is -NR'_cR '_d two groups R_c and R '_g ; R '_c and R "_g ; R_d and R₉ ; R '_d and R " '_g together form a saturated heterocycle or heteroaryl optionally substituted by one or more groups -C₆ alkyl, preferably a heterocycle containing one or two heteroatoms selected from nitrogen and oxygen and comprising from 5 to 7 members; more preferably the heterocycle is selected from morpholinyl, piperazinyl, piperidinyl and pyrrolidinyl;

p0093• R, R ', R¹¹_I1 and R¹¹¹_I, Identical or different, represent a hydrogen atom, or a group dC₄ alkyl;

p0094• Ri, R₂, R₃, R₄, R ', R'₂, R '₃And R '₄, Identical or different, represent a hydrogen atom or a group dC₄ alkyl, CRCI₂ alkoxy, hydroxy, cyano, carboxy, amino, -C₄ alkylamino, -C₄ dialkylamino, said alkyl radicals possibly forming, with the nitrogen atom which bears them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom different or not from nitrogen; preferably R, R₂R 3, R₄, R '₁ , R '₂, R '₃And R '₄ are hydrogen atoms or an amino group; more preferably Ri, R₂, R3, R4, R '1, R'₂, R '3 and R'₄ represent a hydrogen atom; • T_atT_b, Identical or different, represent i) a σ covalent bond, ii) one or more radicals or combinations thereof selected from -SO₂-, -O-, -S-, -N (R) -, -N⁺(R) (R⁰) -, -CO-, With R, R °, identical or different, representing a hydrogen atom, an alkyl radical dC₄Hydroxyalkyl, dC₄; or aryl (Ci-C₄) Alkyl, preferably T_at is identical to T_b and σ represent a covalent bond or a group selected from -N (R) -, -C (O) -N (R) -, -

p0095N (R) -C (O) -, -0-C (O) -, -C (O) -O- and -N⁺(R) (R⁰) -, With R and R ° are identical or different representing a hydrogen atom or a C_rC₄ alkyl; more preferably T_at and T_b represent a σ bond; iii) a heterocycloalkyl or heteroaryl radical, cationic or noncationic, preferably monocyclic, preferably identical, preferably containing two heteroatoms (more preferably two nitrogen atoms) and preferably having from 5 to 7 members such as imidazolium;

p0096identical or different, represent a group <img id="imgf000018_0002" he="15" wi="44" file="imgf000018_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> optionally substituted heterocyclic; preferably heterocycles are identical, monocyclic, saturated, and include a total of two nitrogen atoms and 5 to 8 members;

p0097• <img id="imgf000018_0001" he="12" wi="17" file="imgf000018_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> represent an aryl group or heteroaryl fused to the phenyl ring; or is absent then the phenyl ring; preferably when the ring is present the ring is a benzo;

p0098• m, m ', n and n', identical or different, represent an integer ranging from O to 6 with m + n, m '+ n', identical or different, represents an integer ranging between 1 and 10; preferably n + m = m '+ n' = an integer ranging between 2 and 4; more preferably m + n = m '+ n' = an integer equal to 2; M 'representing against ion or an organic or inorganic acid salt.

p0099Examples of fluorescent disulphide dyes, there may be mentioned the following compounds:

p0100<img id="imgf000019_0001" he="211" wi="117" file="imgf000019_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p010110

p0102<img id="imgf000020_0001" he="225" wi="142" file="imgf000020_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> 10 <img id="imgf000021_0001" he="211" wi="115" file="imgf000021_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000022_0001" he="223" wi="117" file="imgf000022_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /><img id="imgf000023_0001" he="213" wi="141" file="imgf000023_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /><img id="imgf000024_0001" he="224" wi="171" file="imgf000024_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /> 

p0103<img id="imgf000025_0001" he="202" wi="143" file="imgf000025_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0104<img id="imgf000026_0001" he="203" wi="132" file="imgf000026_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /><img id="imgf000027_0001" he="213" wi="115" file="imgf000027_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p010510 <img id="imgf000028_0001" he="218" wi="130" file="imgf000028_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p010610 <img id="imgf000029_0001" he="187" wi="149" file="imgf000029_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p010710

p0108<img id="imgf000029_0002" he="18" wi="117" file="imgf000029_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000030_0001" he="223" wi="142" file="imgf000030_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000031_0001" he="183" wi="161" file="imgf000031_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000032_0001" he="212" wi="150" file="imgf000032_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0109<img id="imgf000033_0001" he="224" wi="148" file="imgf000033_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0110<img id="imgf000034_0001" he="68" wi="88" file="imgf000034_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0111<img id="imgf000034_0002" he="94" wi="103" file="imgf000034_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p011210 <img id="imgf000034_0003" he="42" wi="112" file="imgf000034_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000035_0001" he="225" wi="117" file="imgf000035_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /><img id="imgf000036_0001" he="37" wi="106" file="imgf000036_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> M 'against an anionic ion.

p01131.5. The organic salt and against ion: An "organic or mineral acid salt" is more particularly chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H₂SO₄, Iv) alkylsulfonic acids: AIk-S (O)₂OH such as methylsulphonic acid and ethylsulphonic acid; v) arylsulfonic acids: Ar-S (O)₂OH such as benzenesulfonic and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) of alcoxysulfiniques acids: Alk-OS (O) OH such as from methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulphinic acids such as tolueneoxysulphinic phenoxysulphinic acid and acid; xii) phosphoric acid H₃PO₄; xiii) of acetic acid CH₃COOH; xiv) of triflic acid CF₃SO₃H xv) tetrafluoroboric acid HBF₄. A "against anionic ion" is an anion or an anionic group associated with the cationic charge of the dye; more particularly against the anionic ion is selected from: i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates, including the C_rC₆ alkylsulphonates: Alk-S (O)₂O^" such as methyl sulfonate or mesylate and ethyl sulfonate; iv) arylsulfonates: Ar-S (O)₂O^" such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkylsulfites: Alk-OS (O)^" such as méthysulfite and éthylsulfite; x) arylsulfites: Ar-OS (O)^" such as benzènesulfite and toluènesulfite; xi) alkyl sulfates: Alk-OS (O)₂O^" such as methyl sulfate and ethyl sulfate; xii) arylsulfates: Ar-OS (O)₂O^"Xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate.

p01141.6. Preparation of fluorescent disulphide dyes:

p0115Fluorescent disulphide dyes may be prepared according to methods known to those skilled in the art.

p0116According to a first possibility, one can react a disulfide compound comprising two amine functions, primary or secondary preferably with a sufficient amount of a "reactive fluorescent chromophore" or a compound comprising such a "reactive fluorescent chromophore", in other words comprising one electrophilic function. Among the "fluorescent chromophore reagents" include reactive dyes having a vinylsulfone particular function, sulfatoethyl sulfone, mono- di- chlorotriazine, mono- di-chloropyrimidine, difluoro chloropyrimidine, dichloroquinoxaline, bromo-vinylsulfone.

p0117Also suitable as chromophoric reagents, fluorescent chromophores compounds comprising at least one group capable of reacting with an amine function to give a sulfonamide group (-SO₂-NR-), Amide (-CO-NR-). For example, there may be mentioned the groups -SO₃W, -COOW (W represents a hydrogen atom, an alkali metal such as sodium, potassium, an ammonium group, an ammonium group substituted by one or more alkyl, identical or different, linear or branched CRCI₀Optionally carrying at least one hydroxyl) which can be activated beforehand, by known methods, respectively, a group -SO₂CI, -COCI.

p0118It is thus possible to implement, as a reactive fluorescent chromophore, the Colour Index of acid dyes listed as such. Reference may be made especially to the book Advanced Organic Chemistry,

p0119March 4^th Ed, for more details on the operating conditions implemented.

p0120Still in the context of this first possibility, one can implement fluorescent chromophores comprising a labile group directly bonded or non-fluorescent chromophore and may be substituted by an amino group, such as Cl, Br, F, O-alkyl (eg O-me), O-aryl, O-alkyl aryl (eg O-benzyl).

p0121Disulfides fluorescent dyes may also be obtained in the context of this possibility, using chromophores having an acrylate function (-OCO-C = C-) on which is carried out an addition reaction.

p0122According to another possibility, the fluorescent disulphide dyes may be obtained by reacting a disulfide compound with a compound having two carboxylic acid functions activated according to conventional methods (for example reaction with a carbodiimide or with thionyl chloride). The resulting product is then reacted with a fluorescent chromophore carrying a nucleophilic function, for example primary or secondary amine-type, or aliphatic or aromatic alcohol such as phenol. Again, one can refer to the book Advanced Organic Chemistry, March, 4^th Ed, for more details on the operating conditions implemented.

p0123According to a third possibility, the fluorescent disulphide dyes may be obtained by reacting a compound having a disulfide group and two hydroxyl groups previously activated leaving groups (e.g. mesylate, tosylate) with a fluorescent chromophore which carries a nucleophilic function, preferably such primary amine, secondary or tertiary, heteroaromatic or not, for example, pyridine, imidazole, benzimidazole.

p0124According to a fourth possibility, the fluorescent disulphide dyes may be obtained by oxidation of dyes bearing an SH function.

p0125According to a fifth possibility, and in particular for the preparation of compounds of formula (II), disulfides fluorescent dyes may be obtained by a variant of the possibilities one, two or three described above, using a molar amount of reactant greater than or equal to the molar amount disulfide reagent containing the chromophore group.

p0126The preparation of disulphides fluorescent dyes of formula (I) wherein A and A 'are identical, however, is facilitated by the use of a molar amount of reagent containing the fluorescent chromophore group preferably greater than or equal to twice the amount of disulfide reagents.

p0127According to a sixth possibility, and in particular for the preparation of compounds of formula (I) and the two groups A, A 'on the one hand and X and X' on the other hand, are different, the disulfide compounds may be obtained from fluorescent disulphide compounds of the formula (II).

p0128//. Dye composition: II.1. Dyes: The dye composition according to the invention generally contains an amount of fluorescent dye disulfide between 0.001 and 50% based on 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 dye composition may also contain additional direct dyes. These direct dyes are for example chosen from nitro direct dyes, neutral, acidic or cationic azo direct dyes neutral, acidic or cationic tetraazapentamethine dyes, quinone dyes and in particular anthraquinone, acidic or cationic direct dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural. Among the natural direct dyes include lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin. One can also use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna. The dye composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratin fibers.

p0129Among the oxidation bases, mention may be made of para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts

p0130Among these couplers, mention may be made phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

p0131The coupler or couplers are each present in an amount between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%.

p0132The oxidation of bases present in the dye composition can be present in an amount ranging from 0.001 to 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6% by weight. In general, the addition salts of the oxidation bases and couplers used in the context of the invention are chosen from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the addition salts with a base, such as hydroxides of alkali metal such as sodium, potassium, ammonia, amines or alkanolamines.

p0133The medium suitable for dyeing, also called dye support, is a cosmetic medium consisting of water or a mixture of water and at least one organic solvent. As organic solvent, there may be mentioned are lower alcohols -C₄, Such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and monomethyl ether of diethylene glycol, and aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

p0134The solvents when present are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight.

p0135Alternatively, the invention contains a reducing agent capable of reducing disulfide bonds. This reducing agent is as defined above.

p013611.2. adjuvants:

p0137The dye composition may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants, anionic, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, thickening agents, inorganic or organic, and associative thickeners anionic, cationic, nonionic and amphoteric polymers, antioxidants, penetrants, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents such as for example, volatile or nonvolatile silicones, modified or not, such as amino silicones, film-forming agents, ceramides, preservatives, opacifiers, or conductive polymers. Amount of adjuvants:

p0138The above adjuvants are generally present in an amount for each ranging from 0.01 to 20% by weight relative to the weight of the composition. Of course, the man of the art care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the dye composition according to the invention are not, or not substantially, impaired by the additions envisaged. DH: The pH of the dye composition is generally between 3 and 14 approximately, and preferably between approximately 1 to 1 5. It can be adjusted to the desired value using acidifying or alkalizing agents usually used for dyeing keratin fibers, or alternatively using standard buffer systems.

p0139Among the acidifying agents, mention may, for example, the inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, and sulphonic acids. Among the alkalizing agents include, for example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium or potassium hydroxides and compounds formula (α) below:

p0140<img id="imgf000041_0001" he="20" wi="43" file="imgf000041_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein W_at is a propylene residue optionally substituted with a hydroxyl group or an alkyl radical -C₄ ; R_ati, R_at2, R a3 and R_a4, Identical or different, represent a hydrogen atom, an alkyl radical dC₄ or hydroxyalkyl dC₄.

p014111.3. Forms of composition:

p0142The dye composition may be in various forms, such as in liquid, cream, gel, or in any other form suitable for dyeing keratin fibers, especially the hair.

p0143///. Dyeing process:

p0144The application of the dye composition is generally conducted at room temperature. It may however be carried out at temperatures ranging from 20 to 180^&lt;€.

p0145In a particular process of the invention coloring, the application of disulfide fluorescent dye to keratin materials is carried out together with a reducing agent. The reducing agent is as defined above.

p0146According to another variant, the reducing agent is added to the dye composition containing the disulfide fluorescent dyes (I) and (II) at the time of use.

p0147According to another variant, the method of the invention may be implemented in the presence of an oxidizing agent in post processing when the composition already contains a reducing agent.

p0148The oxidizing agent may be any oxidizing agent conventionally used in the field. Thus, it can be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, and enzymes, among which mention may be made peroxidases, oxido 2-electron such as uricase and 4-electron oxygenases such as laccases. The use of hydrogen peroxide is particularly preferred.

p0149This oxidizing agent may be applied to the fibers before or after applying the composition containing the disulfide fluorescent dyes of formula (I) and (II).

p0150///. Device or "kit" for dyeing:

p0151The invention also relates to a multi-compartment device or

p0152"Kit" in which a first compartment contains a dye composition comprising at least one disulfide fluorescent dye of formulas (I) or (II) and a second compartment contains a reducing agent capable of reducing the disulfide bond of the dye and / or disulfide functions of the keratin materials.

p0153One of these compartments may also contain one or more other dyes direct dye or oxidation dye. It also relates to a multi-compartment device in which a first compartment contains a dye composition comprising at least one disulfide fluorescent dye of formulas (I) or (II); a second compartment contains a reducing agent capable of reducing the disulfide bond of the dye; a third compartment contains an oxidizing agent. Each of the devices mentioned above may be equipped with a means for applying to the hair the desired mixture, for example such as the devices described in patent FR 2 586 913.

p0154The following examples serve to illustrate the invention without being limiting in nature. Disulfide fluorescent dyes of the examples hereinafter have been entirely characterized by conventional spectroscopic and spectrometric methods.

EXAMPLES

p0156SYNTHESIS EXAMPLES example 1

p0157<img id="imgf000043_0001" he="61" wi="152" file="imgf000043_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0158Step 1: dibromide 1, 1 '- (disulfanediyldiéthane-2,1-diyl) bis (2-methyl- pyridinium)

p0159A mixture of 56 g of 1-bromo-2 - [(2-bromoethyl) disulfanyl] methane and 15 ml of Λ / -Méthylpyrrolidone (NMP) is added dropwise to 35 g of 2-picoline under stirring at 80⁹C. The mixture (white suspension) is kept stirred for 30 minutes at 80⁹C, 100 mL acetonitrile are added, stirring is maintained at 80⁰C for 90 min. After cooling, the solid obtained is filtered, washed with 100 mL of acetonitrile and then dried.

p0160Collected 56.2 g of brown powder. 45 g of this powder are suspended in 300 mL of isopropanol at reflux. Once the temperature lowered to 40 ° C, the solid is filtered, washed with 3 times 100 mL of isopropanol and dried under vacuum. beige product, 40.56 g. Analyzes in accordance with the expected structure.

p0161Step 2: dibromide 1, 1 '- (disulfanediyldiéthane-2,1-diyl) bis (2 - {(E) -2- [4- (dimethylamino) phenyl] vinyl} pyridinium)

p0162150 mg of pyrrolidine and 129 mg of acetic acid are added to a solution of 297 mg of 4-dimethylaminobenzaldehyde in 2 mL of methanol.

p0163After stirring for 18 h at room temperature, 495 mg dibromide 1 '- (2,1 disulfanediyldiéthane-diyl) bis (2-methylpyridinium) are added to the mixture and stirring is continued at room temperature for 7 days. After filtration, washing with methanol and drying under vacuum, 312 mg of orange powder are recovered. Analyzes in accordance with the expected structure. NMR¹H (400 MHz, MeOH-Of₄): 3.02 (s, 6H), 3.22 (t, 2H), 5 (t, 2H), 6.72 (m, 2H), 7.19 (d, 1H), 7.63 (m, 3H), 7.76 (d, 1H) 8.3 (m, 2H), 8.59 (m, 1H).

p0164example 2

p0165<img id="imgf000044_0001" he="78" wi="94" file="imgf000044_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0166Step 1: 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde

p016782.3 g of phosphorus oxychloride are added to 500 mL of DMF at 0⁰C. After 30 min stirring at 0 ° C a solution of 47 g of Λ /, Λ / '- (2.1 disulfanediyldiéthane-diyl) bis (N-methylaniline) was added drop by drop. The mixture was stirred 90 min. 0⁰C and 75 min. 10⁹C and 105 min. 40⁹C. It is then poured onto 2.5 L of ice water, 700 mL of 5N sodium hydroxide are added. The yellow precipitate obtained is filtered on celite, dissolved in 200 mL of dichloromethane and the solution obtained is washed with 200 mL of saturated aqueous sodium chloride. After drying over magnesium sulfate and evaporation of the dichloromethane, the yellow residue (80g) was purified by chromatography on silica gel.

p0168After drying, a light yellow powder is collected. The analyzes indicate that the product conforms to the expected structure. Step 2: dichloride of 2,2 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1- phenylene (E) ethene-2,1-diyl]} bis (1-methylpyridinium)

p016925 g of 4,4 '- {disulfanediylbis [2,1-ethane diyl (methylimino)]} dibenzaldehyde and 18.5 g of N-méthylpicolinium are dissolved in 300 mL of methanol. 12.7 ml of piperidine are added to the mixture. The whole is heated with stirring at 55⁹C for 1 1M. Methanol is removed in vacuo at 40⁹C. The solid is mixed with 300 mL of isopropanol. After a further drying by evaporation are introduced 200 ml of isopropanol. The mixture solidifies, it is extended by adding 100 mL of iospropanol and drained on sintered glass. The collected solid is washed with isopropanol then acetone, then dried under vacuum. After drying, 36,7g orange powder is collected. By recrystallisation from isopropanol, 27 g of purity of red orange powder are recovered. The analyzes indicate that the product complies and pure. NMR¹ H (400 MHz, MeOH-Of₄) 2.99 (t, 4H), 3.81 (t, 4H), 4.31 (s, 6H), 6.86 (d, 4H), 7.22 (d, 2H), 7.63 (m, 2H), 7.69 (d, 4H), 7.83 (d, 2H), 8.29 (m, 2H), 8.36 (m, 2H), 8.61 (m, 2H).

p0170Example 3:

p0171<img id="imgf000045_0001" he="99" wi="113" file="imgf000045_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Diméthoxysulfate 4,4 '- disulfanediylbis {[2,1-ethane diyl (methylimino) -4,1 - phenylene (E) ethene 2,1-diyl]} bis (1 -méthylpyridinium)

p01722.62 g of 4-picoline are diluted in 25 ml of dichloromethane, 3 ml of dimethyl sulfate are added to the solution, the temperature rose to reflux (40⁰C). After 40 min. of stirring, 50 mL of isopropanol are added, and the mixture is concentrated by distilling off the dichloromethane (mixture heated at 60⁰C). 1, 83 g of pyrrolidine are introduced into the mixture followed by 4.99 g of 4,4 '- {disulfanediylbis [ethane-2,1 - ethanediyl (methylimino)]} dibenzaldehyde. After stirring for 2 h at 65⁹C, the reaction mixture is cooled to room temperature, the precipitate formed is filtered, washed with 3 times 100 mL of isopropanol. The red paste obtained is dispersed in 200 mL of isopropanol, the mixture thus obtained is refluxed and then cooled. The formed red precipitate is filtered and dried. 8.94 g of red powder are recovered. The analyzes indicate that the product complies and pure. NMR¹ H (400 MHz, DMSO-Of₆) 2.96 (t, 4H), 3.02 (s, 6H), 3.36 (s, 6H), 3.72 (t, 4H), 4.16 (s, 6H), 6.81 (d, 4H), 7.15 (d, 2H), 7.57 (d, 4H), 7.87 (d, 2H), 8.02 (d, 4H), 8.66 (d, 4H).

p0173example 4

p0174<img id="imgf000046_0001" he="49" wi="82" file="imgf000046_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0175Cl 2

p0176Dichloride, 2,2 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1- phenylene (E) ethene-2,1-diyl]} bis (1-ethylpyridinium)

p017710 g of 4,4 '- {disulfanediylbis [2,1-ethane diyl (methylimino)]} dibenzaldehyde and 8,1 g of N-éthylpicolinium are dissolved in 100 mL of isopropanol. 1, 3 g of piperidine are added to the mixture. The whole is heated with stirring at reflux for 5 h. The isopropanol was removed under vacuum at 50⁹C. The resulting gum was triturated with acetone. 18 g of solid are collected and treated carbon black. 7.1 g of product are collected and 4 g are purified by liquid liquid chromatography (water / BuOH). After drying 1, 65 g of red powder are recovered. The analyzes indicate that the product complies and pure. NMR¹H (400 MHz, MeOH-O₄) 1.57 (t, 6H), 2.98 (t, 4H), 3.11 (s, 6H), 3.8 (t, 4H), 4.73 (q, 4H), 6.85 (m, 4H), 7.23 (d, 2H), 7.69 (m, 6H), 7.85 (d, 2H), 8.29 (m, 2H), 8.38 (m, 2H), 8.67 (m, 2H). example 5

p0178<img id="imgf000047_0001" he="143" wi="89" file="imgf000047_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0179Step 1: 2,2 '- (disulfanediyldiéthane-2,1-diyl) bis (6-chloro-1H-benzo [de] - isoquinoline-1, 3 (2H) -dione)

p01809.30 g of 6-chloro-1H, 3H-benzo [de] isochromene-1, 3-dione and 4.46 g of cystamine chlorhydratée hydrochloride are suspended in 50ml of N-methylpyrrolidone (NMP). 5.5 g of diisopropylethylamine were added and the mixture is heated with stirring at 120⁰C. After two hours 50 mL of NMP were added and the mixture is kept stirred at 120⁰C for 3 h. After cooling, the precipitated product is collected, the filtered solution is diluted by addition of 200 ml of water and a second precipitate was collected. The precipitates are washed with water and dried. January 1, 46 g of white powder are collected. Analyses show that the product conforms to the expected Step 2: 2,2 '- (disulfanediyldiéthane-2,1-diyl) bis [6 - {[3- (dimethylamino) propyl] - amino} -1H-benzo [de] isoquinoline-1, 3 (2H) - dione]

p01814 g of (6-chloro-2- (2 - {[2- (6-chloro-1, 3-dioxo-1H-benzo [de] isoquinolin-2 (3H) -yl) ethyl] - disulfanyl} ethyl ) -1 H-benzo [de] isoquinoline-1, 3 (2H) -dione are suspended 40 IML N, N-dimethylpropane-1, 3-diamine. The mixture was heated with stirring at

p0182January 10⁹C for 12 h. After cooling, a yellow precipitate is collected, 500 mL of ethanol / water: 1/1 are added dropwise to the filtrate. The yellow paste obtained is isolated and triturated with 200 mL of acetone. The solids obtained are washed with 300 mL of water and dried. 4.5 g of yellow powder were recovered. Analyses show that the product conforms to the expected.

p0183Step 3: sulfate of 3,3 '- {disulfanediylbis [ethane-2,1-diyl (1, 3-dioxo-1H- benzo [de] isoquinoline-2,6 (3H) diyl) imino]} bis ( N, N, N-triméthylpropan-1-aminium chloride)

p01844 g of 6 - {[3- (dimethylamino) propyl] amino} -2- [2 - ({2- [6 - {[3- (dimethylamino) propyl] - amino} -1, 3-dioxo-1 H -benzo [de] isoquinolin-2 (3H) -yl] ethyl} disulfanyl) ethyl] -1H-benzo [de] isoquinoline-1, 3 (2H) -dione are suspended in 50 ml dimethylformamide 4 ml of dimethyl sulfate are added and the mixture is stirred at room temperature for 4 h. The reaction mixture was poured into 500 mL of ethyl acetate. The precipitate is filtered, washed with 4 times 100 ml of ethyl acetate and dried under vacuum. Is recovered 5.9 g of yellow powder. The analyzes indicate that the product conforms to the expected. NMR¹ H (400 MHz, DMSO-Of₆): 2.13 (m, 4H), 3.06 (m, 4H), 3.09 (s, 18H), 3.46 (m, 4H), 4.36 (m, 4H), 6.85 (d, 2H), 7.71 (m, 2H), 7.82 (t, 2H), 8.28 (d, 2H), 8.29 (dd, 2H), 8.45 (dd, 2H).

p0185example 6

p0186<img id="imgf000049_0001" he="79" wi="148" file="imgf000049_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0187Step 1: dibromide 1, 1 '- (disulfanediyldiéthane-2,1-diyl) bis (4-methyl-pyridinium) 67 g of 4-picoline are diluted in 100 ml of acetonitrile and the mixture is heated to 80⁰C. A mixture of 60 g of 1-bromo-2 - [(2-bromoethyl) disulfanyl] methane and 15 ml N-methylpyrrolidone (NMP) was added in 5 min. After 4 hours of stirring at 85⁰C, the mixture is cooled. The solid obtained is filtered, rinsed with 3 x 200 mL of acetonitrile and then dissolved in 800 mL of isopropanol (to reflux). After cooling, 1 L ethyl ether is added. The precipitate formed is filtered, rinsed with 3 x 200 ml of ethyl ether and then dried. The broken white powder obtained (73,77g) contains vast majority (> 90%) the expected product which is used as such for the next step.

p0188Step 2: dibromide 1, 1 '- (disulfanediyldiéthane-2,1-diyl) bis (4 - {(E) -2- [4- (dimethylamino) phenyl] vinyl} pyridinium)

p018913.2 g of 4-dimethylaminobenzaldehyde are suspended in 100 mL of methanol. 6.2 g of pyrrolidine and 5.3 g of acetic acid diluted in 20 ml of methanol acid are added to the mixture (final pH 5/6). 20 g dibromide 1, 1 '- (disulfanediyldiéthane-2,1 diyl) bis (4-methylpyridinium) obtained in the previous step, dissolved in 80 ml of methanol are introduced, then the reaction mixture is diluted by addition of 100 mL of methanol. After 21 h stirring at room temperature a first precipitate was collected, washed with 3 x 100 mL of ethanol then 3 x 200 mL of ethyl acetate and dried (red powder, 7.4 g) and then a second precipitate in the filtrate was also collected and dried (red powder, 1˝ 1, 44 g). The analyzes indicate that the two fractions are consistent with the expected structure. NMR¹ H (400 MHz, MeOH-Of₄): 3.02 (s, 12H), 3.42 (t, 4H), 4.74 (t, 4H), 6.77 (d, 4H), 7.19 (d, 2H), 7.6 (d, 4H), 7.97 (d, 2H), 8.1 (d, 4H), 8.79 (d, 4H).

p0190example 7

p0191<img id="imgf000050_0001" he="37" wi="106" file="imgf000050_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0192Synthetic Scheme

p0193<img id="imgf000051_0001" he="137" wi="108" file="imgf000051_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0194Step 1: Synthesis of N, N '- (disulfanediyldiéthane-2,1-diyl) bis (2-chloroacetamide)

p019540.3 g of cystamine dihydrochloride are dissolved in 100 mL water, 32 mL of 35% sodium hydroxide are added (pH 9.7) and the temperature is lowered to 5 ° C. 33.5 ml of chloroacetyl chloride are added dropwise, keeping the temperature below 10⁹C and maintaining the pH between 7.9 and 9.3 by adding sodium hydroxide. The medium is kept stirred at room temperature for 2 H. The precipitate is filtered, washed with 5 x 150 ml of water then dried under vacuum in presence of P₂O₅. 35.3 g of white powder are collected, the analysis indicates that the product complies.

p0196Step 2: Synthesis of dichloride 1, 1 '- {disulfanediylbis [ethane-2,1-diylimino (2 oxoethane-2,1-diyl)]} bis (4-methylpyridinium) 6.1 g N, N' (disulfanediyldiéthane 2,1-diyl) bis (2-chloroacetamide) and 4.5 g of 4-picoline are dissolved in 50 ml of NMP and heated to 80 ° C for 19 h. After cooling the mixture, by successive precipitation in acetone and drying under vacuum, 9.2 g of salt were collected. Analyses show that the product complies. NMR¹H (400 MHz, D₂O): 2.61 (s, 6H), 2.82 (t, 4H), 3.56 (t, 4H), 5.31 (s, 4H), 7.85 (d, 4H), 8.51 (d, 4H) .

p0197Step 3: Synthesis of dichloride of 1, 1 '- {disulfanediylbis [ethane-2,1-diylimino (2-oxoethane-2,1-diyl)]} bis {4 - [(E) -2- (3,4 , 5-trimethoxyphenyl) vinyl] pyridinium} [4]

p0198785 mg of 3,4,5-trimethoxy-benzaldehyde, 328 μl_ pyrrolidine, 232 μl_ of acetic acid and 490 mg of dichloride of 1, 1 '- {disulfanediylbis [ethane-2,1 -diylimino (2- oxoéthane- 2,1 diyl)]} bis (4-methylpyridinium) are dissolved in 10 ml of isopropanol and kept stirred at room temperature 3 h 30 min. The mixture was poured into 50 ml of dichloromethane solution / acetone 1: 1. A solid precipitates. It is filtered, washed with three times 20 mL of acetone and dried under vacuum. 509 mg of black powder is collected. Analyses show that the product conforms (LCMS:

p0199100%; mass peak m / z = 388, corresponding to the tender).

EXAMPLES OF COLOUR

p0201Preparation of a composition A

p0202<img id="imgf000052_0001" he="44" wi="112" file="imgf000052_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0203Preparing a composition B

p0204<img id="imgf000052_0002" he="21" wi="112" file="imgf000052_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0205At the time of use, mix compositions A (9 volumes) and B (1 volume) and then apply the mixture on dark hair (tone height 4) for 30 minutes at room temperature. After rinsing with water and drying, there is an optical lightening of the hair thus treated.

p0206The locks thus treated are subjected to 30 shampoos according to a cycle which includes the wetting of the locks with water, washing with shampoos, rinsing with water followed by drying.

p0207The wick is dried before applying the next shampoo.

p0208The color of the locks before and after 30 washes was evaluated in the L^*at^*b^* by means of a spectrophotometer CM 2002 Minolta ® (Illuminant D65).

p0209In the L^* at^* b^*The three parameters respectively denote the intensity (L^*), The shade (a^*) And saturation (b^*). Under this system, the more the value of L, the higher the color lighter or less intense. Conversely, the more the value of L is small, the color is dark or very intense,^* and B^* indicate two color axes, a^* indicates the axis of green / red color and b^* axis blue / yellow color.

p0210<img id="imgf000053_0001" he="76" wi="126" file="imgf000053_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0211The results of the above table show that the color changes very little even after 30 shampoos. Thus, the coloring and the lightening effect on the hair remains virtually unchanged, showing a very good resistance to shampoos dyes of the invention.