BRPI0401190B1 - USE OF A COMPOSITION UNDERSTANDING A FLUORESCENT COLOR, COMPOSITION AND PROCESSES TO COLOR HUMAN KERATIN AND DARK SKIN FIBERS - Google Patents

Description

(54) Title: USE OF A COMPOSITION UNDERSTANDING A FLUORESCENT DYE, COMPOSITION AND PROCESSES TO COLOR HUMAN KERATIN FIBERS AND DARK SKIN (73) Holder: LOREAL, French Company. Address: 14, Rue Royale, 75008 Paris, FRANCE (FR) (72) Inventor: CHRYSTEL POURILLE-GRETHEN; GRÉGORY PLOS

Validity Term: 10 (ten) years from 10/02/2018, subject to legal conditions

Issued on: 10/02/2018

Digitally signed by:

Liane Elizabeth Caldeira Lage

Director of Patents, Computer Programs and Topographies of Integrated Circuits

1/41 “USE OF A COMPOSITION UNDERSTANDING A FLUORESCENT COLORING, COMPOSITION AND PROCESSES FOR COLORING HUMAN KERATIN FIBERS AND DARK SKIN”

Field of the Invention [001] The present invention relates to the use of a cosmetic composition that comprises at least one fluorescent dye and at least one particular amphoteric and / or non-ionic surfactant to color human keratinous materials and more with a lightening effect particularly pigmented or artificially colored hair and dark skin, to new compositions and the processes that use these compositions.

Background of the Invention [002] It is common for people with dark skin to want to lighten their skin and to use cosmetic or dermatological compositions that contain bleaching agents for this purpose.

[003] The substances most used as an optical bleaching agent are hydroquinone and its derivatives, kojic acid and its derivatives, azelaic acid, arbutin and its derivatives, alone or in combination with other assets.

[004] However, these agents are not without drawbacks. In particular, it is necessary to use them in a prolonged manner and in high amounts to obtain a whitening effect on the skin. There is no immediate effect on the application of compositions that comprise them.

[005] In addition, hydroquinone and its derivatives are used in an effective amount to cause a whitening effect. In particular, hydroquinone is known for its cytotoxicity in relation to melanocyte.

[006] On the other hand, kojic acid and its derivatives have the drawback of having a high cost and not being able, for this reason,

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2/41 be used in large quantities in products with wide commercial diffusion.

[007] Therefore, there remains a need for cosmetic compositions that allow to obtain a clearer, uniform, homogeneous complexion, of natural aspect, these compositions presenting a satisfactory transparency after application on the skin.

[008] In the hair field, there are mainly two major types of hair color.

[009] The first is semi-permanent coloring, or direct coloring, which uses dyes capable of giving the natural color of the hair a more or less marked modification that resists several washes. These dyes are called direct dyes and can be used in two different ways. The stains can be carried out by direct application on the keratin fibers of the composition containing the direct dye (s) or by applying an extemporaneous mixture of a composition containing the direct dye (s) (s) with a composition containing an oxidizing bleaching agent which is preferably hydrogen peroxide. Then there is talk of direct whitening coloring.

[0010] The second is permanent staining or oxidation staining. This is carried out with color precursors called “oxidation” which are colorless or slightly colored compounds that, once mixed with oxidizing products, at the time of use, can give rise to an oxidative condensation process to colored and coloring compounds. It is often necessary to associate oxidation bases and couplers with one or more direct dyes in order to neutralize or attenuate tones with an excess of red, orange or gold reflections, or as opposed to accentuating these red, orange or golden reflections.

[0011] Among the direct dyes available, the benzene nitrated direct dyes are not powerful enough, the

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3/41 indoamines, quinonic dyes as well as natural dyes have a low affinity for keratin fibers and therefore lead to stains that are not sufficiently resistant to the different treatments to which the fibers may be subjected, and in particular when washing .

[0012] In addition, there is a need to obtain a lightening effect on human keratin fibers. This lightening is classically achieved by a process of discoloration of the melanins in the hair by an oxidizing system usually constituted by hydrogen peroxide associated or not associated with persals. This discoloration system has the disadvantage of degrading keratin fibers and altering its cosmetic properties.

[0013] The present invention therefore relates to compositions that make it possible to bring solutions to the problems mentioned above, that is to say that it has a good affinity of dye for keratin fibers, good toughness properties before external agents, and in particular when washing, and that also allow to obtain a lightening without alteration of the fiber.

Brief Description of the Invention [0014] It was discovered, therefore, in an unexpected and surprising way that the use of fluorescent dyes and in particular those in the orange range, in the presence of particular surfactants, allowed to achieve these objectives.

[0015] The present invention therefore has as its first object the use of a composition that comprises, in a cosmetically acceptable medium, at least one fluorescent dye soluble in the medium and at least one amphoteric surfactant chosen among the betaines and the imidazolium derivatives and / or at least one nonionic surfactant chosen from among

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4/41 alkylpyrrolidones, oxyalkylenated or glycerolated fatty alcohol ethers, oxyalkylene or glycerolated monoalcohol fatty acid esters, fatty acid and polyester esters, possibly oxyalkylenated or glycerolated, to color the keratinous materials with a lightening effect.

[0016] A second object of the present invention relates to compositions that comprise, in a cosmetically acceptable medium, at least one fluorescent dye soluble in the medium; which does not comprise three condensed cycles, one of which is a monocatonic heterocycle comprising two nitrogen atoms; the composition not comprising, as a fluorescent agent, 2- [2- (4-dialkylamino) -phenylethyl] 1-alkylpyridinium in which the alkyl radical of the pyridinium nucleus represents a methyl radical, ethyl, the one of the benzene nucleus represents a methyl radical and in which the counterion is a halide; and at least one amphoteric surfactant chosen from betaines and imidazolium derivatives and / or at least one nonionic surfactant chosen from alkylpyrrolidones, oxyalkylene or glycerolated fatty alcohol ethers, oxyalkylated or glycerolated monoalcohol and fatty acid esters esters of fatty acids and polyols.

[0017] A third object of the present invention refers to a coloring process with a lightening effect on the hair, in which the following steps are performed:

a) the composition according to the present invention is applied to the hair for a time sufficient to reveal the desired color and lightening,

b) if necessary, rinse the hair,

c) eventually, the hair is washed with shampoo and rinsed,

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5/41

d) dry the hair or let it dry.

[0018] It also has as its object a process for coloring with a lightening effect a dark skin, which consists of applying the composition according to the present invention on the skin, and then the skin is dried or allowed to dry.

[0019] The compositions used according to the present invention allow in particular a better diffusion of the fluorescent dye in the keratin materials, which is translated by an increased fluorescence effect, by a superior lightening effect and, therefore, also by a luminosity higher than those obtained with the fluorescent dye used alone.

[0020] There is also a better tenacity of the result when washing or washing with shampoos.

[0021] Other features and advantages of the present invention will appear more clearly upon reading the description and examples presented below.

Detailed Description of the Invention [0022] Unless otherwise specified, the limits of the ranges of values given in the description are included in these ranges.

[0023] As indicated above, the present invention has for its object the use of a composition that comprises, in a cosmetically acceptable medium, at least one fluorescent dye soluble in the medium and at least one amphoteric surfactant chosen among the betaines and the derivatives of imidazolium and / or at least one nonionic surfactant chosen from alkylpyrrolidones, oxyalkylenated or glycerolated fatty alcohol ethers, oxyalkylenated or glycerolated monoalcoholic fatty acids esters, and glycerolated fatty acid esters and possibly glycerolated polyols, eventually to oxyalkylated polyols. coloring human keratin substances with a lightening effect.

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[0024] Amphoteric betaine type surfactants suitable for the present invention are preferably chosen from alkyl (C8-C20) betaines, alkyl (C8-C20) -amidoalkyl (C1-C8) -betaines, alkyls (C8-C20) amidoalkyl (C1-C8) -sulfobetaines, and sulfobetaines.

[0025] Preferably, betaine type amphoteric surfactants suitable for the present invention are preferably chosen from alkyl (C8-C20) betaines, alkyl (C8-C20) amidoalkyl (C1-C8) sulfobetaines, and sulfobetaines.

[0026] As examples, we can mention in particular all compounds classified in the CTFA dictionary, 9th edition, 2002, under the names: Coco-betaine, Lauryl-betaine, Cetyl-betaine,

Coco / oleamidopropyl-betai'ne, Cocoamidopropyl-betaine, Palmitamidopropylbetaine, Stearamidopropyl-betaine, Cocamidoethyl-betaine, Cocamidopropylhydroxy-sultaine, Oleamidopropyl-hydroxy-sultaine, Coco-hydroxy-sultaine, Lauryl-hydroxy-sul, alone or in mixtures.

[0027] With regard to imidazolium derivatives, the latter are advantageously chosen from amphocarboxyglycinates and amphocarboxypropionates.

[0028] As examples, the compounds classified in the CFTA dictionary, 9th edition, 2002, under the names Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium Caproamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropate, Disodium Lauroamphodipropate, Disodium Lauroamphodipropionate Capryloamphodipropionate,

Lauroamphodipropionic acid, Cocoamphodipropionic acid, alone or in mixtures.

[0029] Among the nonionic surfactants that can be used in the composition according to the present invention, there are

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7/41 particularly non-ionic alkylpyrrolidones. Such surfactants are preferably (C 1 -C 30) alkylpyrrolidones.

[0030] As examples, we can mention the compounds classified in the dictionary CTFA, 9th edition, 2002, under the names Lauryl pyrrolidone, Caprylyl pyrrolidone, Methyl pyrrolidone, alone or in mixtures.

[0031] The oxyalkylenated or glycerolated fatty alcohol ethers are more particularly chosen among the linear or branched, saturated or unsaturated, ethoxylated and / or propoxylated and / or glycerolated fatty alcohols, with a grease chain comprising for example from 8 to 30 carbon atoms, the number of ethylene oxide and / or propylene oxide groups varying in particular from 1 to 200 and the number of glycerol groups varying in particular from 1 to 30.

[0032] It can be mono- or diethers.

[0033] As examples, we can mention the compounds classified in the CTFA dictionary, 9th edition, 2002, under the names Oleyl glyceryl ether, Oleth-2, Oleth-8, Oleth-106, Steareth-20, Laureth- 10, PEG4 ditallow ether, PPG-Beneth-15, PPG-8 Ceteth-1, PPG-50 Cetyl ether, PPG-6Decyltetradeceth-12, PPG-2-isodeceth-9, PPG-30 Isocethylether, PPG-4 Laurylether, PPG -10 Oleylether.

[0034] Preferably, fatty alcohol ethers are chosen from linear or branched, saturated or unsaturated, ethoxylated and propoxylated, or propoxylated, and / or glycerolated fatty alcohols.

[0035] Esters of fatty acids and monoalcohols or oxyalkylene or glycerolated polyols which can be used in the composition of the present invention are preferably chosen from esters of linear or branched, saturated or linear carboxylic acids.

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8/41 unsaturated, with a grease chain that holds for example 8 to 30 carbon atoms.

[0036] In the case of a fatty acid and monoalcohol ester, the latter advantageously has a grease chain comprising, for example, 8 to 30 carbon atoms, linear or branched, saturated or unsaturated, ethoxylated and / or propoxylated or glycerolated. In addition, the number of ethylene oxide or propylene oxide groups of that monoalcohol may be between 1 and 200 and the number of glycerol groups may be between 1 and 30.

[0037] In the case of esters of fatty acids and polyols, the latter can be chosen in particular from glycerin, sorbitol, glucose, methylglucose, sorbitol anhydride, or mixtures thereof. The polyol can also be a polyethylene glycol or a polypropylene glycol.

[0038] In addition, the polyol can be oxyalkylene or glycerol. If this is the case, the number of ethylene oxide and / or propylene oxide groups in this polyol can vary between 1 and 200 and the number of glycerol groups can vary between 1 and 30.

[0039] As examples of these esters, we can mention the compounds classified in the CTFA dictionary, 9th edition, 2002, under the names Steareth-12 stearate, Steareth-15 stearate, PEG-15 Oleate, PEG-20 Palmitate, PEG-6 Isopalmitate, PEG-10 Polyglyceryl-2 Laurate, PEG30 Glyceryl stearate, PEG-32 Dioleate, PEG-30 Dipolyhydroxystearate, PEG-8 Ditallate, PEG-4 Ethylhexanoate, PEG 90 Glyceryl isostearate, PEG 90 20 Methylglucose distearate, PEG-20 Sorbitan cocoate, PPG-17 Dioleate, Methylglucose laurate, Methylglucose dioleate, Sorbitan palmitate, Sorbitan sesquioleate, Sorbitan trioleate.

[0040] The content of amphoteric surfactants and / or nonionic surfactants as just defined represents, more so

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It is advantageous from 0.01% to 30% by weight, more particularly from 0.1% to 20% by weight and preferably from 0.2% to 10% by weight, of the total weight of the composition.

[0041] The composition used in accordance with the present invention further comprises one or more fluorescent dyes.

[0042] Fluorescent dye means, for the purposes of the present invention, a dye that is a molecule that colors by itself, and therefore absorbs light from the visible spectrum and eventually from the ultraviolet (wavelengths ranging from 360 to 760 nanometers) but that, unlike a classic dye, transforms the absorbed energy into fluorescent light of greater wavelength emitted in the visible part of the spectrum.

[0043] The fluorescent dye present in the composition according to the present invention must be distinguished from an optical bleaching agent. Optical whitening agents generally called optical azurants or brighteners, or fluorescent brighteners, or fluorescent brightening agents, or fluorescent whitening agents, or whiteners, or fluorescent whiteners in Anglo-Saxon terminology, are colorless transparent compounds. These compounds do not color, as they do not absorb in visible light, but only in ultraviolet (wavelengths ranging from 200 to 400 nanometers). They transform the energy absorbed into fluorescent light of greater wavelength emitted in the visible part of the spectrum; the color impression is then generated solely by purely fluorescent light with predominantly blue (wavelengths ranging from 400 to 500 nanometers).

[0044] Finally, the fluorescent dye used in the composition is soluble in the middle of the composition. It should be noted that the fluorescent dye is different in this aspect from a fluorescent pigment that is not soluble in the composition.

[0045] More particularly, the fluorescent dye used in

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The present invention, if neutralized, is soluble in the medium of the composition at least 0.001 g / l, more particularly at least 0.5 g / l, preferably at least 1 g / l according to an even further embodiment preferred at least 5 g / l at a temperature between 15 ° C and 25 ° C.

[0046] In addition, according to a characteristic of the present invention, the fluorescent dye that enters the composition according to the present invention does not comprise three condensed cycles of which one is a monocatonic heterocycle comprising two nitrogen atoms.

[0047] Additionally, the composition according to the present invention does not comprise, as a fluorescent dye, a 2- [2- (4dialkylamino) -phenylethyl] -1 alkylpyridinium in which the alkyl radical of the pyridinium nucleus represents a methyl radical, ethyl, the benzene nucleus represents a methyl radical and in which the counterion is a halide.

[0048] According to an even more particular embodiment of the present invention, the composition does not comprise, as a fluorescent dye, a compound chosen from the azoic, azometinic or methyline monocyclic heterocyclic fluorescent dyes.

[0049] The fluorescent dyes preferably used in accordance with the present invention are dyes in the orange range.

[0050] According to a particular embodiment of the present invention, the fluorescent dyes of the present invention lead to a maximum reflectance that lies between the wavelength range ranging from 500 to 650 nanometers, and preferably in the range wavelength ranging from 550 to 620 nanometers.

[0051] Some fluorescent dyes according to the present invention are compounds known per se.

[0052] As examples of fluorescent dyes that can be used, we can mention the fluorescent dyes that

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11/41 belong to the following families: naphthalimides; cationic or non-cationic coumarins; xanthenodiquinolizines (such as sulforodamines in particular); azaxanthenes; naphtholactams; azlactones; oxazins; thiazines; dioxazines; the polycationic fluorescent dyes of the azoic, azometinic, or methylic type, alone or in mixtures, preferably in the following families: naphthalimides; cationic or non-cationic coumarins; azaxanthenes; naphtholactams; azlactones; oxazins; thiazines; dioxazines; the polycationic fluorescent dyes of the azoic, azometinic or methyline type, alone or in mixtures.

[0053] Among the soluble fluorescent dyes of this type, we can notably mention:

the Bright Yellow B6GL sold by Sandoz and which has the following structure:

- Basic Yellow 2, or Auramine O marketed by the companies Prolabo, Aldrich or Cario Erba and which has the following structure:

4,4 '- (imidocarbonyl) -bis- (N, N-dimethylaniline) monohydrochloride Petition 870170094291, dc 12/04/2017, p. 21/59

12/41 CAS number 2465-27-2.

[0054] You can also mention the compounds that have the following formula:

in which Ri, R2, identical or different, represent:

• a hydrogen atom;

• an alkyl radical, linear or branched, comprising 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, optionally interrupted and / or substituted by at least one heteroatom and / or group comprising at least one heteroatom, and / or replaced by at least one halogen atom;

• an aryl or arylalkyl radical, with the aryl group having 6 carbon atoms and the alkyl radical having 1 to 4 carbon atoms; The aryl radical is optionally substituted by one or more linear or branched alkyl radicals comprising 1 to 4 carbon atoms which may be interrupted and / or substituted by at least one heteroatom and / or group comprising at least one heteroatom and / or substituted by minus one atom of hyogen;

• R1 and R2 may eventually be linked to form a heterocycle with 0 nitrogen atom and comprise one or more others

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13/41 heteroatoms, the heterocycle being optionally substituted by at least one linear or branched alkyl radical, which preferably comprises from 1 to 4 carbon atoms and is eventually interrupted and / or substituted by at least one heteroatom and / or group which comprises at least one heteroatom and / or substituted by at least one halogen atom;

• Ri or R2 may possibly be inserted in a heterocycle that comprises the nitrogen atom and one of the carbon atoms of the phenyl group that carries the referred nitrogen atom.

[0055] It should be remembered that the terms hetero atoms represent an atom of oxygen or nitrogen.

[0056] Among the groups carrying such atoms, hydroxyl, alkoxy, carbonyl, amino, ammonium, starch (-NCO-), carboxyl (-O-CO- or -CO-O-) groups can be mentioned, among others. .

[0057] With regard to alkenyl groups, the latter comprise one or more unsaturated carbon-carbon bonds (-C = C-), and preferably a single carbon-carbon double bond.

[0058] In this formula, the radicals Ri and R2, identical or not, represent more particularly:

• a hydrogen atom;

• an alkyl radical comprising 1 to 10 carbon atoms, in particular 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, possibly interrupted by an oxygen atom or possibly replaced by at least one hydroxyl, amino, ammonium, a chlorine or fluorine atom;

• a benzyl, phenyl radical, optionally substituted by an alkyl or alkoxy radical comprising 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms;

• with 0 nitrogen atom, a pyrrole, pyrrolidine,

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14/41 imidazoline, imidazole, imidazolium, pyrazoline, piperazine, morpholine, morphol, pyrazole, triazole, possibly substituted by at least one linear or branched alkyl radical comprising 1 to 4 carbon atoms which may be interrupted and / or replaced by an atom of nitrogen and / or oxygen and / or group that carries a nitrogen and / or oxygen atom.

[0059] With regard to the amino or ammonium radicals in need, the radicals carried by the nitrogen atom may or may not be identical and more particularly represent a hydrogen atom, a C1-C10 alkyl radical, preferably with C1-C4, a aryl radical in which, more especially, the aryl radical comprises 6 carbon atoms and the alkyl radical 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.

[0060] According to an advantageous embodiment of the present invention, the radicals R1 and R2, identical or not, represent a hydrogen atom; a straight or branched C1-C6 alkyl radical; a C2-C6 alkyl radical substituted by a hydroxyl radical; a C2-C6 alkyl radical, which carries an amino or ammonium group; a C2-C6 chloroalkyl radical; a C2-C6 alkyl radical interrupted by an oxygen atom or group that carries one (for example ester); an aromatic radical such as phenyl, benzyl, 4-methylphenyl; a heterocyclic radical such as the pyrrole, pyrrolidine, imidazole, imidazoline, imidazoline, piperazine, morphol, morpholino, pyrazole, triazole radicals, eventually substituted by at least one C1-C6 alkyl or aromatic radical.

Preferably, the radicals R1 and R2, identical or different, represent a hydrogen atom, a linear or branched C1-C6 alkyl radical such as the methyl, ethyl, n-butyl, n-propyl radicals; 2-hydroxyethyl; an alkyltrimethylammonium or alkyltriethylammonium radical, the alkyl radical being linear with C2-C6; a (di) alkylmethylamino or (di) alkylethylamino radical, the alkyl radical being linear with C2-C6; -CH2CH2CI; - (CH2) n-OCH3 or - (CH2) nPetition 870170094291, of 12/04/2017, p. 24/59

15/41

OCH2CH3 where n is an integer ranging from 2 to 6; -CH2CH2OCOCHs; -CH2CH2COOCH3.

[0062] Preferably, the radicals R1 and R2, identical or not, and preferably identical, represent a methyl radical, an ethyl radical.

[0063] The radicals R1 and R2, identical or different, can also represent a heterocyclic radical of the pyrrolidine, 3aminopyrrolidine, 3- (dimethyl) -aminopyrrolidine, 3- (trimethyl) -aminopyrrolidine, 2,5dimethylpyrrole, 0 1 H-imidazole , 4-methylpiperazine, 4-benzylpiperazine, morfol, 3,5 (tert-butyl) -1 H-pyrazole, 1 H-pyrazole, 1H-1,2,4-triazole.

[0064] The radicals R1 and R2, identical or different, can also represent being linked in a way to form a heterocycle of formulas (I) and (II) indicated below:

n \ / ^{N r} '(I) or (ll) in which R' represents a hydrogen atom, a C1-C3 alkyl radical, -CH2CH2OH, -CH2CH2OCH3.

[0065] According to a more particular embodiment of the present invention, Rs, identical or not, represents a hydrogen atom, a fluorine or chlorine atom, a linear or branched alkyl radical comprising 1 to 4 carbon atoms eventually interrupted by an oxygen or nitrogen atom.

[0066] It is necessary that the substituent Rs, if different from hydrogen, is advantageously in position (s) 3 and / or 5 in relation to the carbon of the cycle that carries 0 nitrogen substituted by radicals R1 and R2, and preferably in position 3 with respect to that carbon.

[0067] Advantageously, the radicals Rs, identical or not, represent a hydrogen atom; a straight or branched alkyl radical

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16/41 with C1-C4; where -O-R51 with R51 represents a linear C1C4 alkyl radical; -R52-O-CH3 with R52 represents a linear C2-C3 alkyl radical; -R53 - N (Rõ4) 2 in which R53 represents a linear C2-C3 alkyl radical, where R54, identical or different, represents a hydrogen atom or a methyl radical.

[0068] Preferably Rs, identical or not, represents hydrogen, a methyl, a methoxy, and preferably, Rs represents a hydrogen atom.

[0069] According to a particular embodiment, the radicals R6, identical or different, represent a hydrogen atom; a straight or branched C1-C4 alkyl radical; -X with X representing a chlorine, bromine or fluorine atom; -R61-O-R62 with R61 representing a linear C2-C3 alkyl radical and R62 represents the methyl radical; -R63-N (R64) 2 with R63 representing a C2-C3 linear alkyl radical, R64, identical or different, represent a hydrogen atom or a methyl radical, -N (R6s) 2 in which R65, identical or different, represent a hydrogen atom, a linear C2-C3 alkyl radical; -NHCO R66with R66 representing a C1C2 alkyl radical, a C1-C2 chloroalkyl radical, a -R67-NH2 or -R67-NH (CH3) or R67-N (CH3) 2 or -R67-N ⁺ (CH3) 3 radical or -R67-N ⁺ (CH2CH3) 3 with R67 representing a C1-C2 alkyl radical.

[0070] It is necessary that the substituent R6, if different from hydrogen, is preferably in position 2 and / or 4 in relation to the nitrogen atom of the pyridinium cycle, and preferably in position 4 in relation to that atom of nitrogen.

[0071] More particularly, these radicals R6, identical or not, represent a hydrogen atom or a methyl or ethyl radical, and preferably, R6 represents a hydrogen atom.

[0072] With respect to the radicals R3 and R4, the latter,

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17/41 identical or not, advantageously represent a hydrogen atom, an alkyl radical comprising 1 to 4 carbon atoms, more especially a methyl radical. Preferably, R3 and R4 each represent a hydrogen atom.

[0073] As indicated above, X represents:

• an alkyl, linear or branched radical comprising 1 to 14 carbon atoms, or alkenyl comprising 2 to 14 carbon atoms, which may be interrupted and / or replaced by at least one heteroatom, by at least one group, which bears at least a heteroatom and / or at least one halogen atom;

• a heterocyclic radical comprising 5 or 6 members, optionally substituted by at least one linear or branched alkyl radical comprising 1 to 14 carbon atoms, by at least one aminoalkyl radical, linear or branched, comprising 1 to 4 carbon atoms , eventually replaced by at least one heteroatom and / or at least one halogen atom;

• a condensed or non-condensed aromatic or diaromatic radical, separated or not by an alkyl radical comprising 1 to 4 carbon atoms, the aryl radical (s) being (are) eventually replaced (s) at least one halogen atom or at least one alkyl radical comprising 1 to 10 carbon atoms optionally substituted and / or interrupted by at least one heteroatom and / or group comprising at least one hetero atom;

• a dicarbonyl radical.

[0074] Furthermore, it is indicated that the group X can carry one or more cationic charges.

[0075] Thus X can represent an alkyl radical, linear or branched, comprising 1 to 14 carbon atoms, or alkenyl which

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18/41 comprises 2 to 14 carbon atoms, and can be replaced and / or interrupted by one or more oxygen and / or nitrogen atoms, and / or by one or more groups that carry at least one heteroatom, and / or by an atom of fluorine, chlorine.

[0076] Among the groups of this type, hydroxyl, alkoxy groups (with in particular a R radical of the C 1 -C 4 alkyl type), amino, ammonium, starch, carbonyl, carboxyl (-COO-, -O-CO -) with, in particular, an alkyloxy type radical.

[0077] It should be noted that the nitrogen atom, if present, can be in a quaternized or non-quaternized form. In this case, the two other radicals carried by the quaternized or non-quaternized nitrogen atom, are identical or not and may be a hydrogen atom, a C1-C4 alkyl radical, preferably methyl.

[0078] According to another variant, the group X represents a heterocyclic radical comprising 5 or 6 members, of the imidazole, pyrazole, triazine, pyridine type, optionally substituted by at least one linear or branched alkyl radical comprising 1 to 14 carbon atoms, more particularly 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms; at least one aminoalkyl radical, linear or branched, comprising 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, optionally substituted by a group comprising at least one heteroatom (preferably a hydroxyl radical), or by a halogen atom. It should be noted that the amino group is preferably attached to the heterocycle.

[0079] According to another possibility, the group X represents an aromatic radical (which preferably comprises 6 carbon atoms) or a condensed or non-condensed diarometic (which comprises in particular 10 to 12 carbon atoms), separated or not by a radical

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19/41 alkyl comprising 1 to 4 carbon atoms, the aryl radical (s) being (are) eventually being replaced by at least one halogen atom and / or at least one alkyl radical comprising 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, optionally interrupted by at least one oxygen and / or nitrogen atom, and / or group comprising at least one heteroatom (such as a carbonyl radical , carboxyl, starch, amino, ammonium).

[0080] It should be noted that the aromatic radical, preferably a phenyl radical, is linked to the CR3R4 groups through bonds at positions 1,2; 1.3 or 1.4, preferably in positions 1.3 and 1.4. If the phenyl radical linked via bonds in the 1,4 positions, carries one or two substituents, the latter (s) is (are) preferably located in the 1,4 position in relation to one of the groups CR3R4. If the phenyl radical linked via bonds at positions 1,3, bears one or two substituents, the latter (s) is (are) preferably located in position 1 and / or 3 with respect to a of the CR3R4 groups.

[0081] In the case where the radical is diaromatic, it is preferably non-condensed and comprises two phenyl radicals separated or not by a simple bond (that is, a carbon from each of the two cycles) or by an alkyl radical, preferably of type CH2 or C (CH3) 2. Preferably, the aromatic radicals do not carry a substituent.

[0082] It should be noted that said diaromatic radical is linked to the CR3R4 groups by means of bonds at the 4,4 'positions.

[0083] As examples of appropriate groups X, in particular, linear or branched alkyl radicals comprising 1 to 13 carbon atoms such as methylene, ethylene, propylene, isopropylene, n-butylene, pentylene, hexylene; 0 2-hydroxypropylene, 0 2-hydroxy-n-butylene; C1-C13 alkyl radicals, substituted or interrupted by one or more

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20/41 nitrogen and / or oxygen atoms, and / or groups that carry at least one heteroatom (hydroxyl, amino, ammonium, carbonyl, carboxyl, for example) such as -CH2CH2OCH2CH2-, 0 1,6-dideoxy-d -manitol, -CH2N ⁺ (CH3) 2CH2-, CH2CH2N ⁺ (CH3) 2- (CH2) 6N ⁺ (CH3) 2-CH2CH2-, CO-CO-, 3,3-dimethylpentylene, 0 2-acetoethylene, 0 butylene-1,2,3,4-tetraol; -CH = CH-; aromatic or diaromatic radicals substituted by one or more alkyl radicals, by one or more groups that carry at least one heteroatom and / or by one or more halogen atoms, such as 0 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 2,6fluorobenzene, 4,4'-biphenylene, 1,3- (5-methylbenzene), 1,2-bis- (2-methoxy) benzene, bis- (4-phenyl) -methane, Methyl 3,4-benzoate, 1,4-bis (amidomethyl) -phenyl; radicals of the heterocyclic type such as pyridine, or derivative such as 2,6-bispyridine, imidazole, imidazole, triazine.

[0084] X represents, according to a more particular embodiment of the present invention, a linear or branched C1C13 alkyl radical; -CH ₂ CH (OH) CH2-; -CH ₂ CH (CI) CH2-; -CH2CH2-OCOCH2-; CH2CH2COOCH2-; -Ra-O- Rb- with Ra representing a C2-C6 linear alkyl radical and Rb represents a C1-C2 linear alkyl radical; -RcN (Rd) -Re- with Rc representing a C2-C9 alkyl radical, Rd representing a hydrogen atom, a C1-C2 alkyl radical and Re representing a C1-C6 alkyl radical; -Rf-N ⁺ (Rg) 2-Rh- with Rf representing a linear alkyl radical C2-C9, Rg, preferably identical, represent a alkyl radical C1-C2, Rh represents a linear alkyl radical G1-G6; -GO-GO-.

[0085] X may also represent an imidazole radical, optionally substituted by at least one alkyl radical comprising 1 to 14 carbon atoms, more particularly 1 to 10 carbon atoms, preferably 1 to 4, and for example the divalent radicals with the

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21/41 following formula:

in which Ri and Rj, identical or not, represent a linear C1-C6 alkyl radical;

X can also be chosen from the following triazine-derived bivalent radicals:

CH,

CH,

ΗΝχ ^ Ν NH

II I

N ^ N

OH

CH, CH, ¹ k, ¹

HN ^ N NH

II I

ΝγΝ nh ₂

CH, CH,

I ² I ²

HN ^ .N. ^. NH

I

ΝγΝ ho ^ - ' ⁿ jjCH ₂ ) ₂ (CH ₂ ) ₂ HN..N. NH

YY

N ^ N

OH _| (CH ₂ ) ₂ JCHsh ^HN ^ ^N ^ ^NH TT

N ^ N

NH ₂ [CH ₂ ) ₂ [CH ₂ ) ₂

Ύ I

ΝγΝ

ΗΟ ' ^{ΧΧχ / Ν} ' ^{χ /} ^ ΟΗ _| (CH ₂ ) ₃ jCH ₂ ) ₃ ^HN x / ^N \ x ^NH

II Ί N ^ N

OH, (CH ₂ ) ₃ (ΟΗ ₂ ) ₃

HNx ^ N ^ NH

II I

ΝγΝ nh ₂ pH ₂ ) ₃ j [CH ₂ ) ₃ ^HN x ^ ^N <^ NH

I T

N ^ N ^ N „

HO

ΌΚ

ΌΚ

[0086] According to another possibility, X can represent the following aromatic divalent radicals:

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22/41

CONH

I (CH ₂ ) ₂

CONH. / x .NHCO-CH, »= V

NHCO- (CH ₂ ) ₂ CONH I (CH ₂ ) ₃

CONH I (CH ₂ ) ₃

NHCO.

(CH ₂ ) ₃

NHCO (CH ₂ ) ₃

NHCO— (CH ₂ ) ₃

NHCO- (CH ₂ ) ₃

CONH- (CH ₂ ) ₃

CONH- (CH ₂ ) ₃ [0087] In the general formula of these fluorescent compounds, Y represents an organic or inorganic anion. If there are several Y- anions, the latter may or may not be identical.

[0088] Among anions of inorganic origin, one can mention without limitation, anions from halogen atoms, such as preferably chlorides, iodides, sulfates or bisulfates, nitrates, phosphates, hydrogen phosphates, dihydrogen phosphates, carbonates, bicarbonates.

[0089] Among anions of organic origin, one can mention anions from salts of mono- or polycarboxylic, sulfonic, sulfuric, saturated or unsaturated, aromatic or non-aromatic acids, eventually replaced by at least one hydroxyl radical, amino , or halogen atoms. Non-limiting examples include acetates, hydroxyacetates, aminoacets, (tri) chloroacetates, benzoxyacetates, propionates and derivatives that carry a chlorine atom, fumarates, oxalates, acrylates, malonates, succinates, lactates, tartrates, glycolates, citrates, benzoates and derivatives that carry a methyl or amino radical, alkyl sulfates, tosylates, benzenesulfonates, toluenesulfonates, etc.

[0090] Preferably, the anion (s) Y, identical or not, is (are) chosen (s) among the chlorine, sulfate, methosulfate, ethosulfate.

[0091] Finally, the number n, integer, is at least equal to 2 and at most equal to the number of cationic charges present in the compound

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Fluorescent 23/41.

[0092] Preferably the fluorescent compounds that have just been described are symmetrical compounds.

[0093] These compounds can be synthesized by reacting in a first step α-picoline with a reagent comprising two starting groups that can be chosen from halogen atoms, preferably bromine, possibly chlorine, or groups tolylsulfonyl or methylsulfonyl type.

[0094] This first step can occur in the presence of a solvent, although it is not mandatory, such as dimethylformamide.

[0095] The number of moles of α-picoline is generally close to 2 for one mole of reagent comprising the starting groups.

[0096] In addition, the reaction is usually carried out at reflux of the reagent and / or the solvent if it is present.

[0097] The product from this first stage is then placed in contact with a corresponding aldehyde that has the following formula:

Laugh

OHC

/ in which Ri, R2 and R6 have the same meanings indicated above.

[0098] Also, the reaction can be carried out in the presence of an appropriate solvent, preferably at reflux.

[0099] It should be noted that the radicals R1 and R2 of the aldehyde may have the meaning indicated in the general formula detailed above.

[0100] It is also possible to use an aldehyde in which these radicals represent hydrogen atoms and carry out according to methods

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24/41 classics, the replacement of these hydrogen atoms by appropriate radicals as described in the general formula, once the second stage is finished.

[0101] One can in particular refer to the syntheses as described in US 4,256,458.

[0102] It should be clarified that according to a particular embodiment of the present invention, the composition does not comprise, as a fluorescent dye, a compound comprising three condensed aromatic nuclei, one of which comprises an oxygen atom.

[0103] The fluorescent dye (s) of the present invention generally represent 0.01% to 20% by weight, more particularly 0.05% to 10% by weight, and preferably from 0.1% to 5% by weight, of the total weight of the composition.

[0104] The cosmetically acceptable medium is generally made up of water or a mixture of water and at least one organic solvent.

[0105] Among the appropriate solvents, mention may be made more particularly of alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, and phenyl ethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl ethers, monoethyl and monobutyl ethylene glycol, propylene glycol or their ethers such as, for example, propylene glycol monomethyl, butylene glycol, dipropylene glycol as well as diethylene glycol alkyl ethers, such as diethylene glycol monoethylene or monoethylene glycol . Polyethylene glycols and polypropylene glycols and mixtures of all these compounds can also be used as a solvent.

[0106] The solvents can be present in proportions that generally vary from 1% to 40% by weight, and preferably from 5% to 30% by weight, in relation to the total weight of the composition.

[0107] The pH of the composition is generally between

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25/41 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value using acidifying or alkalizing agents.

[0108] Among acidifying agents, one can mention, for example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid , sulfonic acids.

[0109] Among the alkalizing agents can be mentioned, for example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium hydroxides or potassium hydroxide and the compounds of formula (A) indicated below:

R,

N-W-N (A) in which W is a propylene residue optionally substituted by a hydroxyl group or a C1-C6 alkyl radical; R1, R2, R3 and R4, identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or C1-C6 hydroxyalkyl radical.

[0110] The composition used in the present invention may, according to a preferred embodiment, and in addition to the fluorescent dye (s), comprise one or more additional non-fluorescent direct dyes of a non-ionic nature, cationic or anionic.

[0111] These additional direct dyes can, for example, be chosen from the nitrated benzene dyes, and more particularly from the red or orange nitrated benzene dyes indicated below:

- 0 1-hydroxy-3-nitro-4-N- (Y-hydroxypropyl) -aminobenzene,

- 0 N- (3-hydroxyethyl) -amino-3-nitro-4-aminobenzene,

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26/41

- 1-amino-3-methyl-4-N- (P-hydroxyethyl) -amino-6-nitrobenzene,

- ο 1-hydroxy-3-nitro-4-N- (P-hydroxyethyl) -aminobenzene,

- ο 1,4-diamino-2-nitrobenzene,

- ο 1-amino-2-nitro-4-methylaminobenzene,

- N- (P-hydroxyethyl) -2-nitro-para-phenylenediamine,

- 1-amino-2-nitro-4- (P-hydroxyethyl) -amino-5-chlorobenzene,

- 2-nitro-4-amino-diphenylamine,

- 1-amino-3-nitro-6-hydroxybenzene.

- 1- (P-aminoethyl) -amino-2-nitro-4- (P-hydroxyethyloxy) -benzene,

- o 1 - (P, Y-dihydroxypropyl) -oxy-3-nitro-4- (P-hydroxyethyl) -aminobenzene,

- 1-hydroxy-3-nitro-4-aminobenzene,

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

- 1-methoxy-3-nitro-4- (P-hydroxyethyl) -aminobenzene,

- 2-nitro-4'-hydroxydiphenylamine,

- 1-amino-2-nitro-4-hydroxy-5-methylbenzene.

[0112] The composition usable according to the present invention can also comprise, in addition or replacement of these nitrated benzene dyes, one or more additional direct dyes chosen from the benzene dyes nitrated, yellow, greenish yellow, blue or violet, azo dyes , anthraquinone, naphthoquinone or benzoquinone dyes, indigo dyes, or dyes derived from triarylmethane.

[0113] These additional direct dyes can be in particular basic dyes, among which the dyes known in COLOR INDEX, 3 ^S edition, with the names of Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Red can be mentioned 76, Basic Violet 10, Basic Blue 26 and Basic Blue 99, or direct acid dyes among which dyes can be mentioned more particularly

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27/41 known in COLOR INDEX, 3 ^S edition, with the names “Acid Orange 7, Acid Orange 24, Acid Yellow 36,“ Acid Red 33, Acid Red 184, Acid Black 2, Acid Violet 43, and Acid Blue 62 , or even cationic direct dyes such as those described in WO 95/01772, WO 95/15144 and EP-A0.714.954 and whose content forms an integral part of the present invention.

[0114] Among the additional yellow and greenish yellow nitrate benzene direct dyes, for example, the compounds chosen may be mentioned among:

- 1-3-hydroxyethyloxy-3-methylamino-4-nitrobenzene,

- 1-methylamino-2-nitro-5- (3, Y-dihydroxypropyl) -oxybenzene,

- 1 - (3-hydroxyethyl) -amino-2-methoxy-4-nitrobenzene,

- 1- (3-aminoethyl) -amino-2-nitro-5-methoxybenzene,

- 1,3-di- (3-hydroxyethyl) -amino-4-nitro-6-chlorobenzene,

- 1-amino-2-nitro-6-methylbenzene,

- 1- (3-hydroxyethyl) -amino-2-hydroxy-4-nitrobenzene,

- N- (3-hydroxyethyl) -2-nitro-4-trifluoromethylaniline,

- 4- (3-hydroxyethyl) -amino-3-nitrobenzenesulfonic acid,

- 4-ethylamino-3-nitrobenzoic acid,

- 4- (3-hydroxyethyl) -amino-3-nitro-chlorobenzene,

- 4- (3-hydroxyethyl) -amino-3-nitromethylbenzene,

- 4- (3, Y-dihydroxypropyl) -amino-3-nitro-trifluoromethylbenzene,

- 1- (3-ureidoethyl) -amino-4-nitrobenzene,

- 1,3-diamino-4-nitrobenzene,

- 1-hydroxy-2-amino-5-nitrobenzene,

- 1-amino-2- [tris- (hydroxymethyl) -methyl] -amino-5-nitrobenzene,

- 1- (3-hydroxyethyl) -amino-2-nitrobenzene,

- 4- (3-hydroxyethyl) -amino-3-nitrobenzamide.

[0115] Among the additional benzene-containing direct dyes

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28/41 blue or violet, we can mention for example the compounds chosen among:

- 1- (β-hydroxyethyl) -amino-4-N, N-bis- (β-hydroxyethyl) -amino-2-nitrobenzene,

- 1- (γ-hydroxypropyl) -amino-4-N, N-bis- (β-hydroxyethyl) -amino-2-nitrobenzene,

- 1- (β-hydroxyethyl) -amino-4- (N-methyl, Ν-β-hydroxyethyl) -amino-2-nitrobenzene,

- 1- (β-hydroxyethyl) -amino-4- (N-ethyl, Ν-β-hydroxyethyl) -amino-2-nitrobenzene,

- o 1 - ^, Y-dihydroxypropyl) -amino-4- (N-ethyl, N-hydroxyethyl) -amino-2-nitrobenzene,

- the 2-nitro-para-phenylenediamines of the formula shown below:

NHR ₅

NO2

NRgR?

in which:

- R6 represents a C1-C4 alkyl radical, a β-hydroxyethyl, β-hydroxypropyl or γ-hydroxypropyl radical;

- Rs and R7, identical or different, represent a βhydroxyethyl, -β-hydroxypropyl, γ-hydroxypropyl, or β, γ-dihydroxypropyl radical, with at least one of the radicals Re, R7 or Rs representing an γhydroxypropyl and R6 and R7 they cannot simultaneously designate a βhydroxyethyl radical when R6 is a γ-hydroxypropyl radical, such as those described in patent FR 2,692,572.

[0116] When present, the additional direct coloring (s) represents (s) more especially from 0.0005% to 12% by weight,

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29/41 preferably from 0.005% to 6% by weight, of the total weight of the composition.

[0117] When intended for the oxidation dye, the composition comprises, in addition to the fluorescent dye (s), at least one oxidation base chosen from the oxidation bases classically used for the oxidation dye and among which can be mentioned, in particular, paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, orthoaminophenols and heterocyclic bases and their addition salts with an acid or an alkaline agent.

[0118] Among the para-phenylenediamines, we can mention more particularly by way of example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-paraphenylenediamine, 2,6 -dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, Ν, Ν-diethyl-para-phenylenediamine, to N, N-dipropyl-paraphenylenediamine, to 4-amino-N, N-diethyl-3-methylaniline, to N, N-bis- (P-hydroxyethyl) para-phenylenediamine, to 4-N, N-bis- (P-hydroxyethyl ) -amino-2-methylaniline, 4-N, Nbis- (P-hydroxyethyl) -amino-2-chloroaniline, 2-p-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, a 2-isopropyl-para-phenylenediamine, Ν- (βhydroxypropyl) -para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, to N, N-dimethyl-3-methyl-para-phenylenediamine, to N, N- (ethyl , p-hydroxyethyl) -paraphenylenediamine, N - ^, Y-dihydroxypropyl) -para-phenylenediamine, N- (4'aminophenyl) -para-phenylenediamine, N-phenyl-para-phenylen odiamine, 2-βhydroxyethyloxy-para-phenylenediamine, 2-acetylaminoethyloxy-para-phenylene diamine, N - $ - methoxyethyl) -para-phenylenediamine and 4'-aminophenyl-1- (3-hydroxy) pyrrolidine, and their addition salts with an acid or an alkaline agent.

[0119] Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluylenediamine, 2isopropyl-para-phenylenediamine, 2-hydroxyethyl-para-phenylenediamine, 2-βPetition 870170094291, of 04/4 are particularly preferred. 12/2017, p. 39/59

30/41 hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (Phidroxietil) -para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-βacetylaminoethyloxy-para-phenylenediamine, and their addition salts with an acid or an alkaline agent.

[0120] Among bis-phenylalkylenediamines, one can mention more particularly by way of example, N, N'-bis- (P-hydroxyethyl) -N, N'-bis- (4'aminophenyl) -1,3 -diaminopropanol, to N, N'-bis- (P-hydroxyethyl) -N, N'-bis- (4'aminophenyl) -ethylenediamine, to N, N'-bis- (4-aminophenyl) -tetramethylenediamine, to N , N'-bis- (P-hydroxyethyl) -N, N'-bis- (4-aminophenyl) -tetramethylenediamine, to N, N'-bis (4-methylaminophenyl) -tetramethylenediamine, to N, N'-bis- (ethyl) -N, N'-bis- (4'-amino, 3'methylphenyl) -ethylenediamine, 1,8-bis- (2,5-diaminophenoxy) -3,5-dioxaoctane, and their addition salts with an acid or an alkaline agent.

[0121] Among para-aminophenols, more particularly by way of example, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3- hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2aminomethylphenol, 4-amino-2- (p-hydroxyethylaminomethyl) -phenol , 4-amino-2-fluorophenol, and their addition salts with an acid or an alkaline agent.

[0122] Among the ortho-aminophenols, more particularly, for example, 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6methylphenol, 5-acetamido-2-aminophenol, and their addition salts with an acid or an alkaline agent.

[0123] Among the heterocyclic bases, one can more particularly mention, by way of example, the pyridine derivatives, the pyrimidine derivatives and the pyrazolic derivatives and their addition salts with an acid or an alkaline agent.

[0124] When used, the oxidation base (s)

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31/41 represents (m) more particularly from 0.0005% to 12% by weight, preferably from 0.005% to 6% by weight, of the total weight of the composition.

[0125] When used for oxidation dyeing, the composition may also comprise, in addition to fluorescent dyes and oxidation bases, at least one coupler in order to modify or enrich the shades obtained using fluorescent dyes and reflections. the oxidation base (s).

[0126] The couplers usable in the composition can be chosen from the couplers used in a classic way in oxidation dye and among which we can mention in particular the mefa-phenylenediamines, the mefa-aminophenols, the mefa-diphenols and the heterocyclic couplers and their addition salts with an acid or an alkaline agent.

[0127] These couplers are more particularly chosen from 2-methyl-5-aminophenol, 5-N- (3-hydroxyethyl) -amino-2-methylphenol, 3aminophenol, 1,3-dihydroxybenzene, 1,3 -dihydroxy-2-methylbenzene, 4-chloro1,3-dihydroxybenzene, 2,4-diamino-1- (3-hydroxyethyloxy) -benzene, 2-amino-4 (3-hydroxyethylamino) -1-methoxybenzene, o 1,3-diaminobenzene, 1,3-bis- (2,4-diaminophenoxy) -propane, sesamol, a-naphthol, 6-hydroxy-indole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxy-indoline, 2,6-dihydroxy-4-methylpyridine, 1 H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazole- [1,5 -b] -1,2,4-triazole, 2,6-dimethyl- [3,2-c] -1,2,4-triazole, 6methylpyrazole- [1,5-a] -benzimidazole, and their addition salts with an acid or an alkaline agent.

[0128] When present, the coupler (s) advantageously represents 0.0001% to 10% by weight, preferably 0.005% to 5% by weight, of the total weight of the composition.

[0129] In general, the addition salts with an acid, usable in the compositions (oxidation bases and couplers) are chosen

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32/41 in particular among hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, tosylates, benzenesulphonates, lactates and acetates.

[0130] Usable addition salts with an alkaline agent (oxidation bases and couplers) are chosen in particular from the addition salts with alkali or alkaline earth metals, with ammonia, with organic amines such as alkanolamines and the compounds of formula (A).

[0131] The composition can also comprise various adjuvants used, such as anionic, cationic, non-ionic, amphoteric, zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, cations, cationic or amphoteric polymers, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, stabilizing agents, opacifying agents.

[0132] Among the thickeners, it is more particularly preferred to use thickener systems based on associative polymers well known to the person skilled in the art and in particular non-ionic, anionic, cationic or amphoteric in nature.

[0133] Obviously, the person skilled in the art will take every care to choose that eventual complementary compound (s) in such a way that the advantageous properties intrinsically linked to the composition are not, or are not substantially, altered by the addition (s) considered.

[0134] Finally, the composition used according to the present invention, can be presented in various forms, such as in the form of liquids, shampoos, creams, gels, or in any other appropriate form.

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33/41 [0135] According to a preferred embodiment, the composition is in the form of a coloring and bleaching shampoo.

[0136] In the composition, when one or more oxidation bases are used, possibly in the presence of one or more couplers, or when the fluorescent dye (s) is used in a dye direct bleaching agent, then the composition may still contain at least one oxidizing agent, chosen for example from hydrogen peroxide, urea peroxide, alkali metal bromates, persals such as perborates and persulfates, and enzymes such as peroxidases and oxidoreductases with two or four electrons.

[0137] The use of hydrogen peroxide or enzymes is particularly preferred.

[0138] The composition just described is, therefore, used to color human keratinous materials with a lightening effect.

[0139] It should be remembered that human keratin substances include skin, hair, nails, eyelashes, and eyebrows, and more particularly dark skin and pigmented or artificially colored hair.

[0140] For the purposes of the present invention, dark skin is defined as a skin whose luminance L * measured in the C.I.E.L. L * a * b * is less than or equal to 45 and preferably less than or equal to 40, knowing that L * = 0 is equivalent to black and L * = 100 to white. The types of skin that correspond to this luminance are African skin, African-American skin, Hispanic-American skin, Indian skin and Maghreb skin.

[0141] In addition, the present invention is particularly suitable for the treatment of hair, pigmented or artificially colored, the shade of which is less than or equal to 6 (dark blond), and preferably less than or equal to 4 (brown).

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34/41 [0142] In what follows, the term hair will be used interchangeably both for hair and for the hair system (eyelashes, eyebrows, etc.).

[0143] The lightening of the hair is evaluated by the “tonality” that characterizes the degree or the level of lightening. The notion of “tone” rests on the classification of natural tones, with a tone separating each tone from the one that follows or immediately precedes it. This definition and the classification of natural shades are well known to hairdressers and was published in Charles ZVIAK 1988's “Sciences des traitements capillaires”, Ed. Masson, p. 215 and 278.

[0144] The shades vary from 1 (black) to 10 (light blond), and one unit corresponds to a tone; the higher the value, the clearer the hue.

[0145] A coloring process with hair lightening effect represents another object of the present invention.

[0146] It consists of a first step in applying to the hair a composition that comprises at least fluorescent dye and at least one amphoteric and / or non-ionic surfactant, for a time sufficient to reveal the desired color and lightening. Then, eventually, in a second stage, the hair is eventually rinsed. You can eventually wash your hair with shampoo, then rinse it. Finally, in a last step, the hair is dried or allowed to dry.

[0147] Thus, the process according to the present invention may consist of applying the composition for the time necessary for the development of coloring and lightening, and then letting the hair dry or dry the hair, without final rinse.

[0148] According to a first variant, the process of

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35/41 hair dyeing and lightening is carried out with a composition as defined above, in the absence of oxidation dyes and oxidizing agents.

[0149] According to a second variant, the process is carried out with a composition as defined above, in the absence of oxidation dyes but in the presence of oxidizing agents.

[0150] According to a third variant of the dyeing process according to the present invention, the dyeing process comprises a preliminary step which consists of storing separately, on the one hand, a composition comprising, in a cosmetically acceptable medium, at at least one fluorescent dye and at least one amphoteric and / or non-ionic surfactant, as defined above, and on the other hand, a composition comprising, in a cosmetically acceptable medium, at least one oxidizing agent, and then proceed to its mixture at the time of use before applying this mixture on the hair for a sufficient time to reveal the desired color and lightening, after which the hair is rinsed, washed with shampoo, rinsed again and dried.

[0151] Another object of the present invention is an oxidation dyeing process using a composition as previously defined in the presence of oxidation dyes.

[0152] According to this embodiment, the dyeing process comprises a preliminary step which consists of storing separately, on the one hand, a composition comprising, in a cosmetically acceptable medium, at least one fluorescent dye and at least one surfactant as defined above and at least one oxidation base and, on the other hand, a composition that comprises, in a cosmetically acceptable medium, at least one oxidizing agent, and to mix them in the

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36/41 moment of use before applying this mixture on the hair for a sufficient time to reveal the desired color, and after that, the hair is rinsed, washed with shampoo, rinsed again and dried.

[0153] Another object of the present invention is a device with several compartments for dyeing and lightening hair, comprising at least one compartment containing a composition comprising at least one fluorescent dye and at least one surfactant as defined above, and at least one other compartment containing a composition comprising at least one oxidizing agent. This device can be equipped with a means that allows the desired mixture to be applied to the hair, such as the devices described in the patent FR 2,586,913.

[0154] The time required to develop color and obtain the lightening effect on the hair is approximately 5 to 60 minutes and more particularly approximately 5 to 40 minutes.

[0155] The temperature required for the development of color and the achievement of the lightening effect on the hair is generally between ambient temperature (15 ^S C to 25 ° C) and 80 ° C and more particularly between 15 ^S C and 40 ° C .

[0156] Another object of the present invention is the use of a composition that comprises in a cosmetically acceptable medium, at least one fluorescent dye soluble in the medium and at least one amphoteric surfactant chosen from betaines and imidazole derivatives and / or at least one non-ionic surfactant chosen from alkylpyrrolidones, oxyalkylenated or glycerolated fatty alcohol ethers, oxyalkylenated or glycerolated monoalcoholic fatty acid esters, and possibly oxyalkylenated or fatty acid esters

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37/41 glycerolates, to color human keratin substances with a lightening effect.

[0157] According to this use, the fluorescent compound can be chosen from the fluorescent compounds that belong to the following families: naphthalimides; cationic or non-cationic coumarins; xanthenodiquinolizines (such as sulforodamines in particular); azaxanthenes; naphtholactams; azalactones; oxazins; thiazines; dioxazines; the fluorescents monocatonic and polycationic of the azoic, azometinic or methyline type, alone or in mixtures.

[0158] For more particular compounds, we can mention the compounds of formulas F1, F2 and F3 already detailed above.

[0159] You can also use the following compounds of structure (F4):

formula in which R represents a methyl or ethyl radical; R 'represents a methyl radical, X' an anion of the chloride, iodide, sulfate, methosulfate, acetate, perchlorate type. As an example of such a compound, the Photosensitiving Dye NK-557 marketed by Ubichem can be mentioned, in which R represents an ethyl radical, R 'a methyl radical and X' an iodide.

[0160] Everything described above about the natures and contents of the various additives present in the composition remains valid and will not be taken up in this part.

[0161] The present invention makes it possible to obtain treated keratin materials, and in a particularly advantageous way, pigmented or artificially colored hair that has a reflectance in the range of

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38/41 wavelengths ranging from 500 to 700 nanometers, preferably from 540 to 700 nanometers, greater than the reflectance of the same keratinous materials not treated according to the present invention.

[0162] This means that, in the wavelength range ranging from 500 to 700 nanometers, and preferably from 540 to 700 nanometers, there is at least one range in which the reflectance curve corresponding to the treated materials, and more particularly the hair, is higher than the reflectance curve corresponding to untreated materials. “Superior” means a deviation of at least 0.05% reflectance, and preferably at least 0.1%.

[0163] It is necessary, however, that it can exist in the wavelength range that varies from 500 to 700 nanometers, and preferably from 540 to 700 nanometers, one or more bands in which the reflectance curve corresponding to the treated materials is superimposed , or less than the reflectance curve corresponding to the untreated material.

[0164] Preferably, the wavelength over which the deviation is maximum between the reflectance curve of treated and untreated materials, lies in the wavelength range ranging from 500 to 650 nanometers, and preferably in the wavelength range ranging from 550 to 620 nanometers.

[0165] Preferably, the lightening effect is at least

0.5 ton.

[0166] Furthermore, and preferably, the use of the compositions according to the present invention allows to lighten the hair and skin in a shade that, measured in the C.I.E.L. L * a * b *, presents a variable b * greater than or equal to 6, with a ratio b * / absolute value of a *, greater than 1.2 according to the selection test described below.

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39/41

Selection test [0167] The composition is applied to brown hair at a rate of 10 grams of composition to 1 gram of brown hair. The composition is spread to cover all hair. The composition is left to act for 20 minutes at room temperature (20 ^s C to 25 ° C). The hair is then rinsed with water and then washed with a shampoo based on lauryl sulfate. Then they are dried. The spectrocolorimetric characteristics of the hair are then measured to determine the coordinates L * a * b *.

[0168] In CIEL L * a * b *, a * and b * indicate two color axes, a * indicates the green / red color axis (+ a * is red, -a * is green) and b * the axis blue / yellow (+ b * is yellow and -b * is blue); values close to zero for a * and b * correspond to gray tones.

[0169] The following examples are intended to illustrate the present invention without, however, limiting its scope.

Examples

Example 1 [0170] The following two compositions were prepared:

Composition 1 2 Fluorescent Dye NK-557 0.5% 0.5% N-cocoylamidoethyl-N-ethoxycarboxymethylglycinate sodium (Rhodia Chimie; Miranol C 2M Cone. NP) - 2% M.A. Distilled water q.s.p 100% q.s.p 100%

[0171] Composition 2 is part of the present invention while composition 1 serves as a reference.

[0172] Each of the compositions is applied on natural brown hair (shade 4) for 20 minutes at room temperature.

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40/41 [0173] The bath ratio is fixed at 5.

[0174] At the end, the strands are rinsed and dried.

[0175] The strands are read on the Varian Cary spectrofluorimeter

Eclipse equipped with an optical fiber (excitation 480 nm, emission 580 nm, bandwidth 5 nm).

[0176] 8 measurements are made along the lock.

[0177] The results are shown below:

Untreated HT4 hair HT4 hair + composition 1 HT4 hair + composition 2 Measuring 1 0.26 55.24 59.68 Measuring 2 0.17 46.69 61.43 3 ^the measurement 0.26 50.35 58.05 4 ^the measurement 0.25 51.47 59.98 5 ^the measurement 0.34 52.77 57.32 6 ^the measurement 0.29 44.61 60.52 7 ^the measurement 0.29 44.32 59.77 8 ^the measurement 0.37 46.68 54.75 Average 0.28 49.01 58.94 Standard deviation 0.06 4.02 2.14 Confidence interval (5%) 0.04 2.78 1.48

[0178] It is found, therefore, that the composition of the present invention leads to greater fluorescence.

Example 2

Fluorescent Compound

[0179] 93 g of 2-picoline are reacted with 120 g of 1.6Petition 870170094291, of 04/12/2017, pg. 50/59

41/41 dibromohexane in dimethylformamide at 110 ° C for 5 hours.

[0180] The precipitated product is recovered and filtered.

[0181] 109 g of the product obtained previously are solubilized in methanol and 82.82 g of p-dimethylaminobenzaldehyde are added twice, in the presence of pyrrolidine.

[0182] It is then left for 30 minutes.

[0183] The product is recovered in a precipitated form.

[0184] Analysis by mass spectroscopy: 266.

[0185] Elemental analysis: C: 62.43%; H: 6.40%; Br: 23.07%; N:

8.09%.

[0186] The formula is as follows C36H44N4.2Br.

Composition [0187] The following composition was prepared:

Fluorescent compound 0.6% Sodium N-cocoylamidoethyl-N-ethoxycarboxymethylglycinate 2% Hexylene glycol 7% Distilled water q.s.p 100 g

[0188] The percentages are expressed in weight of active matter.

Coloring [0189] The composition is applied to a lock of natural brown hair (shade 4) with a resting time of 20 minutes.

[0190] Then, the strands are rinsed and dried under a helmet for 30 minutes.

[0191] A clear whitening effect is obtained for the strands treated in this way.

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1/7

Claims (35)

Claims 1. USE OF A COMPOSITION, characterized by the fact that it is used to color the human dark skin or artificially colored or pigmented human keratin fibers, with the said composition comprising, in a cosmetically acceptable medium, a fluorescent dye soluble in the medium , in which said fluorescent dye is in the orange range and chosen from among the fluorescent dyes belonging to the following families: naphthalimides; cationic or non-cationic coumarins; xanthenodiquinolizines; azaxanthenes; naphtholactams; azalactones; oxazins; thiazines; dioxazines; the monocyonic or polycationic fluorescent dyes of the azoic, azometinic, or methenic type, alone or in mixtures, and an amphoteric surfactant chosen from betaines and imidazole derivatives and / or a nonionic surfactant chosen from alkylpyrrolidones, alcohol ethers glycerolated fatty and fatty acid esters of glycerolated monoalcohols, in the absence of oxidation dyes and oxidizing agents. 2. USE, according to claim 1, characterized by the fact that said fibers have a shade less than or equal to 6, and preferably less than or equal to 4. USE, according to any one of claims 1 to 2, characterized by the fact of coloring the hair with a lightening effect of at least 0.5 ton. USE, according to any one of claims 1 to 3, characterized by the fact that betaine-type amphoteric surfactants are chosen from alkyl (C8-C2o) -betaines, alkyl (C8-C2o) -amidoalkyl (CiCe) -betaine, alkyl (C8-C2o) -amidoalkyl ( C1-C8) -sulfobetaines, sulfobetaines or their mixtures. USE, according to any one of claims 1 to Petition 870170094291, of 12/04/2017, p. 52/59 2/7 3, characterized by the fact that imidazolium derivatives are chosen from amphocarboxyglycinates and amphocarboxypropionates, or mixtures thereof. 6. USE, according to any one of claims 1 to 3, characterized in that the nonionic alkylpyrrolidones are alkyl (C1 C3) -pyrrolidones. 7. USE, according to any one of claims 1 to 3, characterized in that the glycerolated fatty alcohol ethers are chosen from any hydroxylated, linear or branched, saturated or unsaturated, glycerolated fatty alcohols, with a chain comprising 8 to 30 carbon atoms. 8. USE, according to any one of claims 1 to 3, characterized in that the esters of fatty acids and glycerolated monoalcohols are chosen from esters of carboxylic acids, linear or branched, saturated or unsaturated, with a grease chain that holds 8 to 30 carbon atoms and one or more monoalcohols with a grease chain that holds 8 to 30 carbon atoms, linear or branched, saturated or unsaturated, glycerolated. 9. USE, according to any one of claims 1 to 8, characterized by the fact that the amphoteric surfactant (s) and / or nonionic surfactant (s) represent (s) from 0.01% to 30% by weight, more particularly from 0 , 1% to 20% by weight and preferably 0.2% to 10% by weight of the total weight of the composition. 10. USE, according to any one of claims 1 to 9, characterized in that the fluorescent dye, eventually neutralized, is soluble in the cosmetically acceptable medium at 0.001 g / l, more particularly at 0.5 g / l, preferably at 1 g / l according to an yet further embodiment more preferred, at 5 g / l, at a temperature between 15 ° C and 25 ° C. Petition 870170094291, of 12/04/2017, p. 53/59 3/7 11. USE, according to any one of claims 1 to 10, characterized by the fact that the fluorescent dye leads to a maximum reflectance that is in the wavelength range ranging from 500 to 650 nanometers, and preferably in the wavelength range ranging from 550 to 620 nanometers. 12. USE, according to any one of claims 1 to 11, characterized by the fact that the fluorescent dye is chosen from the group formed by the dyes that have the following structures: (F2) (F1) 13. USE, according to any one of claims 1 to 12, characterized by the fact that the fluorescent dye (s) is present in a weight concentration ranging from 0.01% to 20% by weight, more particularly 0.05% to 10% by weight, preferably from 0.1% to 5% by weight, based on the total weight of the composition. 14. USE, according to any one of claims 1 to 13, characterized by the fact that the composition also includes additional non-fluorescent direct dye of a nonionic, cationic or anionic nature. 15. USE, according to claim 14, characterized by Petition 870170094291, dc 12/04/2017, p. 54/59 4/7 the fact that additional direct dyes are chosen from nitrated benzene dyes, azo dyes, anthraquinone, naphthoquinone or benzoquinone dyes, indigo dyes, or dyes derived from triarylmethane, or mixtures thereof. 16. USE, according to any one of claims 14 to 15, characterized by the fact that the additional direct coloring (s) represent (s) from 0.0005% to 12% by weight, preferably from 0.005% to 6% by weight, in relation to the total weight of the composition. 17. USE, according to any one of claims 1 to 16, characterized by the fact that the composition is in the form of a whitening and coloring shampoo. 18. USE, according to any one of claims 1 to 17, characterized by the fact that the following steps are performed: a) the composition comprising a fluorescent dye and an amphoteric and / or non-ionic surfactant is applied over the keratin fibers, for a time sufficient to reveal the desired color and lightening, b) the said fibers are eventually rinsed, c) eventually, said fibers are washed with shampoo and rinsed, d) the fibers are dried or allowed to dry. 19. USE, according to any one of claims 1 to 15, characterized by the fact that the following steps are performed: a) apply the composition comprising fluorescent dye and an amphoteric and / or non-ionic surfactant on the skin, and b) then dry the skin or let it dry. 20. COMPOSITION, in the absence of oxidation dyes and oxidizing agents, characterized by the fact that it comprises, in a cosmetically acceptable medium, fluorescent dye soluble in the medium, in which the Petition 870170094291, of 12/04/2017, p. 55/59 5/7 said fluorescent dye is in the orange range and is chosen from the group formed by the dyes that have the following structures: 21. COMPOSITION, according to claim 20, characterized in that the fluorescent dye, eventually neutralized, is soluble in the composition at 0.001 g / l, more particularly 0.5 g / l, preferably at 1 g / l and according to an even more preferred embodiment, at 5 g / l, at a temperature between 15 ^Q Ce25 ° C. 22. COMPOSITION according to any one of claims 20 to 21, characterized in that the fluorescent dye leads to a maximum reflectance that is in the wavelength range ranging from 500 to 650 nanometers, and preferably in the range wavelength ranging from 550 to 620 nanometers. 23. COMPOSITION according to any one of claims 20 to 22, characterized in that the betaine-type amphoteric surfactants are chosen from alkyl (C8-C2o) -betaines, alkyl (CsC2o) -amidoalkyl (Ci-C8) -betaines, alkyl (C8-C2o) -amidoalkyl (C1-C8) sulfobetaines, sulfobetaines or their mixtures. 24. COMPOSITION according to any one of claims 20 to 23, characterized in that the imidazolium derivatives are chosen from amphocarboxyglycinates and amphocarboxypropionates, or mixtures thereof. 25. COMPOSITION, according to any of the Petition 870170094291, dc 12/04/2017, p. 56/59 6/7 claims 20 to 24, characterized in that the nonionic alkylpyrrolidones are (C 1 -C 3) alkylpyrrolidones. 26. COMPOSITION according to any one of claims 20 to 25, characterized in that the oxyalkylenated or glycerolated fatty alcohol ethers are chosen from the possibly hydroxylated, linear or branched, saturated or unsaturated, ethoxylated and / or propoxylated or glycerolates, with a chain containing 8 to 30 carbon atoms. 27. COMPOSITION according to any one of claims 20 to 26, characterized in that the esters of fatty acids and oxyalkylenated or glycerolated monoalcoholes are chosen from esters of carboxylic acids, linear or branched, saturated or unsaturated, with a chain that holds 8 to 30 carbon atoms and a monoalcohol with a chain comprising 8 to 30 carbon atoms, linear or branched, saturated or unsaturated ethoxylated and / or propoxylated or glycerolated. 28. COMPOSITION, according to any one of claims 20 to 27, characterized by the fact that the amphoteric surfactant (s) and / or nonionic surfactant (s) represent (s) 0 , 01% to 30% by weight, more particularly from 0.1% to 20% by weight, and preferably from 0.2% to 10% by weight, of the total weight of the composition. 29. COMPOSITION according to any one of claims 20 to 28, characterized in that the fluorescent dye (s) is present in a weight concentration ranging from 0.01% to 20% by weight, more particularly from 0.05% to 10% by weight, preferably from 0.1% to 5% by weight, based on the total weight of the composition. 30. COMPOSITION according to any one of claims 20 to 29, characterized by the fact that it comprises additional non-fluorescent direct dye of a nonionic, cationic or anionic nature. Petition 870170094291, of 12/04/2017, p. 57/59 1Π 31. COMPOSITION, according to claim 30, characterized by the fact that additional direct dyes are chosen from nitrated benzene dyes, azoic, anthraquinone, naphthoquinone, benzoquinone, phenothiazine dye, indigo, xanthene, phenanthridine, phthalocyanine dyes, as well such as colorants derived from triarylmethane, alone or in mixtures. 32. COMPOSITION according to any one of claims 30 to 31, characterized in that the additional direct coloring (s) represent (s) from 0.0005% to 12% by weight, preferably from 0.005% to 6% by weight, of the total weight of the composition. 33. COMPOSITION, according to any one of claims 20 to 32, characterized by the fact that it is in the form of a whitening and coloring shampoo. 34. PROCESS FOR COLORING HUMAN KERATIN FIBERS, pigmented or artificially colored, with a lightening effect, in the absence of oxidation dyes and oxidizing agents, characterized by the fact that it consists of performing the following steps: a) a composition as defined in one of claims 20 to 33 is applied to said fibers for a time sufficient to reveal the desired color and lightening, b) the fibers are eventually rinsed, c) eventually, the fibers are washed with shampoo and rinsed, d) the fibers are dried or allowed to dry. 35. PROCESS FOR COLORING DARK SKIN with a lightening effect, characterized by the fact that a composition as defined in one of claims 20 to 33 is applied to the skin and then dries or dries the skin. Petition 870170094291, of 12/04/2017, p. 58/59 1/1