FR3004927A1 - COMPOSITION COMPRISING AT LEAST THREE ACTIVE INGREDIENTS FOR COLORING AND / OR PIGMENTING KERATINIC MATERIALS. - Google Patents

Abstract

The present invention relates to a composition comprising, in a physiologically acceptable medium, at least one - a peptide corresponding to the formula (I) R-V1-Ala2-His3-X4-Y5-Tp6-N H2 (I) - a Xantic base of general formula (II) and a compound corresponding to formula (III) The present invention also relates to the cosmetic use of such a composition for dyeing and / or pigmenting keratin materials and / or promoting the pigmentation of materials. keratin, as well as a cosmetic treatment method.

Description

The present invention relates to a composition comprising, in a physiologically acceptable medium, a combination of at least three active agents as well as the use of this composition for dyeing and / or pigmenting keratin materials and / or promoting the pigmentation of keratin materials .

The invention also relates to the use of this composition for browning and / or tanning of the skin and / or for intensifying the tanning, and / or for homogenizing the complexion, as well as a cosmetic treatment method. The color of human skin is a function of various factors including seasons of the year, ethnicity, sex and age. It is mainly determined by the concentration in keratinocytes of melanin produced by melanocytes. Melanocytes are specialized cells that, via particular organelles, melanosomes, synthesize melanin.

The synthesis of melanin or melanogenesis is particularly complex and involves schematically the following main steps: Tyrosine ---> Dopa ---> Dopaquinone ---> Dopachrome ---> Melanin Tyrosinase (monophenol dihydroxyl phenylalanine: oxygen oxidoreductase / EC 1,14,18,1) is the essential enzyme involved in this series of reactions. In particular, it catalyzes the conversion reaction of tyrosine to Dopa (dihydroxyphenylalanine) and the conversion reaction of Dopa to Dopaquinone. In the epidermis, the melanocyte is involved in the epidermal melanic unit which comprises a melanocyte surrounded by about 36 neighboring keratinocytes. All individuals, regardless of phototype, have approximately the same number of melanocytes for a given skin area. The ethnic differences, in terms of pigmentation, are not due to the number of melanocytes, but to the properties of their melanosomes. Melanosomes are aggregated into complexes and are small in size. These are highly specialized organelles whose sole function is the production of melanin. They are born from the endoplasmic reticulum in the form of spherical vacuoles called premelanosomes. Premelanosomes contain an amorphous protein substrate, but no melanogenic enzymes. During the maturation of the premelanosome, the amorphous substrate is organized into a fibrillar structure oriented in the longitudinal axis of the melanosome. There are four stages of development of melanosome corresponding to the intensity of melanization. Melanin is uniformly deposited on the inner fibrillar network of the melanosome and the opacity of the organelle increases to saturation. As melanin is synthesized in the melanosomes, they move from the perinuclear region to the end of the melanocyte dendrites. By phagocytosis, the end of the dendrites is captured by keratinocytes, degraded membranes and redistributed melanosomes in the keratinocytes. Although the level of melanin varies from one population to another, the amount of tyrosinase does not vary significantly and the messenger RNA level of tyrosinase is identical in white or black skin. Variations in melanogenesis are therefore due to variations in either the activity of tyrosinase or the ability of keratinocytes to phagocytose melanosomes. Nowadays, it is important to look good and tanned skin is always a sign of good health. However, natural tanning is not always desirable since it requires prolonged exposures to UV radiation, especially UV-A radiation. They cause browning of the skin but in return are likely to induce an alteration thereof, especially in the case of sensitive skin or a continuous exposure to solar radiation. The skin ages prematurely, becomes dry and is characterized by numerous wrinkles and age spots. It is therefore desirable to find an alternative to natural tanning that is compatible with the requirements of such skins. There is therefore a real need for a product that facilitates and / or improves the pigmentation of the skin. Many solutions have been proposed in the field of artificial coloring. In the field of exogenous dyes, dihydroxyacetone, or DHA, is a particularly valuable product that is commonly used in cosmetics as an artificial tanning agent for the skin; applied on the latter, especially on the face, it provides a tanning effect or browning appearance similar to that which may result from prolonged exposure to the sun (natural tanning) or under a UV lamp. Erythrulose is also a substance used for the same purpose. These compounds act by binding to the amino acids, peptides and proteins of the stratum corneum, depending on the Maillard reaction (non-enzymatic reaction between a sugar and an amine). These colorations obtained with self-tanning type compounds as defined above appear after a few hours, but disappear rather quickly, and are not always homogeneously distributed on the skin. In order to obtain staining that lasts over time, it has been proposed in the prior art to act directly on the biological process of melanogenesis, so as to stimulate the biosynthesis of melanin. Thus, the preparation and use of activators of melanogenesis have been widely illustrated, these activators being either substrates for the biosynthesis of melanin or stimulators of melanin biosynthesis. In particular, it has been described that acetyl-hexapeptide-1, described in patent FR2835528, also known under the trade name "Melitane®", is a synthetic peptide, ligand of MC1R, which has a melanotropic activity. In fact, the activation of the MC1R receptor of melanocytes by its natural ligand alpha-MSH ("Melanocyte Stimulating Hormone") stimulates the synthesis of melanins in keratinous substances such as the skin. This alpha-MSH / MC1R pathway is recognized as a major UV-activated biological pathway involved in tanning of skin. The Applicant has now surprisingly found that the combination of at least one peptide of the formula ( I) as defined below, with a xanthan base of general formula (II) as defined below, and with a compound corresponding to formula (III) as defined below, significantly potentiates pigmentation keratin materials, such as skin. Unexpectedly, the coloration of the keratin materials, such as the skin, and its pigmentation, obtained by combining the three active ingredients of formulas (I) (II) and (III) according to the invention is amplified and is more intense by compared to that obtained by adding the effects of the different assets taken individually. The subject of the present invention is thus a composition comprising, in a physiologically acceptable medium, at least a) a peptide corresponding to formula (I) R-V1-Ala2-H is3-X4-Y5-Trp6-N H2 (I) in which - R represents a hydrogen atom or a protecting group which may be selected from an acetyl group, a benzoyl group, a tosyl group, a benzenesulphonyl group, a benzyloxycarbonyl group or a pyridinepropionyl group; - represents a natural amino acid or not, of configuration L, chosen from norleucine, norvaline and 2-N-Me-norleucine, 15-X represents a natural or non-natural amino acid, of L or D configuration, with an aromatic character chosen from phenylalanine, 1- naphthylalanine, 2-naphthylalanine, phenylglycine, benzothienylalanine, 4,4'-biphenylalanine, 3,3-diphenylalanine, homophenylalanine, indanylglycine, 4-methylphenylalanine, thienylalanine, p-nitro-phenylalanine, halophenylalanine where the halogen is selected by a chlorine, bromine, iodine or fluorine atom in meta, ortho or para phenyl group, Y represents a natural amino acid of L configuration, basic character selected from arginine, lysine or ornithine, as well as its optical isomers, the amino acids Ala, His and Trp at positions 2, 3 and 6 respectively being of L configuration; b) a xantoid base of general formula (II) wherein R1, R2 and R3 independently of one another represent a hydrogen atom or a linear or branched C1-alkyl radical; - C4, as well as its optical isomers and tautomers; and c) a compound of the formula (III) wherein R4 represents a hydrogen atom, a hydroxy, or a -CO-R5 group represents a hydroxy group, or a group -Si (OH) 2R9, - R6 represents a hydrogen atom or a hydroxyl radical, - R7 represents a radical -O-M, - M represents a hydrogen atom; a linear or branched C1-C4 alkyl radical; or a metal cation which is alkaline, alkaline earth metal or a transition metal, - R8 represents a linear or branched C1-C20 saturated alkyl; alkylene, linear or branched, C2-C20; a -CH 2 NH 2 group; a hydroxy radical; or a linear or branched C2-C20 ketone group; Rg represents a linear or branched C1-C4 alkyl radical, as well as its optical isomers. For the purposes of the present invention, the term "physiologically acceptable medium" means a medium that is suitable for administering a composition topically, and compatible with all the keratin materials of human beings such as the skin, the lips, nails, mucous membranes, eyelashes, eyebrows, scalp and / or hair, or any other skin area of the body. According to the invention a physiologically acceptable medium is preferably a cosmetically acceptable medium, that is to say without odor, or unpleasant appearance, and which is perfectly compatible with the topical route of administration. By way of example, the composition according to the invention may be intended to be administered topically, that is to say by surface application of the keratin material in question, such as the skin under consideration. The term "keratin materials" according to the invention is understood to mean the skin, the body, the face and / or the contour of the eyes, the lips, the nails, the mucous membranes, the eyelashes, the eyebrows, the hairs, the scalp and / or the hair, or any other skin area of the body. More particularly, the keratin materials according to the invention are the scalp, the hair, and / or the skin. Preferably, the keratin materials according to the invention are the scalp and / or the hair. Preferably the keratin materials according to the invention is the skin. By "skin" is meant all of the skin of the body, and preferably, the skin of the face, décolleté, neck, arms and forearms, or even more preferably, the skin of the skin. face, including forehead, nose, 10 cheeks, chin, eye area. The composition of the invention may be a cosmetic or dermatological composition. Preferably, according to the invention, the composition is a cosmetic composition and even more preferentially a cosmetic composition for topical application. The term "cosmetic composition" is understood to mean a substance or a preparation intended to be brought into contact with the various superficial parts of the human body, in particular the epidermis, the hair and hair systems, the nails, the lips, the oral mucosa, in view , exclusively or mainly, to clean, embellish, perfume, modify the appearance, protect, maintain or repair body odors. According to the invention is meant by Ac = acetyl; Nle = Norleucine; Ala = Alanine; His = Histidiine; DPhe = D-phenylalanine (or phenylalanine of configuration D); Arg = Ariginine; Trp = Tryptophan. According to the invention, optical isomers of compounds are understood to mean their enantiomers or diastereoisomers, as well as mixtures thereof, including racemic mixtures. The peptides of formula (I) can comprise one or more asymmetric carbon atoms. According to the invention, the peptides of formulas (I) comprise its optical isomers. They may exist as enantiomers or diastereoisomers. These enantiomers, diastereoisomers, as well as their mixtures, including the racemic mixtures are part of the invention.

The peptides of formula (I) can be obtained by those skilled in the art by synthesis according to the usual methods, in particular by using the processes described in patent application FR2835528.

Among the peptides corresponding to the formula (I) according to the present invention, mention may be made of the preferred peptides which are defined as follows: R represents a protective group which may be chosen from an acetyl group, a benzenesulphonyl group, a tosyl group or a pyridinepropionyl group, - V represents a natural amino acid or not selected from norleucine and 2N-Me-norleucine, configuration L. - X represents a natural or non-aromatic amino acid selected from phenylalanine, 2-naphthylalanine, homophenylalanine, thienylalanine or p-nitro-phenylalanine, of D or L-Y configuration, represents a natural amino acid of L configuration, with a basic character chosen from arginine or lysine. Alanine, histidine and tryptophan, respectively at the 2,3 and 6 positions in the peptide of formula (I), are of L configuration.

More particularly, the peptide of formula (I) is chosen from; ## STR1 ## BzISO 2 -Nle-Ala-His-DPhe-Arg-Trp-NH 2, Tos-Nle-Ala-His-DPhe-Arg-Trp-NH 2, -BzISO 2 -Nle-Ala-His-DPhe-Lys-Trp -NH2, -Bz1SO2-Nle-Ala-His-DpNO2Phe-Lys-Trp-NH2, -BzISO2-Nle-Ala-His-DThi-Lys-Trp-NH2, -Ac-Nle-Ala-His-DThi-Lys- Trp-N H 2, -PyrProp-Nle-Ala-His-DpNO 2 Phe-Lys-Trp-N H 2, -PyrProp-Nle-Ala-His-DpNO 2 Phe-Arg-Trp-NH 2, -Ac-Nle-Ala-His- L2, Nap-Lys-Trp-NH2, -Ac-MeNle-Ala-His-DhomoPhe-Arg-Trp-NH2, -Ac-Nle-Ala-His-DhomoPhe-Arg-Trp-NH2, their enantiomers or diastereoisomers, and mixtures thereof, including racemic mixtures.

According to the present invention, the following terms are understood to mean: Ac represents an acetyl group; BzI502 represents a benzenesulphonyl group; PyrProp represents a pyridinepropionyl group; and Tos represents a tosyl group. DHomoPhe represents the homophenylalanine of the D configuration. DThi represents thienylalanine of configuration D, - DpNO2Phe represents p-nitrophenylalanine of configuration D, - L2, Nap represents 2-naphthylalanine of configuration L, 10 - DPhe represents phenylalanine of configuration D, - Nle represents norleucine of configuration L - NMe-Nle represents 2-N-Me-Norleucine L-configuration. Advantageously the peptide corresponding to formula (I) is Ac-Nle-Ala15 His-DPhe-Arg-Trp-NH2. The peptide is Ac-Nle-Ala-His-DPhe-Arg-Trp-NH2 or N-acetyl-L-norleucinealanine-histidine-D-phenylalanine-arginine-tryptophan (INCI name: ACETYL HEXAPEPTIDE-1). Such a peptide may be marketed under the name Melitane® by Lucas Meyer Cosmetics (formerly Unipex solutions). Preferably, said Acetyl-hexapeptide-1 pepitate is in a mixture of water, glycerine and dextran (0.02%). Such a peptide is marketed under the name MELITANE® GL 200 by the company Unipex Innovations). The acetyl-hexapeptide-1 peptide may also be in a mixture of water, butylene glycol and dextran. Such a peptide is marketed under the name MELITANE® BG by the European Institute of Cell Biology. The peptide acetyl-hexapeptide-1 may also be in solution in a mixture of water and dextran. Such a peptide is marketed under the name MELITANE® PS by the European Institute of Cell Biology. The peptide acetyl-hexapeptide-1 may also be in the form of a powder mixed with dextran. Such a peptide is marketed under the name MELITANE® PP by the European Institute of Cell Biology. The peptide of formula (I) may be present in the composition at a content of between 0.0001% and 1%, by weight relative to the total weight of the composition, in particular is present in a content of between 0.001% and 0.5%, by weight relative to the total weight of the composition, and particularly is present at a content of between 0.001% and 0.1%, by weight relative to the total weight of the composition. More particularly, the peptide of formula (I) is present in the composition at a content of 0.001%, by weight relative to the total weight of the composition. Among the xanthine bases having the formula (II) according to the present invention, mention may be made of the preferred xanthine bases which are defined as follows: R 1, R 2 and R 3 represent, independently of one another, a hydrogen atom or a methyl radical. Among the xanthine bases having the formula (II) according to the present invention, mention may also be made of the preferred xanthine bases which are defined as follows: R 1 and R 3 represent a hydrogen atom, or a linear or branched C 1 -C alkyl radical; C4, R1 and R3 can not however simultaneously represent a hydrogen atom, and R2 represents a linear or branched C1-C4 alkyl radical. Preferably a xanthine base of formula (II) is selected from the group consisting of 1,3-dimethylxanthine, 3,7-dimethylxanthine, 1,3,7-trimethylxanthine and 1,7-dimethylxanthine. Preferably, a composition according to the invention thus comprises a xanthine base of formula (II) which is chosen from caffeine (xanthine of formula (II) with R1 = R2 = R3 = CH3), theobromine (xanthine of formula ( II) with R1 = H, R2 = R3 = CH3), theophylline (xanthine of formula (II) with R1 = R2 = CH3, R3 = H) or paraxanthine (xanthine of formula (II) with R1 = R3 = CH3 , R2 = H). The xanthine bases of formula (II) used in the compositions according to the present invention are commercial, or can be easily prepared by those skilled in the art according to conventional synthesis methods. More particularly, a composition according to the invention comprises a xanthine base of formula (II) which is 1,3,7-trimethylxanthine or caffeine. 1,3,7-trimethylxanthine or caffeine can be easily prepared by those skilled in the art according to conventional synthesis methods, such as those described in; "Synthetic caffeine" from Schwaneberg, Herbert, Pharmazeutische Industrie (1943), 10, 109-1; - "Physical and chemical properties of xanthine derivatives" by Zuidema, J., Current Clinical Practice Series (1983), 3 (Sustained Release Theophylline), 11-25; "Reactions with dimethyl carbonate", Part VI - "An advantageous procedure for the preparation of caffeine" by Jansen in de Wal, Helmut; Lissel, Manfred, Zeitschrift fuer Chemie (1989), 29 (7), 253-4: this document describes an improved method of synthesis of caffeine I (R1 = R2 = R3 = Me). Methylation of xanthine I (R1 = R2 = R3 = H) with (Me0) 2CO in DMF in the presence of 1,4,7,10,13,16-hexaoxacyclooctadecane results in 74% of I (R1 = R2 = R3 = Me). Similarly, caffeine was prepared with a yield of 78 and 67% from I (R 1 = R 3 = Me, R 2 = H, R 1 = R 2 = 15 Me, R 3 = H) resp .; - "A Novel Method of Caffeine Synthesis from Uracil" by Zajac, Matthew A .; Zakrzewski, Anthony G .; Kowal, Mark G .; Narayan, Saraswathi, Synthetic Communications (2003), 33 (19), 3291-3297: This paper describes an inexpensive and novel method of synthesizing caffeine from uracil in six simple steps. Uracil is first converted to 1,3-dimethyluracil, followed by a nitration, reduction, then cyclization step in theophylline, and finally the methylation of theophylline to form caffeine. Caffeine or 1,3,7-trimethylxanthine (CAS: 58-08-02), perhaps particularly in the form of an anhydrous powder, and is marketed under the name AEC Caffeine Powder® by A & E Connock (Perfumery & By way of example, caffeine is also marketed under the name Caffeine® by EMD Chemicals Inc., under the name Caffeine® by Merck KGaA / EMD Chemicals, Inc., under the name Camellia. Sinensis @ by MMP, Inc., under OriStract CF @ by Orient Stars LLC, and under the name CAFEINE ANHYDRE POUDRE @ by BASF Caffeine is also manufactured and marketed by Sigma Aldrich, Caffeine @ (code 27600 Fulka), or under the name C075035 Caffeine powder, ReagentPlus®. 3004 92 7 11 Theobromine, or 3,7-dimethylxanthine, is an alkaloid that can be extracted from the cocoa seed, Theobroma cacao, of the family Sterculiaceae; it is also found in small quantities in tea and coffee. By way of example, theobromine is marketed under the name OriStar TBM® by the company Orient Stars LLC, under the name Teobromina / Theobromine® by the company Ricerca & Comunicazione srI., Or under the name T4500-Sigma® by the company Sigma Aldrich . Theophylline, or 1,3-dimethylxanthine, is an isomeric alkaloid of the former, which can be extracted from tea leaves, Thea sinensis, of the family Ternstrcemiaceae. For example, theophylline is marketed under the name OriStar TPL® by Orient Stars LLC, or under the name T1633-Sigma® by Sigma Aldrich.

By way of example, paraxanthine, or 1,7-dimethylxanthine, is sold under the name Slimexir® by the company Rahn AG under the name Sveltam® by the company Libragen), or under the name A005-Sigma® by the company Sigma Aldrich.

The xanthic base of formula (II) may be present in the composition at a content of between 0.01% and 10% by weight relative to the total weight of the composition, in particular is present in a content of between 0.01% and 5%, by weight relative to the total weight of the composition, and particularly is present at a content of between 0.1% and 3%, by weight relative to the total weight of the composition. More particularly, the xanthine base of formula (II) is present in the composition at a content of 1%, by weight relative to the total weight of the composition. Among the compounds corresponding to formula (III) according to the present invention, mention may be made of the preferred compounds of formula (III) in which; R 4 represents a hydrogen atom, a hydroxyl or a group -CO-Ra, -R 5 represents a hydroxyl radical, or a group -Si (OH) 2R 9, -R 6 represents a hydrogen atom, -R 7 represents a radical -O-M, - M represents a hydrogen atom; a methyl group; or a metal cation which is alkaline such as sodium or potassium, alkaline earth metal or a transition metal such as copper; - R8 represents an alkyl which is selected from a methyl group; a linear C5-C10 saturated alkyl; linear C15-20 alkylene; a group - CH2NH2; or a group - (CH 2) 6 -CO (CH 2) 6 -Cl-13, - R 6 represents a methyl radical. Among the compounds corresponding to formula (III) according to the present invention, mention may be made of the more preferred compounds of formula (III) in which; M represents a hydrogen atom; R 8 represents an alkyl which is chosen from a methyl group; a linear C5-C10 saturated alkyl; linear C17 alkylene; or a group - CH2NH2.

The compounds of formula (III) used in the compositions according to the present invention are commercial, or can be easily prepared by those skilled in the art according to conventional synthesis methods. In the context of the present invention, unless otherwise indicated, a C 1 -C 4 alkyl is a saturated linear or branched alkyl group having from 1 to 4 carbon atoms. Preferably, the saturated, linear or branched C 1 -C 20 alkyl groups may be chosen from: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. Preferably, the saturated, linear or branched, C 1 -C 20 alkyl group is methyl, a heptyl, or a nonyl. In the context of the present invention, a C 1 -C 4 alkylene denotes a linear or branched alkylene group comprising from x to y carbon atoms. Preferably, the C2-C20 linear or branched alkylene groups may be chosen from: allyl, vinyl, butylene, isobutylene, pentylene, hexylene, heptylene, 2-ethylhexylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene and eicosylene.

Preferably, the linear or branched C 1 -C 20 unsaturated alkyl group is heptadecy-8-ene. In the context of the present invention, a C2-C20 linear or branched ketone group denotes a linear or branched ketone group comprising from 2 to 5 carbon atoms. More particularly, said ketone group is a keto group, linear or branched, C 2 -C 15. Preferably, said ketone group is the - (CH 2) 6 -CO (CH 2) 6 -CH 3 group. In the context of the present invention a metal cation is alkaline, alkaline earth, or a transition metal such as copper. Preferably an alkali metal cation is sodium or potassium. Preferably an alkaline earth metal cation is calcium or magnesium. Preferably, the transition metal is copper. In the context of the present invention, the optical isomers are especially enantiomers and diastereoismers, as well as their racemic mixture. More particularly, a compound of formula (III) is selected from the group consisting of N-acetyl-L-tyrosine, N-hydroxy-L-tyrosine, Néthanoyl-tyrosine (INCI name: Acetyl tyrosine Methyl), tyrosine, glycintyrosine, caproyl tyrosine, capryloyl tyrosine, oleoyl acetyl tyrosine, glycyl-L-Tyrosine (INCI name: Glycyl-L-Tyrosine dihydrate), N-acetyl methylsilanol tyrosine (INCI name methylsilanol acetyl ttyrosine), N-acetyl methylsilanol tyrosinate Copper (INCI name: copper acetyl tyrosinate methylsilanol, oleyl acetyl-tyrosine, N-caproyl-tyrosinate potassium (INCI name: potassium Caproyl tyrosine), methyl tyrosinate capryloyl (INCI name: methyl capryloyl tyrosinate), L-3,4-dihydroxyphenylalanine, and hexyldioxodecyl-methyl tyrosinate (INCI name: Hexyldioxodecyl methyl tyrosinate), with no specific mention of INCI names. the compound of formula (II I) is N-acetyl-tyrosine, or Acetyl tyrosine. N-Acetyl-L-tyrosine can be readily prepared by one skilled in the art according to tyrosine acylation methods. Methods for the preparation of N-acetyl-L-tyrosine are for example those described in; the patent application CN1594283 "Preparation of N-acetyl-L-tyrosine" by Liu, Aifu, Faming Zhuanli Shenqing Gongkai Shuomingshu, which describes a method comprising a step of acetylation of L-tyrosine with an acylating agent (acetic anhydride). molar ratio of 1: 3-5) at 50-80 ° C for 45-75 minutes, then concentration, removal of the acid, then crystallization to give the crude product, dissolution of the crude product in 75% water. 80 ° C, bleaching, filtering, concentration, crystallization, and drying to give the final product; - "Resolution of N-protected amino acid esters using whole cells of Candida parapsilosis ATCC 7330" from Stella, Selvaraj; Chadha, Anju, Tetrahedron: Asymmetry (2010), 21 (4), 457-460; this document notably describes that whole Candida parapsilosis ATCC 7330 cells were used for the resolution of N-acetylated amino acid esters. Good enantioselectivities (E = 40 to> 500) were obtained for the resolution of the N-protected protein and the non-protein amino acid esters, which give good yields (28-50%) and high enantiomeric excesses. (up to> 99%) for both enantiomers.

By way of example, N-acetyl-L-tyrosine is marketed under the name Melanowhite-A® by the company Ichimaru Pharcos Company, Ltd., or under the name Tanogen NB® by the company Caribia, Inc.. By way of example, N-acetyl-L-tyrosine is manufactured and sold by PharmaZell GmbH under the name N-Acetyl Tyrosine® and by Sigma-Aldrich N-Acetyl-L-Tyrosine® (code A2513 Sigma). ). By way of example, Hexyldioxodecyl Methyl Tyrosinate is marketed under the name K6EAAL-19® by the company NeoPharm Co., Ltd. ; Caproyl Tyrosine is sold under the name Tyrosinol® by the company Sinerga S.P.A; Glycyl-L-Tyrosine Dihydrate by Kyowa Hakko Kogyo Co., Ltd .; Methylsilanol acetyltyrosine is sold under the name Tyrosilane® by the company Exsymol; Oleoyl Tyrosine is marketed under the name TYR-OL® by Sederma, Inc. / Croda Inc.; Tyrosine is marketed under the name AEC Tyrosine® by the company A & E Connock (Perfumery & Cosmetics) Ltd., under the name OriStar LT @ by the company Orient Stars LLC, or under the name L-Tyrosine® by the company Bretagne Fine chemistry ; Potassium Caproyl Tyrosine is sold under the name Tyrostan® by the company Sinerga S.P.A; Methyl Capryloyl Tyrosinate is marketed under the name Defensamide-8® by Neopharm Co., Ltd. The compound of formula (III) may be present in the composition at a content of between 0.01% and 10%, by weight relative to the total weight of the composition, in particular is present in a content of between 0.01% and 5%, by weight relative to the total weight of the composition, and particularly is present at a content of between 0.1% and 3%, by weight relative to the total weight of the composition. More particularly, the xanthine base of formula (II) is present in the composition at a level of 0.5%, by weight relative to the total weight of the composition. Preferably, a composition according to the invention comprises, in a physiologically acceptable medium, at least one peptide corresponding to formula (I) which is Ac-Nle-Ala-His-DPhe-Arg-Trp-NH2, a compound of formula (III) which is N-acetyl tyrosine, and a xanthine base of formula (II) which is 1,3,7-trimethylxanthine or caffeine. The compositions according to the invention can be prepared according to the techniques well known to those skilled in the art. The compositions of the invention may be in any of the galenical forms conventionally used, in particular for topical application, and such as in the form of aqueous, hydroalcoholic or oily solutions, of oil-in-water (O / W) emulsions. or water-in-oil (W / O) or multiple (triple: W / O / W or W / O / H), aqueous or oily gels, liquid, pasty or solid anhydrous products, or dispersions of a fatty phase in an aqueous phase using spherules, these spherules may be polymeric nanoparticles such as nanospheres and nanocapsules, or lipid vesicles of ionic and / or nonionic type. These compositions are prepared according to the usual methods. The compositions according to the invention may be more or less fluid and have the appearance of a white or colored cream, a cream gel, an ointment, a milk, a lotion, a serum, a paste, a mousse. They can optionally be packaged in an aerosol and be applied to the skin in the form of foam or spray. They can also be in solid form, and for example in the form of a stick. The compositions according to the invention may also be in anhydrous form, for example in the form of an oil. The term "anhydrous composition" means a composition containing less than 1% by weight of water, or even less than 0.5% of water, and especially free of water, the water not being added during the preparation of the composition but corresponding to the residual water provided by the mixed ingredients.

The compositions used according to the invention may comprise an oily phase. For the purposes of the invention, the term "oily phase" is intended to mean a phase comprising at least one oil and all the liposoluble and lipophilic ingredients and fatty substances used for the formulation of the compositions of the invention. The term "oil" means any fatty substance in liquid form at ambient temperature (20-25 ° C.) and at atmospheric pressure (760 mmHg). An oil suitable for the invention may be volatile or non-volatile. An oil suitable for the invention may be selected from hydrocarbon oils, silicone oils, fluorinated oils and mixtures thereof. A hydrocarbon oil suitable for the invention may be an animal hydrocarbon oil, a vegetable hydrocarbon oil, a mineral hydrocarbon oil, or a synthetic hydrocarbon oil. An oil suitable for the invention may advantageously be selected from mineral hydrocarbon oils, vegetable hydrocarbon oils, synthetic hydrocarbon oils, silicone oils, and mixtures thereof. For the purposes of the present invention, the term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group. The term "hydrocarbon oil" means an oil containing mainly hydrogen and carbon atoms. The term "fluorinated oil" means an oil comprising at least one fluorine atom. A hydrocarbon oil which is suitable for the invention may, in addition, optionally comprise oxygen, nitrogen, sulfur and / or phosphorus atoms, for example, in the form of hydroxyl, amine, amide, ester or ether groups. and in particular in the form of hydroxyl, ester, ether or acid groups. The oily phase generally comprises, in addition to the at least one lipophilic UV filter, at least one volatile or non-volatile hydrocarbon oil and / or a volatile and or non-volatile silicone oil. For the purposes of the invention, the term "volatile oil" means an oil capable of evaporating on contact with the skin or the keratin fiber in less than one hour, at ambient temperature and atmospheric pressure. The volatile oil (s) of the invention are volatile cosmetic oils which are liquid at ambient temperature and have a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular from 0.13 Pa to 40,000 Pa (10). 3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg); 25 mm Hg). By "non-volatile oil" is meant an oil remaining on the skin or the keratin fiber at ambient temperature and atmospheric pressure for at least several hours and in particular having a vapor pressure of less than 10 -3 mmHg (0.13 Pa). ). Hydrocarbon oils As non-volatile hydrocarbon oils that may be used according to the invention, mention may be made in particular of: (i) hydrocarbon-based oils of vegetable origin, such as triesters of glycerides, which are generally triesters of fatty acids and of glycerol, the fatty acids may have various chain lengths of C4 to C24, the latter may be linear or branched, saturated or unsaturated; these oils include wheat germ, sunflower, grape seed, sesame, maize, apricot, castor, shea, avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, pumpkin, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passiflora, muscat rose; or alternatively caprylic / capric acid triglycerides, such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel, (ii) synthetic ethers having from 10 to 40 carbon atoms; (iii) linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam, squalane, and mixtures thereof; (iv) synthetic esters such as oils of formula RCOOR 'in which R represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R' represents a hydrocarbon chain, in particular branched, containing from 1 to 40 carbon atoms with the proviso that R + R 'is 10, such as, for example, purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alcohols benzoate, and the like. product sold under the trade name "Finsolv TN®" or "Witconol TN®" by WITCO or "TEGOSOFT TN C" by EVONIK GOLDSCHMIDT, 2-ethylphenyl benzoate as the commercial product sold under the name "X TEND 226® by the company ISP, isopropyl lanolate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate , isostearyl isostearate, diisopropyl sebacate, a product sold under the name "Dub Dis" by Stearinerie Dubois, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxyl esters such as isostearyl lactate, diisostearyl malate; and pentaerythritol esters; citrates or tartrates such as linear C12-C13 di-alkyl tartrates such as those sold under the name COSMACOL ETI® by the company ENICHEM AUGUSTA INDUSTRIALE as well as linear C14-C15 di-alkyl tartrates such as those sold under the name COSMACOL ETL® by the same company; acetates. (y) branched-chain and / or unsaturated carbon-chain liquid fatty alcohols having from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2- butyloctanol, undecylpentadecanol; (vi) higher fatty acids such as oleic acid, linoleic acid, linolenic acid; (vii) carbonates, such as dicaprylyl carbonate, such as the product sold under the name "Cetiol CC®" by the company Cognis; (viii) fatty amides, such as Isopropyl N-lauroyl sarcosinate, such as the product sold under the trade name Eldew SL 205® from Ajinomoto, and mixtures thereof, Among the non-volatile hydrocarbon oils which can be used according to the invention, it is preferable to particularly the glyceride triesters and in particular the caprylic / capric acid triglycerides, the synthetic esters and in particular the isononyl isononanoate, the oleyl erucate, the C12-C15 alcohol benzoate, the benzoate of 2 ethylphenyl and fatty alcohols, in particular octyldodecanol As volatile hydrocarbon oils that may be used according to the invention, hydrocarbon-based oils having from 8 to 16 carbon atoms, and especially C8-C16 branched alkanes such as isoalkanes, may be mentioned in particular. C8-C16 of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, oils sold under the The trade names are Isopars or permetyls, branched C8-C16 esters, isohexyl neopentanoate, and mixtures thereof.

Mention may also be made of the alkanes described in the patent applications of Cognis WO 2007/068371, or WO2008 / 155059 (mixtures of distinct alkanes and differing from at least one carbon). These alkanes are obtained from fatty alcohols, themselves obtained from coconut oil or palm oil. mention may be made of the mixtures of n-undecane (Cil) and n-tridecane (C13) obtained in Examples 1 and 2 of Application WO2008 / 155059 from Cognis. Mention may also be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 1497®, and mixtures thereof.

Other volatile hydrocarbon oils such as petroleum distillates, in particular those sold under the name Shell Soit® by the company SNELL, may also be used. According to one embodiment, the volatile solvent is chosen from volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof. b) Silicone oils The non-volatile silicone oils may be chosen in particular from non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes containing alkyl or alkoxy groups, during and / or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms. carbon, phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates; As volatile silicone oils, mention may be made, for example, of volatile linear or cyclic silicone oils, in particular those having a viscosity of 8 centistokes (8 10-6 m 2 / s), and having in particular 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil that can be used in the invention, mention may be made in particular of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl disiloxane, octamethyltrisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.

Mention may also be made of linear alkyltrisiloxane linear oils of general formula (IV): ## STR2 ## where R represents an alkyl group comprising from 2 to 5 carbon atoms. to 4 carbon atoms and one or more hydrogen atoms may be substituted by a fluorine or chlorine atom.

Among the oils of general formula (IV), mention may be made of: 3-butyl 1,1,1,3,5,5,5-heptamethyltrisiloxane, 3-propyl 1,1,1,3,5,5 , 5-heptamethyltrisiloxane, and 3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, corresponding to the oils of formula (IV) for which R is respectively a butyl group, a propyl group or a ethyl group. Fluorinated oils Fluorinated volatile oils such as nonafluoromethoxybutane, nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane and mixtures thereof can also be used. An oily phase according to the invention may further comprise, mixed with or solubilized in oil, other fatty substances. Another fatty substance that may be present in the oily phase may be, for example: a fatty acid chosen from fatty acids containing from 8 to 30 carbon atoms, such as stearic acid, lauric acid, acid, palmitic and oleic acid; a wax chosen from waxes such as lanolin, beeswax, carnauba or candelilla wax, paraffin waxes, lignite waxes or microcrystalline waxes, ceresin or ozokerite, synthetic waxes such as waxes polyethylene, Fischer-Tropsch waxes; a gum chosen from silicone gums (dimethiconol), a pasty compound, such as polymeric or non-polymeric silicone compounds, esters of an oligomeric glycerol, arachidyl propionate, triglycerides of fatty acids and their derivatives , and their mixtures. These fats may be varied in their choice by those skilled in the art to prepare a composition having the desired properties, for example of consistency or texture. Preferably, the overall oily phase, including all the lipophilic substances in the composition capable of being solubilized in this same phase, represents from 5 to 95% by weight, and preferably from 10 to 80% by weight relative to total weight of the composition. According to a particular embodiment, the composition according to the invention is a water-in-oil (W / O) or oil-in-water (O / W) emulsion. In the case of compositions in the form of oil-in-water or water-in-oil emulsions, the emulsification processes that can be used are of the pale type or helix, rotor-stator and HHP type. To obtain stable emulsions with a low level of polymer (oil / polymer ratio> 25), it is possible to disperse in concentrated phase and then dilute the dispersion with the rest of the aqueous phase. It is also possible, by HHP (between 50 and 800b), to obtain stable dispersions with drop sizes of up to 100 nm. The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture and optionally a co-emulsifier. The emulsifiers are suitably selected according to the emulsion to be obtained (W / O or O / W).

The emulsifier and the co-emulsifier are generally present in the composition, in a proportion ranging from 0.3 to 30% by weight, and preferably from 0.5 to 20% by weight relative to the total weight of the composition. The emulsion may further contain lipid vesicles.

As examples of W / O emulsifying surfactants, mention may be made of alkyl esters or ethers of sorbitan, glycerol, polyol, glycerol or sugars; silicone surfactants such as dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name "DC 5225 C®" by the company Dow Corning, and alkyl dimethicone copolyols such as Laurylmethicone copolyol sold under the name " Dow Corning 5200 Formulation Aid "by Dow Corning; cetyl dimethicone copolyol such as the product sold under the name Abil EM 90R® by the company Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the name ABIL WE 09 ® by the company Goldschmidt. One or more co-emulsifiers may also be added, which advantageously may be chosen from the group comprising the alkyl esters of polyol.

Mention may also be made of non-silicone emulsifying surfactants, in particular alkyl esters or sorbitan, glycerol, polyol or sugar ethers. As polyol alkyl esters, polyethylene glycol esters such as PEG-30 Dipolyhydroxystearate such as product marketed under the name Arlacel P135® by the company ICI. Examples of glycerol and / or sorbitan esters that may be mentioned are polyglycerol isostearate, such as the product sold under the name Isolan GI 34® by Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987® by the company ICI; sorbitan isostearate and glycerol, such as the product sold under the name Arlacel 986® by the company ICI, and mixtures thereof. For O / W emulsions, mention may be made, for example, of nonionic emulsifying surfactants of polyoxyalkylenated fatty acid and glycerol esters (more particularly polyoxyethylenated and / or polyoxypropylenated); oxyalkylenated fatty acid and sorbitan esters; esters of polyoxyalkylenated fatty acids (in particular polyoxyethylenated and / or polyoxypropylenated) optionally in combination with a fatty acid and glycerol ester, such as the PEG-100 Stearate / Glyceryl Stearate mixture marketed for example by the company ICI under the name Arlacel 165; oxyalkylenated fatty alcohol ethers (oxyethylenated and / or oxypropylenated); sugar esters such as sucrose stearate; fatty alcohol and sugar ethers, especially alkylpolyglucosides (APG) such as decylglucoside and laurylglucoside sold, for example, by Henkel under the respective names Plantaren 2000® and Plantaren 1200®, cetostearylglucoside, optionally in admixture with cetostearyl alcohol, sold for example under the name Montanov 68® by Seppic under the name Tegocare CG90® by Goldschmidt and under the name Emulgade KE3302® by Henkel, and arachidyl glucoside, for example under the name form of the mixture of arachidic and behenic alcohols and arachidylglucoside sold under the name Montanov 202® by the company Seppic. According to a particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition, as described for example in WO- A-92/06778. The compositions according to the invention may further comprise at least one aqueous phase. The aqueous phase contains water, and optionally other organic solvents that are soluble or miscible with water. An aqueous phase suitable for the invention may comprise, for example, a water selected from natural spring water, such as La Roche-Posay water, Vittel water, or Vichy waters, or flower water. Solvents or miscible in water suitable for the invention include diols or polyols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycerol, and sorbitol, and mixtures thereof.

According to a preferred embodiment, ethanol, propylene glycol, glycerine, and mixtures thereof may be used more particularly. According to one particular form of the invention, the overall aqueous phase, including all the hydrophilic substances of the composition capable of being solubilized in this same phase, represents from 5 to 95% by weight, and preferably from 10 to 80% by weight. weight relative to the total weight of the composition.

The compositions according to the invention may also contain adjuvants which are conventional in the cosmetic or dermatological field, such as hydrophilic or lipophilic gelling agents, preservatives, antioxidants, solvents, perfumes, fillers, odor absorbers, substances colorants, salts. These adjuvants, depending on their nature, can be introduced into the fatty phase, into the aqueous phase and / or into the lipid spherules. The aqueous compositions in accordance with the present invention may also comprise conventional cosmetic adjuvants, chosen in particular from organic solvents, ionic or nonionic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-corrosive agents and the like. foam, perfumes, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, active ingredients, fillers, polymers, propellants, alkalizing or acidifying agents or any other ingredient usually used in the cosmetic field and / or dermatological. Among the organic solvents, mention may be made of alcohols other than the C1-C4 monoalkanols as defined above, and in particular short-chain C2-C8 polyols, such as glycerine, diols such as caprylylglycol, pentanedio1-1,2 propanediol, butanediol, glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol. As thickeners, there may be mentioned carboxyvinyl polymers such as Carbopols® (Carbomers) and Pemulen such as Pemulen TRI® and Pemulen TR2® (acrylate / C10-C30-alkylacrylate copolymer); polyacrylamides, for example crosslinked copolymers sold under the names Sepigel 305® (CTFA name: polyacrylamide / C13-14 isoparaffin / Laureth 7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by the company Seppic; polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally cross-linked and / or neutralized, such as poly (2-acrylamido-2-methylpropanesulphonic acid) marketed by Hoechst under the trademark "Hostacerin AMPS®" ( CTFA name: ammonium polyacryloyldimethyl taurate or SIMULGEL 800® marketed by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate / polysorbate 80 / sorbitan oleate), copolymers of 2-acrylamido-2-methylpropanesulfonic acid and hydroxyethyl acrylate as the SIMULGEL NS® and SEPINOV EMT 10® sold by the company SEPPIC, cellulose derivatives such as hydroxyethylcellulose, polysaccharides and especially gums such as Xanthan gum, water-soluble or water-dispersible silicone derivatives such as acrylic silicones and silicones polyethers and cationic silicones and mixtures thereof. Examples include, for example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric, lactic acid, sulfonic acids.

Among the alkalinizing agents that may be mentioned, for example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, hydroxides of sodium or potassium.

Preferably, the cosmetic composition comprises one or more alkalinizing agents chosen from alkanolamines, in particular triethanolamine, and sodium hydroxide. In the case of a direct emulsion, the pH of the composition according to the invention is generally between 3 and 12 approximately, preferably between 5 and 11 approximately, and even more particularly from 6 to 8.5.

According to a preferred embodiment of the invention, the compositions according to the invention may also contain one or more additional UV screening agents chosen from hydrophilic, lipophilic or insoluble organic UV filters and / or one or more inorganic pigments. Preferably, it will consist of at least one hydrophilic organic UV filter, lipophilic or insoluble. By "hydrophilic UV filter" is meant any organic or inorganic cosmetic or dermatological compound filtering the UV radiation capable of being completely dissolved in the molecular state in a liquid aqueous phase or of being solubilized in colloidal form (for example in the form of micellar) in a liquid aqueous phase. By "lipophilic filter" is meant any organic or inorganic cosmetic or dermatological compound filtering UV radiation capable of being completely dissolved in the molecular state in a liquid fatty phase or to be solubilized in colloidal form (for example in micellar form ) in a liquid fatty phase. By "insoluble UV filter" is meant any organic or inorganic cosmetic or dermatological compound filtering UV radiation having a solubility in water of less than 0.5% by weight and a solubility of less than 0.5% by weight in most organic solvents such as paraffin oil, fatty alcohol benzoates and triglycerides of fatty acids, for example Miglyol 812® marketed by the company DYNAMIT NOBEL. This solubility, performed at 70 ° C is defined as the amount of product in solution in the equilibrium solvent with an excess of suspended solid after return to room temperature. It can easily be evaluated in the laboratory. The organic UV filters are especially chosen from cinnamic compounds; anthranilate compounds; salicylic compounds, dibenzoylmethane compounds, benzylidene camphor compounds; benzophenone compounds; the compounds 8,8-diphenylacrylate; triazine compounds; benzotriazole compounds; benzalmalonate compounds in particular those cited in patent U55624663; benzimidazole derivatives; imidazoline compounds; bis-benzoazolyl compounds as described in patents EP669323 and US 2,463,264; p-aminobenzoic compounds (PABA); methylene bis (hydroxyphenyl benzotriazole) compounds as described in US5,237,071, US 5,166,355, GB2303549, DE 197 26 184 and EP893119; benzoxazole compounds as described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844; filter polymers and silicone filters such as those described in particular in the application WO93 / 04665; dimers derived from α-alkylstyrene such as those described in patent application DE19855649; 4,4-diarylbutadiene compounds as described in applications EP0967200, DE19746654, DE19755649, EP-A1008586, EP1133980 and EP133981 and mixtures thereof.

Examples of organic photoprotective agents that may be mentioned are those referred to below under their INCI name: cinnamic compounds: Ethylhexyl methoxycinnamate sold in particular under the trade name PARSOL MCX® by DSM Nutritial Products Isopropyl Methoxycinnamate Isoamyl p-Methoxycinnamate sold under the trade name NEO HELIOPAN E 1000 @ by Symrise DEA Methoxycinnamate, Diisopropyl Methylcinnamate, Glyceryl Ethylhexanoate Dimethoxycinnamate. Para-Aminobenzoic Compounds: PABA, Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the name "ESCALOL 507®" by ISP, Glyceryl PABA, PEG-25 PABA sold under the name "UVINUL P 25®" by BAS F Salicylic compounds: Homosalate sold under the name "Eusolex HMS®" by Rona / EM Industries, Ethylhexyl Salicylate sold under the name "NEO HELIOPAN OS @" by Symrise, Dipropylene glycol salicylate sold under the name "DIPSAL®" by SCHER, TEA Salicylate, sold under the name "NEO HELIOPAN TS @" by Symrise, Compounds 6,13-diphenylacrylate: cyano-3,3-diphenylacrylate of 2-ethylhexyl or Octocrylene sold in particular under the trade name "UVINUL N 539®" by BASF , or also sold by the company MFCI under the trade name OCTOCRYLENE®. Etocrylene, sold in particular under the trade name "UVINUL N 35®" by BASF. Benzophenone compounds: 10 Benzophenone-1 sold under the trade name "UVINUL 400®" by BASF, Benzophenone-2 sold under the trade name "Uvinul D 50®" by BASF Benzophenone-3 or Oxybenzone, sold under the trade name "Uvinul M 40® "by BASF, Benzophenone-4 sold under the trade name" UVINUL MS 40® "by BASF, Benzophenone-5 Benzophenone-6 sold under the trade name" Helisorb 11® "by Norquay Benzophenone-8 sold under the trade name "Spectra-Sorb UV-24®" by American Cyanam ID 20 Benzophenone-9 sold under the trade name "UVINUL DS 49®" by BASF, Benzophenone-12 2- (4-diethylamino-2-hydroxybenzoyl) benzoate hexyl sold under the trade name "UVINUL A Plus C," or in admixture with octylmethoxycinnamate under the trade name "UVINUL A Plus B®" by BASF, 25 1,1 '- (1,4-piperazinediyl) bis [14244- (diethylamino) -2-hydroxybenzoyl] phenyl] methanone (CAS 919803-06-8) as described in WO2007 / 071584; this compound being advantageously used in micronized form (average size of 0.02 to 2 μm) obtainable for example according to the micronization process described in Applications GB-A-2 303 549 and EP-A-893119 and in particular under aqueous dispersion form. Benzylidene camphor compounds: 3-Benzylidene camphor manufactured under the name "MEXORYL SDC," by CHIMEX, 4-Methylbenzylidene camphor sold under the name "EUSOLEX 6300®" by MERCK, Benzylidene Camphor Sulfonic Acid manufactured under the name "MEXORYL SLC," by CHIMEX, Camphor Benzalkonium Methosulfate manufactured under the name "MEXORYL SO®" by CHIMEX, Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name "MEXORYL SX ^ 0" by CHIMEX, Polyacrylamidomethyl Benzylidene Camphor manufactured under the name "MEXORYL SW®" by CHIMEX. Phenylbenzimidazole compounds: Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name "Eusolex 232®" by Merck. Bis-benzoazolyl compounds Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name "NEO HELIOPAN AP®" by HAARMANN and REIMER. Phenyl benzotriazole compounds: Drometrizole Trisiloxane sold under the name Silatrizole® by Rhodia Chimie. Methylene bis-benzotriazolyl tetramethylbutylphenol compounds, especially in solid form, such as the product sold under the trade name MIXXIM BB / 100 C, by FAIRMOUNT CHEMICAL or in the form of an aqueous dispersion of micronized particles having an average size; particles which vary from 0.01 to 5 μm and more preferably from 0.01 to 2 μm and more particularly from 0.020 to 2 μm with at least one alkylpolyglycoside surfactant of structure 0 (C61-11005) xH in which n is an integer from 8 to 16 and x is the average degree of polymerization of the unit (C8H1005) and varies from 1.4 to 1.6 as described in GB-A-2 303 549 sold especially under the trade name "TINOSORB M® by BASF or in the form of an aqueous dispersion of micronized particles having an average particle size which varies from 0.02 to 2 μm and more preferably from 0.01 to 1.5 μm and more particularly from 0.01 to 1.5 μm. 0.02 to 1 μm in the presence of at least one mono- (C 8 -C 20) alkyl polyglycerol ester having a glycerol polymerization degree of at least 5 such as the aqueous dispersions described in the application WO2009 / 063392. Triazine Compounds: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name Tinosorb S® by BASF, Ethylhexyl Triazone sold in particular under the trade name Uvinul T150® by BASF, Diethylhexylbutamido triazone sold under the trade name UVASORB HEB C, by SIGMA 3V, 2,4,6-tris (4'-amino benzalmalonate dineopentyl) -s-triazine, 2,4,6-tris- (4'-amino benzalmalonate diisobutyl) - s-triazine, -2,4-bis (n-butyl 4'-aminobenzoate) -6- (aminopropyltrisiloxane) -s-triazine, dineopentyl 10-2,4-bis (4'-aminobenzalmalonate) -6- ( 4'-N-tributyl aminobenzoate) -s-triazine, the symmetrical triazine filters substituted by naphthalenyl groups or polyphenyl groups described in U56,225,467, the application WO2004 / 085412 (see compounds 6 and 9) or the document " Symetrical Triazine 15 Derivatives »IP.COM IPC0M000031257 Journal, INC. WEST HENRIETTA, NY, US (September 20, 2004) including 2,4,6-tris (di-phenyl) -triazine e and 2,4,6-tris (ter-phenyl) -triazine which is incorporated in the patent applications W006 / 035000, W006 / 034982, W006 / 034991, W006 / 035007, WO2006 / 034992, WO2006 / 034985, these compounds being advantageously used in micronized form (average particle size of 0.02 to 3 μm) obtainable, for example, according to the micronisation process described in Applications GB-A-2 303 549 and EP-A-893119 and in particular in aqueous dispersion; the triazine silicones substituted by two aminobenzoate groups as described in patent EP0841341, in particular 2,4-bis (n-butyl 4'-aminobenzalmalonate) -6 - [(3- {1, 3, 3, 3-tetramethyl-1 - [(trimethylsilyloxe disiloxanyllpropyl) amino] -s-triazine Anthranilic compounds: Menthyl anthranilate sold under the trade name "NEO HELIOPAN MA®" by Symrise Imidazoline Compounds: Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate, 35 Compounds benzalmalonate: Polyorganosiloxane with benzalmalonate functions, such as Polysilicone-15 sold under the trade name "PARSOL SLX C," by HOFFMANN LA ROCHE.

4,4-Diarylbutadiene compounds: -1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene. Benzoxazole compounds: 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine sold under the name of Uvasorb K2A® by Sigma 3V. Carbonyl Merocyanine Derivatives: These compounds are described in U54195999, WO2004 / 006878 and IP COM Journal 4 (4), No. IPCOM000011179D published 04/03/2004. Dibenzoylmethane compounds: Butyl Methoxydibenzoylmethane sold in particular under the trade name "PARSOL 1789®" by DSM Nutritional Products, Inc .; or under the trade name EUSOLEX 9020® c by Merck. Isopropyl Dibenzoylmethane. The preferred organic screening agents are selected from ethylhexyl methoxycinnamate ethylhexyl salicylate, homosalate, octocrylene, phenylbenzimidazole sulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, and the like. hexyl. 4-Methylbenzylidene camphor, Terephthalylidene Dicamphor Sulfonic Acid, Disodium Phenyl Dibenzimidazole Tetrasulfonate, Methylene bis-Benzotriazolyl Tetramethylbutylphenol Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Ethylhexyl Triazone, Diethylhexyl Butamido Triazone, 2,4,6-tris (4'-amino benzalmalonate dineopentyl) ) -s-triazine 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine 2,4-bis- (n-butyl 4-aminobenzoate) -6- (aminopropyltrisiloxane) -s triazine, 2,4-bis (dineopentyl 4'-aminobenzalmalonate) -6- (n-butyl 4'-aminobenzoate) -s-triazine, 2,4-bis (n-butyl 4'-aminobenzalmalonate) -6 - [(3- {1,3,3,3-tetramethyl-1-trimethylsilyloxy] disiloxanyllpropyl) amino] -s-triazine, 2,4,6-tris- (di-phenyl) -triazine, 2,4,6 Trisiloxane Polysilicone-1,1-dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -tris- (tert-phenyl) -triazine ) -imino] -6- (2-ethylhexyl) imino-1,3,5-triazine Butyl Methoxydibenzoylmethane and their mixtures.

Particularly preferred organic screening agents are selected from ethylhexyl salicylate, homosalate, octocrylene, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate. Terephthalylidene Dicamphor Sulfonic Acid, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Ethylhexyl Triazone, Diethylhexyl Butamido Triazone, 2,4-bis (n-butyl 4'-aminobenzalmalonate) -6 - [(3- {1,3,3,3-tetramethyl) 1- (trimethylsilyloxy) disiloxanyllpropyl) amino] -s-triazine, Drometrizole Trisiloxane Butyl Methoxydibenzoylmethane and mixtures thereof.

The inorganic UV filters used in accordance with the present invention are metal oxide pigments. More preferably, the inorganic UV filters of the invention are metal oxide particles having an average element particle size less than or equal to 0.5 μm, more preferably between 0.005 and 0.5 μm and even more preferentially between 0.01 and 0.2 .mu.m, more preferably between 0.01 and 0.1 .mu.m, and more preferably between 0.015 and 0.05 .mu.m. They may be chosen in particular from oxides of titanium, zinc, iron, zirconium, cerium or their mixtures.

Such metal oxide pigments, coated or uncoated are in particular described in the patent application EP-A-0518 773. As commercial pigments can be mentioned products sold companies SACHTLEBEN PIGMENTS, TAYCA, MERCK and DEGUSSA .

The metal oxide pigments may be coated or uncoated. The coated pigments are pigments which have undergone one or more surface treatments of a chemical, electronic, mechanochemical and / or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (of titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin) , alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

The coated pigments are more particularly titanium oxides coated with: - silica such as the product "SUNVEILOE from the company IKEDA, - silica and iron oxide such as the product" SUNVEIL FOE from the company IKEDA, - silica and alumina such as the products "MICROTITANIUM DIOXIDE MT 30 500 SAC" and "MICROTITANIUM DIOXIDE MT 100 SA" from the company TAYCA, "TIOVEIL" from the company TIOXIDE, - alumina such as the products "TIPAQUE TTO- 55 (B) Cr and "TIPAQUE TTO55 (A) Cr from the company ISHIHARA, and" UVT 14/4 "from the company SACHTLEBEN PIGMENTS, 35 - alumina and aluminum stearate such as the products" MICROTITANIUM DIOXIDE MT 100 TC), MT 100 TXC), MT 100 ZC), MT-01C) from the company 3004 92 7 35 TAYCA, the products "Solaveil CT-10 WC" and "Solaveil CT 100O" from the company UNIQEMA and the product "Eusolex T-AVOO" from MERCK, - silica, alumina and alginic acid such as the product "MT-100 AQO" from the company TAYCA, 5 - alumina and laura aluminum such as the product "MICROTITANIUM DIOXIDE MT 100 SO" from the company TAYCA, iron oxide and iron stearate such as the product "MICROTITANIUM DIOXIDE MT 100 FO" from the company TAYCA, - d ' zinc oxide and zinc stearate such as the product "BR 351O" from the company TAYCA, silica-alumina and treated with a silicone such as the products "MICROTITANIUM DIOXIDE MT 600 SASO", "MICROTITANIUM DIOXIDE MT 500 SASO "or" MICROTITANIUM DIOXIDE MT 100 SASO "from TAYCA, 15 - silica, alumina, aluminum stearate and treated with a silicone such as the product" STT-30-DSO "from TITAN KOGYO, of silica and treated with a silicone such as the product "UV-TITAN X 195O" from the company SACHTLEBEN PIGMENTS, and alumina treated with a silicone such as the products "TIPAQUE TTO-55 20 (S) ® "from the company ISHIHARA, or" UV TITAN M 262O "from SACHTLEBEN PIGMENTS, - triethanolamine such as the product" STT-65-S " from the company TITAN KOGYO, - stearic acid such as the product "TIPAQUE TTO-55 (C) O" of the company ISHIHARA, sodium hexametaphosphate such as the product "MICROTITANIUM DIOXIDE MT 150 WO" of the company Tayca. TiO 2 treated with octyl trimethyl silane sold under the trade name "T 805O" by the company Degussa Silices, TiO 2 treated with a polydimethylsiloxane sold under the trade name "70250 Cardre UF Ti025I3O" by CARDRE, TiO2 anatase / rutile treated with a polydimethylhydrogensiloxane sold under the trade name "MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBICO" by the company COLOR TECHNIQUES.

It is also possible to mention TiO 2 pigments doped with at least one transition metal such as iron, zinc, manganese and more particularly manganese. Preferably, said doped pigments are in the form of an oily dispersion. The oil present in the oily dispersion is preferably chosen from triglycerides including those of capric / caprylic acids. The oily dispersion of titanium oxide particles may additionally comprise one or more dispersing agents, for example a sorbitan ester such as sorbitan isostearate, a polyoxyalkylenated fatty acid and glycerol ester such as TRI-PPG3 MYRISTYLETHER CITRATE and POLYGLYCERYL-3 POLYRICINOLEATE. Preferably, the oily dispersion of titanium oxide particles comprises at least one dispersing agent chosen from fatty acid esters and polyoxyalkylenated glycerol. Mention may more particularly be made of the oily dispersion of manganese doped TiO 2 particles in capric / caprylic acid triglyceride in the presence of TRI-PPG-3 MYRISTYLETHER CITRATE and POLYGLYCERYL-3-POLYRICINOLEATE and SORBITAN ISOSTERATE INCI name: TITANIUM DIOXIDE (and) TRI-PPG-3 MYRISTYLETHER CITRATE (and) POLYGLYCERYL-3 RICINOLEATE (and) SORBITAN ISOSTEARATE as the product sold under the trade name OPTISOL TD50®by the company CRODA.

Uncoated titanium oxide pigments are for example sold by the company Tayca under the trade names "MICROTITANIUM DIOXIDE MT 500 B" or "MICROTITANIUM DIOXIDE MT600 B @", by the company DEGUSSA under the name "P 25", by the company WACKHER under the name "transparent titanium oxide PW @", by the company MIYOSHI KASEI under the name "UFTR @", by the company TOMEN under the name "ITS @" and by the company TIOXIDE under the name "TIOVEIL AQ ". The uncoated zinc oxide pigments are, for example: those marketed under the name "Z-cote" by the company Sunsmart; those marketed under the name "Nanox @" by the company Elementis; those marketed under the name "Nanogard WCD 2025®" by the company Nanophase Technologies; The coated zinc oxide pigments are, for example: those marketed under the name "Zinc Oxide CS-5®" by the company Toshibi (ZnO coated with polymethylhydrogenosiloxane); those marketed under the name "Nanogard Zinc Oxide FNC" by Nanophase Technologies (as a 40% dispersion in Finsolv TN®, C12-C15 alcohol benzoate); those marketed under the name "DAITOPERSION Zn-30®" and "DAITOPERSION Zn-50®" by the company Daito (dispersions in cyclopolymethylsiloxane / polydimethylsiloxane oxyethylenated, containing 30% or 50% of zinc oxides coated with silica and the polymethylhydrogensiloxane); Those marketed under the name "NFD Ultrafine ZnOC" by the company Daikin (ZnO coated with perfluoroalkylphosphate and copolymer based on perfluoroalkylethyl dispersed in cyclopentasiloxane); those marketed under the name "SPD-Z1C" by the company ShinEtsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); those marketed under the name "Escalol Z100®" by the company ISP (ZnO treated alumina and dispersed in the mixture methoxycinnamate ethylhexyl / PVP-hexadecene copolymer / methicone); those marketed under the name "Fuji ZnO-SMS-10®" by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); those marketed under the name "Nanox Gel TNC" by Elementis (ZnO dispersed at 55% in C12-C15 alcohols benzoate with hydroxystearic acid polycondensate). The uncoated cerium oxide pigments can be, for example, those sold under the name "Colloidal Cerium Oxidecp" by the company Rhone-Poulenc The uncoated iron oxide pigments are for example sold by the company ARNAUD under the names " NANOGARD WCD 2002® (FE 30 45B®) "," NANOGARD IRON FE 45 BL AQ "," NANOGARD FE 45R AQ®, "NANOGARD WCD 2006® (FE 45R®)", or by the company MITSUBISHI under the name "TY -220® ". The coated iron oxide pigments are for example sold by ARNAUD under the names "NANOGARD WCD 2008 (FE 45B FN) ®", "NANOGARD WCD 2009® (FE 45B 556®)", "NANOGARD FE 45 BL 345® "," NANOGARD FE 45 BLC) ", or by the company BASF under the name" OXYDE DE FER TRANSPARENTC ". Mention may also be made of mixtures of metal oxides, in particular of titanium dioxide and cerium dioxide, of which the titanium dioxide and silica-coated cerium dioxide equivalent compound, sold by the company IKEDA under the name "SUNVEIL" AC) ", as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as the product" M 261C "sold by SACHTLEBEN 10 PIGMENTS or coated with alumina, silica and glycerine such as the product "M 211C" sold by SACHTLEBEN PIGMENTS. According to the invention, titanium oxide pigments, coated or uncoated, are particularly preferred. The amount of UV filters depends on the desired end use. The UV filters according to the invention are preferably present in the compositions according to the invention at a content ranging from 0.1% to 45% by weight, and in particular from 5% to 30%, by weight, relative to the total weight. The present invention also relates to the cosmetic use of a composition according to the invention as defined above for dyeing and / or pigmenting keratin materials, and / or promoting the pigmentation of keratin materials. More particularly, the present invention relates to the cosmetic use of a composition according to the invention as defined above for coloring and / or pigmenting the skin and / or promoting skin pigmentation. The present invention further relates to the cosmetic use of a composition according to the invention as defined above to ensure a browning of the skin and / or a tan of the skin and / or to intensify the tan, and / or to homogenize the complexion of the skin. Preferably the cosmetic use according to the invention is characterized in that said composition is applied to the skin. The present invention also relates to a cosmetic treatment method for dyeing and / or pigmenting keratin materials and / or promoting the pigmentation of keratin materials, characterized in that a composition is applied to said keratin materials. according to the invention as defined above. More particularly, the subject of the present invention is also a cosmetic treatment method for dyeing and / or pigmenting the skin and / or promoting the pigmentation of the skin, characterized in that a composition according to the invention is applied to the skin. as defined above. The present invention further relates to a cosmetic treatment method for ensuring a browning of the skin and / or a tan of the skin and / or for intensifying the tan, and / or for homogenizing the complexion of the skin. The cosmetic compositions according to the invention may, for example, be used as a skincare and / or sun protection product for keratin materials, in particular for the skin of the face and / or the body, of liquid to semi-liquid consistency, such as milks, creams more or less creamy, gel-creams, pasta. They may optionally be packaged in aerosol and be in the form of foam or spray. The compositions according to the invention in the form of vaporizable fluid lotions in accordance with the invention are applied to keratin materials, such as the skin and / or the hair, in the form of fine particles by means of pressurizing devices. The devices according to the invention are well known to those skilled in the art and include non-aerosol pumps or "atomizers", aerosol containers comprising a propellant and aerosol pumps using compressed air as a propellant. These are described in US Pat. Nos. 4,077,441 and 4,850,517. The aerosol-conditioned compositions according to the invention generally contain conventional propellants such as, for example, hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane and trichlorofluoromethane. They are preferably present in amounts ranging from 15 to 50% by weight relative to the total weight of the composition. Throughout the description, including the claims, the phrase "having one" should be understood as being synonymous with "having at least one", unless the opposite is specified.

Expressions "between ... and ..." and "from ... to ..." must be understood as inclusive terms unless otherwise specified. The following examples serve to illustrate the invention without being limiting in nature. The names are, as the case may be, in chemical names or International Cosmetic Ingredient Dictionary and Handbook (CTFA) names, and the percentages by weight unless otherwise indicated. EXAMPLE 1 Demonstration of the Modulating Effect on Melanogenesis MATERIAL AND METHOD Pigmented epidermis was reconstructed by inoculating normal human melanocytes and normal human keratinocytes onto a collagenous carrier, according to the protocol of EPISKIN. The following controls are carried out: - negative control: untreated; positive melanogenesis stimulation control: 10 nM of alpha 25 MSH The products tested are the following: the acetyl-hexapeptide-1 peptide (MELITANE @ GL 200 from Unipex Innovations), the active principle being at 200 ppm). 10 nM; - the peptide acetyl-hexapeptide-1 (MELITANE @ GL 200) at 10nM with the active N30 acetyl-L-tyrosine (N ac Tyrosine @ marketed by Sigma, code A2513) at 700pM; the peptide acetyl-hexapeptide-1 (MELITANE @ GL 200) at 10nM with the caffeine active ingredient (Caffeine® sold by the company Sigma, code 27600 Fulka) 35 50 μM;) the peptide acetyl-hexapeptide-1 (MELITANE® GL) 200) at 10nM with the two active N-acetyl-L-tyrosine (Sigma N ac Tyrosine®, code A2513) at 700pM and caffeine (Sigma Caffeine®, code 27600 Fulka) at 50pM Active treatment took place systemically, and was renewed every day except at weekends. from OJ (day of cell seeding) to D9 (day 9).

The histological quality of the epidermis after treatment is evaluated on histological sections after HES staining in order to determine the impact of the treatment on the epidermis. Also, the physiology of melanocytes is studied to detect possible melanocytotoxicity. If no histological alteration or melanotoxic effect of the evaluated products is revealed, quantification of the pigmentation is carried out by quantification of melanin on histological sections by image analysis (Fontana Masson stain) using the Histolab software. RESULTS: Reconstructed epidermis treated with 10nM alpha MSH and 10nM acetylhexapeptide-1 combined or not with 50pM caffeine and / or 700pM N-acetyl-Lysrosine have good histological quality, comparable to that of untreated control epidermides . There is no visible cytotoxic effect.

The physiological aspect of the melanocytes also remains unchanged after these different treatments showing the absence of cytotoxic effect of the products and the various combinations of active agents on the melanocytes. Histological sections stained by the Fontana Masson method were performed to reveal the melanin grains. Between 45 and 60 images corresponding to an identical length of epidermis were acquired by experimental condition. The area occupied by melanin was quantified in each image. The average number of pixels per image is compared.35 Melitane N Acetyl Caffeine Caffeine 50pM + N Acetyl Tyrosine 0.7mM 10nM Melitane + 0.7mM Nitro Tyrosine + Caffeine 50pM 10nM Tyrosine 50pM 0.7mM Acquired 42 61 39 38 31 58 Average number of pixels per image 20.6 102.2 37.8 32.5 24.2 162.6 Sem 1.7 5.7 3.2 2.8 2.1 6.7 Effects 396% 84% 58% 18 % 690% versus control Additive effect 3 individual actives 538% The results show a very significant pro-pigmenting effect of acetyl hexapeptide-1 compared to the untreated control (p-value <0.05). The pro-pigmenting effect obtained with the combination of the three active ingredients, acetylhexapeptide-1, N-acetyl-L-Tyrosine and caffeine is very significantly greater than the effect of acetyl-hexapeptide-1 alone, very significantly higher than the effect of N-acetyl-L-Tyrosine alone, and very significantly greater than the effect of caffeine alone. (P-value <0.05). The results also highlight an activation of the pigmentation of the skin by the combination of acetyl-hexapeptide-1 / N-acetyl-L-tyrosine / Caffeine (+ 690%) greater than the cumulation of the activations obtained with the compounds alone (+ 538%), thus demonstrating an unexpected synergistic effect. These results show that a composition comprising acetyl hexapeptide, N-acetyl-L-Tyrosine and caffeine is significantly more efficient for the propigmenting response than the addition of the effects of acetylhexapeptide-1, N -acetyl-L-Tyrosine and caffeine taken separately. Thus, surprisingly, a synergistic effect is observed when the three compounds are used in combination. EXAMPLE 2 The following compositions are prepared in a manner conventional to those skilled in the art: In these examples, the amounts of the ingredients of the compositions are given in% by weight of raw material relative to the total weight of the composition. EXAMPLE 2A: Direct Fluid Emulsion with Filtering System The aqueous A and oily B phases were prepared by mixing the raw materials with mechanical stirring at 80.degree. Once aqueous A and oily B solutions were macroscopically homogeneous, the emulsion was prepared by introducing phase B into phase A with stirring using a rotor-stator homogenizer under one speed. stirring of 4500 RPM for 20 minutes. The C2, C3 and then D phases were then introduced, and the emulsion was cooled to room temperature. After addition of the E, F and G phases, stirring was maintained for 10 min. The final emulsion is characterized by drops of size between 1 mm and 20 mm. Phase Ingredients% A WATER qs 100 GLYCERIN 5.00 Disodium salt of ethylene diamine tetracetic acid 0.10 ACETYL HEXAPEPTIDE-1; 200 ppm (MELITANE® 5.00 GL 200 from UNIPEX INNOVATIONS (ATRIUM BIOTECHNOLOGIES)) CAFFEINE (CAFEINE ANHYDROUS POWDER® 1.00 sold by the company BASF) N-ACETYL-L-TYROSINE (N-ACETYLTYROSINE ® 0.50 from PHARMAZELL) STEAROYL DISODIUM GLUTAMATE (MISOFT 0.50 HS 21P® from AJINOMOTO) B TROCOPHERYL ACETATE (DL ALPHA 0.20 3004 92 7 44 TOCOPHERYL ACETATE® marketed by the company DSM NUTRITIONAL PRODUCTS) CETYL ALCOHOL 0.50 MIXTURE LINEAR ALCOHOLS (C18 / C20 / C22) 1.00 (NAFOL 1822 C® marketed by SASOL) MONO-STEARATE OF POLYETHYLENE GLYCOL (100 OE) (MYRJ S100-PA- (SG) ® from CRODA) 0, MIXTURE OF CETYLSTEARYL GLUCOSIDE AND 0.32 OF CETYLIC ALCOHOLS, STEARYLIC (12/46/42) (MONTANOV 68® marketed by the company SEPPIC) ISOPRPYL ISOSTEARATE 1.50 cyano-3,3-diphenylacrylate of 2-ethyl Hexyl 3.00 (OCTOCRYLENE® sold by the company MFCI) BUTYL METHOXYDIBENZOYLMETHANE (EUSOLEX 3.00 9020® marketed by the company summer Merck) ETHYLHEXYL SALICYLATE (NEO HELIOPAN OS / H® sold by the company Symrise) 5,00 CONSERVATIVE 1,00 Cl AMPS COPOLYMER / ALCOHOL METHACRYLATE 0,50 C16 / C18 ETHOXYL (8 EO MOLES) 80/20 (ARISTOFLEX SNC® from Clariant) C2 Carboxyvinyl polymer (Synthalen K® from 3V) 0.07 C3 Copolymer acrylamide / acrylamido 2-methyl propane 1.30 sodium sulfonate in 40% inverse emulsion in isoparaffin / water (Sepigel 305® from at Seppic) D PTFE (FLUOROPURE 103 C® sold by 2.00 companies Shamrock Technologies) E Poly dimethylsiloxane mixture alpha-omega 2.50 dihydroxyl / poly dimethylsiloxane 5 cst; Dow Corning 1503 Fluid® marketed by the company Dow Corning Perfume 0,20 DIMETHICONE CO-POLYMER / VINYL 0,50 DIMETH ICON (DOW CORNING 9506 POWDER® marketed by Dow Corning) F Mixture of cross-linked poly (dimethylsiloxane) and poly (1) 50 dimethylsiloxane (6 cst) (24/76) (KSG 16® from Shin Etsu) G ALCOHOL DENATURE 2.00 This cosmetic composition can be used as a care product, such as a daily care product, with solar filter .

Example 2B: Emulsified gel Aqueous phase A was prepared by mixing the raw materials with mechanical stirring at 80 ° C.

While allowing the mixture to cool to room temperature, preparations B and then C (macroscopically homogeneous) were stirred with a rotor-stator homogenizer at a stirring speed of 4000 RPM for 20 minutes. minutes. Phases C1, C2 and C3 then D were then introduced and the emulsion was cooled to room temperature. After addition of the D and E phases, the stirring was maintained for 10 min. The final emulsified gel is characterized by drops of size between 1 mm and 20 mm. phase Ingredients% A WATER 24,64 Polyethylene glycol (20 OE) (CARBOWAX SENTRY POLYETHYLENE GLYCOL 1000 NF, FCC GRADE® 3.00 from Dow Chemical) Dimethylsiloxane oxyethylenated (16 OE) at the end 5.00 methoxy (DOW CORNING 2501 COSMETIC WAX @ from Dow Corning) GLYCERIN 5.00 DIPROPYLENE GLYCOL 8.00 PRESERVATIVE 0.00 ADENOSINE 0.04 Disodium salt of ethylene diamine tetracetic acid 0.10 B Carboxyvinyl polymer (Synthalen K @ from 3V) 0.40 Acid partially saturated with ammonia and highly crosslinked polyacrylamidomethyl propanesulfonic acid 0.20 (Hostacerin AMPS from Clariant) Xanthan gum (RHODICARE XC @ from 0.05 Rhodia) C WATER qs 100 ACETYL HEXAPEPTIDE-1; 200 ppm (MELITANE @ 5.00 GL 200 from UNIPEX INNOVATIONS (ATRIUM BIOTECHNOLOGIES)) CAFFEINE (CAFEINE ANHYDROUS POWDER @ 1.00 marketed by BASF) N-ACETYL-L-TYROSINE (N-ACETYLTYROSINE @ 0.50 from PHARMAZELL) BALLS OF POLY DIMETHYLSILOXANE 2.00 RETICLE GLOVES COATED WITH RESIN SILSESQUIOXANE (92/8) (KSP 100® from SHIN ETSU) WATER 1.00 TRIETHANOLAMINE 0.40 This cosmetic composition can be used as a product of care, such as a daily care product.

EXAMPLE 2C: Photoprotective composition The aqueous A and oily B phases were prepared by mixing the raw materials with mechanical stirring at 80 ° C.

Once aqueous A and oily B solutions were macroscopically homogeneous, the emulsion was prepared by introducing phase B into phase A with stirring using a rotor-stator homogenizer under one speed. stirring of 4500 RPM for 20 minutes. After returning to ambient temperature, phases B2 and C, D, E (macroscopically homogeneous) were then introduced with stirring. After addition of G, the final emulsion is characterized by drops of size between 1 mm and 20 mm.

Phase Ingredients% A WATER qs 100 Disodium salt of ethylene diamine tetracetic acid 0,20 PROPYLENE GLYCOL 6,00 GLYCERIN 6,00 XANTHAN GUM (RHODICARE XC® of 0,50 at Rhodia) B1 ALCOHOL CETEARYL (MINACARE OCTIOL®) 1.50 at MINASOLVE) MYRISTIC ALCOHOL PROPIONATE 3.00 OXYPROPYLENE (2 OP) (CRODAMOL PMP-LQ- (MH) ® from CRODA) STEARYL ALCOHOL OXYPROPYLENE (15 OP) 3.00 PROTECTED (ARLAMOL PS15E-LQ- (RB) @ from CRODA) STEARYL ALCOHOL / STEARATE MIXTURE 4.50 GLYCEROL / PEG STEARATE (75 MOLES) / CETYLIC ALCOHOLS AND STEARYLIC OXYETHYLENE (20%) (EMULIUM DELTA @ from GATTEFOSSE) C12 Alcohols / C15 (TEGOSOFT TN @ 5.00 at Goldschmidt) DIISOPROPYL SEBACATE 5.00 BIS-ETHYLHEXYLOXYPHENOL METHOXYPHENYL 1.00 TRIAZINE (TINOSORB S @ from BASF) DROMETRIZOLE TRISILOXANE (SILATRIZOLE @ 3.00 at RHODIA CHEMISTRY) DIETHYLAMINO HYDROXYBENZOYL HEXYL 1.00 BENZOATE (UVINUL A PLUS GRANULAR @ from BASF) BUTYL METHOXYDIBENZOYLMETHANE 3.00 (EUSOLEX 9020 @ c sold by the company Merck) ETHYLHEXYL SALICYLATE (NEO HELIOPAN 5.00 OS / H @ sold by the company Symrise) Cyano-3,3-diphenylacrylate of 2-ethylhexyl 3.50 (OCTOCRYLENE @ sold by the company MFCI) ETHYLHEXYL TRIAZONE (UVINUL T 150® 2.30 sold by the company BASF) CONSERVATIVE 1.1 B2 Poly dimethylsiloxane mixture alpha-omega 2.00 dihydroxyl / poly dimethylsiloxane 5 cst; Dow Corning 1503 Fluid @ marketed by the company Dow Corning Alcohol 3.00 D Corn starch esterified with anhydride 3.00 octenyl succinic, aluminum salt (Dry Flo Plus® from National Starch) E SILICA (SILICA BEAD SB 150® from MIYOSHI 2.00 KASEI) WATER 4.40 ACETYL HEXAPEPTIDE-1; 200 ppm (MELITANE® 5 GL 200 from UNIPEX INNOVATIONS (ATRIUM BIOTECHNOLOGIES)) CAFFEINE (CAFFEINE ANHYDROUS POWDER® 1 sold by the company BASF) N-ACETYL-L-TYROSINE (N-ACETYLTYROSINE® 0.5 from PHARMAZELL) G ACID CITRIC 0.12 This cosmetic composition can be used as a sunscreen product, such as sunscreen.

These compositions according to the invention, applied to the skin, make it possible to dye and / or pigment keratinous substances, and / or to promote the pigmentation of keratin materials, such as the skin. These compositions according to the invention, applied to the skin, also make it possible to ensure a browning of the skin and / or a tan of the skin and / or the intensification of tanning, and / or the homogenization of the complexion of the skin. skin.

Claims (15)

REVENDICATIONS1. A composition comprising, in a physiologically acceptable medium, at least a) a peptide having the formula (I) R-V1-Ala2-H is3-X4-Y5-Trp6-N H2 (I) wherein - R represents an atom hydrogen or a protecting group which may be selected from an acetyl group, a benzoyl group, a tosyl group, a benzenesulphonyl group, a benzyloxycarbonyl group or a pyridinepropionyl group; - represents a naturally occurring or non-naturally occurring amino acid of configuration L, chosen from norleucine, norvaline and 2-N-Me-norleucine, 15-X represents a natural or non-natural amino acid, of L or D configuration, of aromatic character selected from phenylalanine, 1-naphthylalanine, 2-naphthylalanine, phenylglycine, benzothienylalanine, 4,4'-biphenylalanine , 3,3-diphenylalanine, homophenylalanine, indanylglycine, 4-methylphenylalanine, thienylalanine, p-nitro-phenylalanine, halophenylalanine where the halogen is selected from a chlorine, bromine, iodine or fluorine atom in meta, ortho or Y is a natural amino acid of L configuration, of basic character selected from arginine, lysine or ornithine, as well as its optical isomers, the amino acids Ala, His and Trp, respectively, positions 2,3 and 6 being of configuration L; b) a xanthic base of general formula (II) wherein R1, R2 and R3 represent, independently of one another, a hydrogen atom or a linear or branched C1-C4 alkyl radical, as well as its optical isomers and its tautomers; etc) a compound corresponding to the formula (III) CH-COR7 NHR4 (III) C H2 in which - R4 represents a hydrogen atom, a hydroxy, or a group -CO- - R5 represents a hydroxyl radical, or a group -Si (OH) 2R9, - R6 represents a hydrogen atom or a hydroxyl radical, - R7 represents a radical -O-M, - M represents a hydrogen atom; a linear or branched C1-C4 alkyl radical; or a metal cation which is alkaline, alkaline earth metal or a transition metal, - R8 represents a saturated, linear or branched C1-C20 alkyl; alkylene, linear or branched, C2-C20; a -CH 2 NH 2 group; a hydroxy radical; or a linear or branched C2-C20 ketone group; Rg represents a linear or branched C1-C4 alkyl radical, as well as its optical isomers. 2. Composition according to Claim 1, characterized in that the peptide corresponds to formula (I) in which: R represents a protective group which may be chosen from an acetyl group, a benzenesulphonyl group, a tosyl group or a pyridinepropionyl group, - V represents a natural amino acid or not selected from norleucine and 2N-Me-norleucine, configuration L. - X represents a natural or non-aromatic amino acid selected from phenylalanine, 2-naphthylalanine, homophenylalanine the thienylalanine or p-nitro-phenylalanine, of D or L-Y configuration, represents a natural amino acid of L configuration, with a basic character chosen from arginine or lysine. Alanine, histidine and tryptophan, at positions 2, 3 and 6, respectively, in the peptide of formula (I) are of L configuration. 3. Composition according to claim 1 or 2, characterized in that the peptide corresponding to formula (I) is Ac-Nle-Ala-His-DPhe-Arg-Trp-NH2. 4. Composition according to any one of claims 1 to 3 characterized in that the xanthine base has the formula (II) wherein R1, R2 and R3 represent independently of each other a hydrogen atom or methyl radical. 5. Composition according to any one of claims 1 to 4 characterized in that the xanthine base of formula (II) is selected from the group consisting of 1,3-dimethylxanthine, 3,7-dimethylxanthine, 1,3 7-trimethylxanthine and 1,7-dimethylxanthine. 6. Composition according to claim 5 characterized in that the xanthan base of formula (II) is 1,3,7-trimethylxanthine. 7. Composition according to any one of claims 1 to 6 characterized in that the compound has the formula (III) wherein: - R4 represents a hydrogen atom, a hydroxyl or a group -CO-Ra, - R5 represents a hydroxy radical, or a group -Si (OH) 2R9, -R6 represents a hydrogen atom, -R7 represents a radical -O-M, -M represents a hydrogen atom; a methyl group; or a metal cation which is alkaline such as sodium or potassium, alkaline earth such as calcium, or magnesium, or a transition metal such as copper, - R8 represents an alkyl which is selected from a methyl group; a linear C5-C10 saturated alkyl, a linear C15-C20 alkylene; a -CH 2 NH 2 group; or a group - (CH 2) 6 -CO (CH 2) 6 -Cl-13, - R 6 represents a methyl radical. 8. Composition according to any one of claims 1 to 6 characterized in that the compound of formula (III) is selected from the group consisting of N-acetyl-L-tyrosine, N-hydroxy-L-tyrosine , N-ethanoyltyrosine, tyrosine, glycin-tyrosine, caproyl tyrosine, capryloyl tyrosine, oleoyl acetyl tyrosine, glycyl-L-tyrosine, N-acetyl methylsilanol-tyrosine, N-acetyl methylsilanol tyrosine, Copper, oleyl acetyl tyrosine, potassium N-caproyl-tyrosinate, methyl capryloyl tyrosinate, L3,4-dihydroxyphenylalanine, and hexyldioxodecyl-methyl tyrosinate. 9. Composition according to any one of claims 1 to 8, characterized in that the compound corresponding to formula (III) is N-acetyl-L-tyrosine. 10. Composition according to any one of Claims 1 to 9, characterized in that the peptide corresponding to formula (I) is Ac-Nle-Ala-His-DPhe-Arg10 Trp-NH, the xanthic base of formula ( II) is 1,3,7-trimethylxanthine, the compound of formula (III) is N-acetyl-L-tyrosine. 11. Composition according to any one of claims 1 to 10, characterized in that said peptide corresponding to formula (I) is present in the composition at a content of between 0.0001% and 1%, weight relative to the total weight. of the composition, in particular is present in a content of between 0.001% and 0.5%, by weight relative to the total weight of the composition, and is particularly present at a content of between 0.001% and 0.1%, by weight relative to the total weight of the composition, more particularly the peptide of formula (I) is present in the composition at a content of 0.001%, by weight relative to the total weight of the composition. 12. Composition according to any one of claims 1 to 11, characterized in that said xanthine base of formula (II) is present in the composition at a content of between 0.01% and 10%, weight relative to the total weight of the composition, in particular, is present in a content of between 0.01% and 5%, by weight relative to the total weight of the composition, and is particularly present in a content of between 0.1% and 3% by weight relative to to the total weight of the composition, more particularly the xanthine base of formula (II) is present in the composition at a level of 1%, by weight relative to the total weight of the composition. 13. Composition according to any one of claims 1 to 12, characterized in that said compound corresponding to formula (III) is present in the composition at a content of between 0.01% and 10%, weight relative to the total weight. of the composition, in particular, is present in a range of between 0.01% and 5%, by weight relative to the total weight of the composition, and is particularly present in a content of between 0.1% and 3% by weight relative to to the total weight of the composition, more particularly the xanthine base of formula (II) is present in the composition at a content of 0.5%, by weight relative to the total weight of the composition. 14. Cosmetic use of a composition as defined in any one of claims 1 to 13 for dyeing and / or pigmenting keratin materials, and / or promoting the pigmentation of keratin materials. 15. Cosmetic treatment process for dyeing and / or pigmenting keratin materials, and / or promoting the pigmentation of keratin materials, such as the skin, the scalp and / or the hair, characterized in that it applies on said keratin materials a composition as defined according to any one of claims 1 to 13.