WO2014177406A1 - Composition comprising at least three active agents for colouring and/or pigmenting keratin materials - Google Patents

Abstract

The present invention relates to a composition comprising, in a physiologically acceptable medium, at least: - one peptide corresponding to formula (I): R-V¹-Ala²-His³-X⁴-Y⁵-Trp⁶-NH₂; - one xanthine base chosen from the group consisting of 3,7-dimethylxanthine, 1,3,7-trimethylxanthine and 1,7-dimethylxanthine, and - one compound corresponding to formula (III). The present invention also relates to the cosmetic use of such a composition for colouring and/or pigmenting keratin materials and/or promoting the pigmentation of keratin materials, and also to a cosmetic treatment process.

Description

Composition comprising at least three active agents for colouring and/or pigmenting keratin materials

The present invention relates to a composition comprising, in a physiologically acceptable medium, a combination of at least three active agents, and also to the use of this composition for colouring 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 the skin and/or giving the skin a tan and/or for strengthening the tan, and/or for making the complexion uniform, and also to a cosmetic treatment process.

The colour of human skin depends on various factors and in particular the seasons of the year, race, sex and age. It is mainly determined by the concentration, in the keratinocytes, of melanin produced by the melanocytes. Melanocytes are specialized cells which, by means of particular organelles, the melanosomes, synthesize melanin.

Melanin synthesis or melanogenesis is particularly complex and schematically involves 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 sequence of reactions. In particular, it catalyzes the conversion reaction of tyrosine to give Dopa (dihydroxyphenylalanine) and the conversion reaction of Dopa to give dopaquinone.

In the epidermis, the melanocyte is involved in the epidermal melanin unit which comprises a melanocyte surrounded by approximately 36 neighboring keratinocytes. All individuals, without phototype distinction, have approximately the same number of melanocytes for a given area of skin. Ethnic differences, in terms of pigmentation, are not due to the number of melanocytes, but to the properties of their melanosomes. Melanosomes are aggregated in complexes and are small in size. These are highly specialized organelles, the sole function of which is melanin production. They arise from the endoplasmic reticulum in the form of spherical vacuoles called premelanosomes. Premelanosomes contain an amorphous protein substrate, but no melanogenic enzymes. During maturation of the premelanosome, the amorphous substrate is organized into a fibrillar structure oriented along the longitudinal axis of the melanosome. Four stages of development of the melanosome are distinguished, corresponding to the intensity of the melanization. Melanin is deposited uniformly on the internal fibrillar network of the melanosome and the opacity of the organelle increases until saturation occurs. As the melanin is synthesized in the melanosomes, the latter move from the perinuclear region to the end of the melanocyte dendrites. By means of phagocytosis, the end of the dendrites is taken up by the keratinocytes, the membranes are degraded and the melanosomes are redistributed in the keratinocytes.

Although the level of melanin varies from one population to another, the amount of tyrosinase does not significantly vary and the level of tyrosinase RNA messengers is identical in white or black skins. Variations in melanogenesis are therefore due to variations either in tyrosinase activity or in the ability of keratinocytes to phagocytose melanosomes.

Nowadays, it is important to look healthy, and a tanned skin is always a sign of good health. However, a natural tan is not always desirable since it requires prolonged exposure to UV radiation, in particular to UV-A radiation. This radiation causes browning of the skin but, on the other hand, it is liable to induce an adverse change therein, in particular in the case of sensitive skin or of continual exposure to solar radiation. The skin ages prematurely, becomes dry and is characterized by numerous wrinkles and age spots. It is thus desirable to find an alternative to a natural tan that is compatible with the requirements of such skin types.

There is therefore a real need for a product which facilitates and/or improves the pigmentation of the skin.

Many solutions have been proposed in the artificial colouring field.

In the field of exogenous colouring agents, dihydroxyacetone, or DHA, is a particularly advantageous product which is commonly used in cosmetics as an agent for artificially tanning the skin; when applied to the skin, in particular to the face, it makes it possible to achieve a tanning or browning effect which is similar in appearance to that which may result from prolonged exposure to sunlight (natural tan) or under a UV lamp.

Erythrulose is also a substance that is used for the same purpose. These compounds act by binding to the amino acids, peptides and proteins of the stratum corneum, according to the Maillard reaction (non-enzymatic reaction between a sugar and an amine).

These colourations obtained with compounds of self-tanning type as previously defined appear after a few hours but disappear quite rapidly, and are not always uniformly distributed on the skin.

In order to obtain colourations which last over time, it has been proposed in the prior art to act directly on the biological process of melanogenesis, so as to stimulate melanin biosynthesis. Thus, the preparation and the use of melanogenesis activators have been widely illustrated, these activators being either substrates for melanin biosynthesis or stimulators of melanin biosynthesis. It has in particular been described that acetyl hexapeptide-1 , described in patent FR 2 835 528, also known under the trade name Melitane®, is a synthetic peptide which is an MC1 R ligand and which has a melanotropic activity. Indeed, the activation of the MC1 R receptor of melanocytes by its natural ligand alpha-MSH (Melanocyte Stimulating Hormone) stimulates melanin synthesis in keratin materials such as the skin. This alpha-MSH/MC1 R pathway is acknowledged to be a main biological pathway activated by UV radiation and involved in tanning of the skin.

The Applicant has now discovered, surprisingly, that the combination of at least one peptide corresponding to formula (I) as defined hereinafter, with a xanthine base as defined hereinafter, and with a compound corresponding to formula (III) as defined hereinafter, considerably potentiates the pigmentation of keratin materials, such as the skin.

Unexpectedly, the colouration of keratin materials, such as the skin, and the pigmentation thereof, obtained by means of the combination of the three active agents (compounds of formulae (I), (II) and xanthine base) according to the invention is amplified and is stronger compared with that obtained by adding the effects of the various active agents taken individually. A subject of the present invention is thus a composition comprising, in a physiologically acceptable medium, at least

a) one peptide corresponding to formula (I) R-V¹-Ala²-His³-X⁴-Y⁵-Trp⁶-NH₂ (I) in which:

- R represents a hydrogen atom or a protective group which can be chosen from an acetyl group, a benzoyl group, a tosyl group, a benzenesulfonyl group, a benzyloxycarbonyl group or a pyridinepropionyl group,

- V represents a natural or unnatural amino acid, of L configuration, chosen from norleucine, norvaline and 2-N-Me-norleucine,

- X represents a natural or unnatural amino acid, of L or D configuration, which is aromatic in nature, chosen from phenylalanine, 1 -naphthylalanine, 2- naphthylalanine, phenylglycine, benzothienylalanine, 4,4'-biphenylalanine, 3,3- diphenylalanine, homophenylalanine, indanylglycine, 4-methylphenylalanine, thienylalanine, p-nitrophenylalanine, and halophenylalanine, where the halogen is chosen from a chlorine, bromine, iodine or fluorine atom in the meta, ortho or para position with respect to the phenyl group,

- Y represents a natural amino acid of L configuration, which is basic in nature, chosen from arginine, lysine or ornithine,

and also optical isomers thereof, the Ala, His and Trp amino acids respectively in positions 2, 3 and 6 being of L configuration;

b) one xanthine base which is chosen from the group consisting of 3,7- dimethylxanthine, 1 ,3,7-trimethylxanthine and 1 ,7-dimethylxanthine ; and

c) one compound corresponding to formula (III)

(III)

in which:

- R₄ represents a hydrogen atom, a hydroxyl or a -CO-Rs group,

- R₅ represents a hydroxyl radical or an -Si(OH)₂Rg group,

- R6 represents a hydrogen atom or a hydroxyl radical,

- R₇ represents an -O-M radical,

- M represents a hydrogen atom; a linear or branched Ci-C₄ alkyl radical a metal cation which is an alkali metal, an alkaline-earth metal or a transition metal,

- Rs represents a linear or branched, saturated C1-C20 alkyl; a linear or branched C2-C20 alkylene; a -CH₂NH₂ group; a hydroxyl radical; or a linear or branched C2-C20 ketone group,

- R9 represents a linear or branched Ci-C₄ alkyl radical,

and also optical isomers thereof.

For the purposes of the present invention, the term "physiologically acceptable medium" is intended to mean a medium suitable for the topical administration of a composition, and compatible with all the keratin materials of human beings, such as the skin, the lips, the nails, the mucous membranes, the eyelashes, the eyebrows, the scalp and/or the hair, or any other area of bodily skin.

According to the invention, a physiologically acceptable medium is preferentially a cosmetically acceptable medium, that is to say a medium which is devoid of unpleasant odour or appearance and which is entirely compatible with the topical administration route.

By way of example, the composition according to the invention may be intended to be administered topically, that is to say by application at the surface of the keratin material under consideration, such as the skin under consideration.

The term "keratin materials" according to the invention is intended to mean the skin, of the body, face and/or area around the eyes, the lips, the nails, the mucous membranes, the eyelashes, the eyebrows, body hair, the scalp and/or the hair, or any other area of bodily skin. 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 are the skin.

The term "skin" is intended to mean all of the skin of the body, and preferably the skin of the face, of the neckline, of the neck, of the arms and forearms, or even more preferably still the skin of the face, in particular of the forehead, nose, cheeks, chin and area around the eyes. The composition of the invention can be a cosmetic or dermatological composition. Preferentially, 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 intended 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 body-hair and head- hair systems, the nails, the lips and the oral mucous membranes, with a view, exclusively or mainly, to cleaning them, making them more attractive, fragrancing them, modifying their appearance, protecting them, keeping them in good condition, or correcting body odours.

According to the invention, Ac= acetyl; Nle= norleucine; Ala= alanine; His= histidine; DPhe= D-phenylalanine (or phenylalanine in the D configuration); Arg= arginine; and Trp= tryptophan.

According to the invention, the expression "optical isomers of compounds" is intended to mean the enantiomers or diastereoisomers thereof, and also mixtures thereof, including racemic mixtures.

The peptides of formula (I) may comprise one or more asymmetric carbon atoms. According to the invention, the peptides of formula (I) comprise the optical isomers thereof. They may exist in the form of enantiomers or of diastereoisomers. These enantiomers and diastereoisomers, and also mixtures thereof, including racemic mixtures, form 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 using the processes described in application FR 2 835 528. Among the peptides corresponding to 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 can be chosen from an acetyl group, a benzenesulfonyl group, a tosyl group or a pyridinepropionyl group,

- V represents a natural or unnatural amino acid chosen from norleucine and 2N-Me-norleucine, of L configuration, - X represents a natural or unnatural amino acid which is aromatic in nature, chosen from phenylalanine, 2-naphthylalanine, homophenylalanine, thienylalanine or p-nitrophenylalanine, of D or L configuration,

- Y represents a natural amino acid of L configuration, which is basic in nature, chosen from arginine or lysine,

- the alanine, histidine and tryptophan, respectively in positions 2, 3 and 6 in the peptide of formula (I) are of L configuration.

More particularly, the peptide of formula (I) is chosen from:

- Ac-Nle-Ala-His-DPhe-Arg-Trp-NH₂,

- Ac-Nle-Ala-His-DPhe-Lys-Trp-NH₂,

- Ac-Nle-Ala-His-DThi-Arg-Trp-NH₂,

- BzlSO₂-Nle-Ala-His-DPhe-Arg-Trp-NH₂,

- Tos-Nle-Ala-His-DPhe-Arg-Trp-NH₂,

- BzlSO₂-Nle-Ala-His-DPhe-Lys-Trp-NH₂,

- BzlSO₂-Nle-Ala-His-DpNO₂Phe-Lys-Trp-NH₂,

- BzlSO₂-Nle-Ala-His-DThi-Lys-Trp-NH₂,

-Ac-Nle-Ala-His-DThi-Lys-Trp-NH₂,

-PyrProp-Nle-Ala-His-DpNO₂Phe-Lys-Trp-NH₂,

- PyrProp-Nle-Ala-His-DpNO₂Phe-Arg-Trp-NH₂,

- 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,

enantiomers and diastereoisomers thereof, and also mixtures thereof, including racemic mixtures.

According to the present invention:

- Ac represents an acetyl group,

- BzlSO₂ represents a benzenesulfonyl group,

- PyrProp represents a pyridinepropionyl group,

- Tos represents a tosyl group,

- DHomoPhe represents homophenylalanine of D configuration,

- DThi represents thienylalanine of D configuration,

- DpNO₂Phe represents p-nitrophenylalanine of D configuration,

- L₂, Nap represents 2-naphthylalanine of L configuration,

- DPhe represents phenylalanine of D configuration,

- Nle represents norleucine of L configuration, - NMe-Nle represents 2-N-Me-norleucine of L configuration.

Advantageously, the peptide corresponding to formula (I) is Ac-Nle-Ala-His- DPhe-Arg-Trp-NH₂.

The peptide is Ac-Nle-Ala-His-DPhe-Arg-Trp-NH₂ or N-acetyl-L-norleucine- alanine-histidine-D-phenylalanine-arginine-tryptophan (INCI name: ACETYL HEXAPEPTIDE-1 ). Such a peptide may be sold under the name Melitane® by the company Lucas Meyer Cosmetics (formerly Unipex Solutions). Preferably, said acetyl hexapeptide-1 peptide is in a mixture of water, glycerol and dextran (0.02%). Such a peptide is sold 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 sold under the name Melitane® BG by the "Institut Europeen de Biologie Cellulaire" [European Cell Biology Institute].

The acetyl hexapeptide-1 peptide may also be in solution in a mixture of water and dextran. Such a peptide is sold under the name Melitane® PS by the "Institut Europeen de Biologie Cellulaire" [European Cell Biology Institute].

The acetyl hexapeptide-1 peptide may also be in the form of a powder as a mixture with dextran. Such a peptide is sold under the name Melitane® PP by the "Institut Europeen de Biologie Cellulaire" [European Cell Biology Institute].

The peptide of formula (I) may be present in the composition in 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 in 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 in a content of 0.001 % by weight relative to the total weight of the composition.

According to the invention, a xanthine base is chosen from the group consisting of 3,7-dimethylxanthine, 1 ,3,7-trimethylxanthine and 1 ,7- dimethylxanthine. The xanthine bases used in the compositions according to the present invention are commercially available, or can be easily prepared by those skilled in the art according to the conventional synthesis methods. More particularly, a composition according to the invention comprises a xanthine base 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 the conventional synthesis methods, for instance those described in:

- "Synthetic caffeine" by 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), 1 1 -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 for synthesizing caffeine I (R1 = R2 = R3 = Me). The methylation of xanthine I (R1 = R2 = R3 = H) with (MeO)₂CO in DMF in the presence of 1 ,4,7,10,13,16-hexaoxacyclooctadecane results in the obtaining of 74% of I (R1 = R2 = R3 = Me). Likewise, caffeine has been prepared with a yield of 78% and 67% starting from I (R1 = R3 = Me, R2 = H; R1 = R2 = Me, R3 = 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 document describes an inexpensive and original method for synthesizing caffeine from uracil in six simple steps. Uracil is first converted to 1 ,3-dimethyluracil, followed by a step of nitration, reduction, then cyclization to theophylline and, finally, methylation of the theophylline to form caffeine.

Caffeine or 1 ,3,7-trimethylxanthine (CAS: 58-08-02) can in particular be in the form of an anhydrous powder, and is sold under the name AEC Caffeine Powder® by A & E Connock (Perfumery & Cosmetics) Ltd.

By way of example, caffeine is also sold under the name Caffeine® by the company EMD Chemicals Inc., under the name Caffeine® by the company Merck KGaA /EMD Chemicals, Inc., under the name Camellia Sinensis® by the company M.M.P., Inc., under the name OriStract CF® by the company Orient Stars LLC, and under the name Cafeine Anhydre Poudre® by the company BASF.

Caffeine is also manufactured and sold by the company Sigma Aldrich, Caffeine® (code 27600 Fulka), or under the name C0750-Caffeine powder, ReagentPlus®.

Theobromine, or 3,7-dimethylxanthine, is an alkaloid that can be extracted from the cacao seed, Theobroma cacao, of the family sterculiaceae; it is also found in small amounts in tea and coffee. By way of example, theobromine is sold under the name OriStar TBM ® by the company Orient Stars LLC, under the name Teobromina/Theobromine ® by the company Ricerca & Comunicazione s.r.l., or under the name T4500-Sigma® by the company 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 xanthine base may be present in the composition in 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 in a content of between 0.1 % and 3% by weight relative to the total weight of the composition. More particularly, the xanthine base is present in the composition in 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:

- R₄ represents a hydrogen atom, a hydroxyl or a -CO-Rs group,

- R₅ represents a hydroxyl radical or an -Si(OH)₂R9 group,

- R6 represents a hydrogen atom,

- R₇ represents an -O-M radical,

- M represents a hydrogen atom; a methyl group; or a metal cation which is an alkali metal such as sodium or potassium, an alkaline-earth metal or a transition metal such as copper,

- Rs represents an alkyl which is chosen from a methyl group; a saturated linear C5-C10 alkyl; a linear C15-C20 alkylene; a -CH₂NH₂ group; or a -(CH₂)6-CO(CH₂)6-CH3 group,

- R₉ 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,

- Rs represents an alkyl which is chosen from a methyl group; a saturated linear C5-C10 alkyl; a linear C17 alkylene; or a -CH₂NH₂ group.

The compounds of formula (III) used in the compositions according to the present invention are commercially available, or can be easily prepared by those skilled in the art according to the conventional synthesis methods.

In the context of the present invention, unless otherwise indicated, a C_x-C_y alkyl denotes a linear or branched, saturated alkyl group comprising from x to y carbon atoms.

Preferentially, the linear or branched, saturated Ci-C₂o alkyl groups can 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.

Preferentially, the linear or branched, saturated Ci-C₂o alkyl group is methyl, a heptyl or a nonyl.

In the context of the present invention, a C_x-C_y alkylene denotes a linear or branched alkylene group comprising from x to y carbon atoms.

Preferentially, the linear or branched C₂-C₂o alkylene groups can 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. Preferentially, the linear or branched, unsaturated C1-C20 alkenyl group is heptadecyl-8-ene.

In the context of the present invention, a linear or branched C2-C20 ketone group denotes a linear or branched ketone group comprising from 2 to 20 carbon atoms.

More particularly, said ketone group is a linear or branched C2-C15 ketone group. Preferentially, said ketone group is the -(CH₂)6-CO(CH₂)6-CH₃ group.

In the context of the present invention, a metal cation is an alkali metal, an alkaline-earth metal, or a transition metal such as copper. Preferentially, an alkali metal cation is sodium or potassium. Preferentially, an alkaline-earth metal cation is calcium or magnesium. Preferentially, the transition metal is copper. In the context of the present invention, the optical isomers are in particular the enantiomers and the diastereoisomers, and also the racemic mixture thereof.

More particularly, a compound corresponding to formula (III) is chosen from the group consisting of N-acetyl-L-tyrosine, N-hydroxy-L-tyrosine, N- ethanoyltyrosine (INCI name: acetyl tyrosine methyl), tyrosine, glycine-tyrosine, caproyl tyrosine, capryloyl tyrosine, oleoyl acetyl tyrosine, glycyl-L-tyrosine (INCI name: glycyl-L-tyrosine dihydrate), N-acetyl methylsilanol-tyrosine (INCI name methylsilanol acetyl-tyrosine), copper N-acetyl tyrosinate methylsilanol (INCI name: copper acetyl tyrosinate methylsilanol), oleyl acetyl tyrosine, potassium N-caproyl tyrosinate (INCI name: potassium caproyl tyrosine), methyl capryloyl tyrosinate (INCI name: methyl capryloyl tyrosinate), L-3,4- dihydroxyphenylalanine, and hexyldioxodecyl methyl tyrosinate (INCI name: hexyldioxodecyl methyl tyrosinate).

Unless specifically mentioned, the INCI names are used.

Preferably, the compound corresponding to formula (III) is N-acetyl-L-tyrosine or acetyl tyrosine.

N-Acetyl-L-tyrosine can be easily prepared by those skilled in the art according to tyrosine acylation methods.

Methods for preparing N-acetyl-L-tyrosine are, for example, those described in: - patent application CN1594283 "Preparation of N-acetyl-L-tyrosine" by Liu, Aifu, Fanning Zhuanli Shenqing Gongkai Shuomingshu, which describes a method comprising a step of acetylation of L-tyrosine with an acylating agent (acetic anhydride in the molar ratio of 1 :3-5) at 50-80°C for 45 to 75 minutes, then concentration, elimination of the acid, then crystallization to give the crude product, dissolution of the crude product in water at 75-80°C, discolouration, 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" by Stella, Selvaraj; Chadha, Anju, Tetrahedron: Asymmetry (2010), 21 (4), 457-460; this document indicates in particular that whole Candida parapsilosis ATCC 7330 cells were used to resolve the N- acetylated amino acid esters. Good enantioselectivities (E = 40 > 500) were obtained for the resolution of the N-protected protein and the esters of the nonprotein amino acid, which give good yields (28-50%) and high enantiomeric excesses (up to > 99%) for the two enantiomers.

By way of example, N-acetyl-L-tyrosine is sold under the name Melanowhite- A® by the company lchimaru Pharcos Company, Ltd., or under the name Tanogen HB® by the company Caribia, Inc.. By way of example, N-acetyl-L- tyrosine is manufactured and sold by the company PharmaZell GmbH under the name N-AcetylTyrosine®, and also by the company Sigma-Aldrich N-Acetyl-L- Tyrosine® (code A2513 Sigma).

By way of example, hexyldioxodecyl methyl tyrosinate is sold under the name K6EAAL-19® by the company NeoPharm Co., Ltd.; caproyi tyrosine is sold under the name Tyrosinol® by the company Sinerga S.P.A; glycyl-L-tyrosine dihydrate by the company Kyowa Hakko Kogyo Co., Ltd; methylsilanol acetyltyrosine is sold under the name Tyrosilane® by the company Exsymol; oleoyl tyrosine is sold under the name TYR-OL® by the company Sederma, Inc./Croda Inc.; tyrosine is sold 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 Chimie Fine; potassium caproyi tyrosine is sold under the name Tyrostan® by the company Sinerga S.P.A; methyl capryloyl tyrosinate is sold under the name Defensamide-8® by the company Neopharm Co., Ltd.

The compound of formula (III) may be present in the composition in 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 in a content of between 0.1 % and 3% by weight relative to the total weight of the composition. More particularly, the compound of formula (III) is present in the composition in a content 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, one compound of formula (III) which is N-acetyl tyrosine, and one xanthine base which is 1 ,3,7- trimethylxanthine, or caffeine.

The compositions according to the invention may be prepared according to the techniques that are well known to those skilled in the art.

The compositions of the invention may be in any galenical form conventionally used, in particular for topical application, and such as in the form of aqueous, aqueous/alcoholic or oily solutions, of oil-in-water (O/W), water-in-oil (W/O) or multiple (triple: W/O/W or O/W/O) emulsions, of aqueous or oily gels, of liquid, pasty or solid anhydrous products, or of dispersions of a fatty phase in an aqueous phase using spherules, it being possible for these spherules to be polymeric nanoparticles, such as nanospheres and nanocapsules, or lipid vesicles of ionic and/or non-ionic type. These compositions are prepared according to the usual methods.

The compositions according to the invention may be more or less fluid and may have the appearance of a white or coloured cream, a cream-gel, an ointment, a milk, a lotion, a serum, a paste or a foam. They may optionally be packaged in aerosol form and may be applied to the skin in the form of a foam or a spray. They can also be in solid form, for example in the form of a stick.

The compositions according to the invention may also be in anhydrous form, for instance in the form of an oil. The term "anhydrous composition" is intended to mean a composition containing less than 1 % by weight of water, or even less than 0.5% of water, and in particular 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 of the liposoluble and lipophilic ingredients and the fatty substances used for the formulation of the compositions of the invention. The term "oil" is intended to mean any fatty substance that is in liquid form at ambient temperature (20-25°C) and at atmospheric pressure (760 mmHg).

An oil that is suitable for use in the invention may be volatile or non-volatile. An oil that is suitable for use in the invention may be chosen from hydrocarbon- based oils, silicone oils and fluoro oils, and mixtures thereof.

A hydrocarbon-based oil that is suitable for use in the invention may be an animal hydrocarbon-based oil, a plant hydrocarbon-based oil, a mineral hydrocarbon-based oil or a synthetic hydrocarbon-based oil.

An oil that is suitable for use in the invention may be advantageously chosen from mineral hydrocarbon-based oils, plant hydrocarbon-based oils, synthetic hydrocarbon-based oils and silicone oils, and mixtures thereof.

For the purposes of the present invention, the term "silicone oil" is intended to mean an oil comprising at least one silicon atom, and in particular at least one Si-O group. The term "hydrocarbon-based oil" is intended to mean an oil comprising mainly hydrogen and carbon atoms.

The term "fluoro oil" is intended to mean an oil comprising at least one fluorine atom.

A hydrocarbon-based oil that is suitable for use in the invention may also optionally comprise oxygen, nitrogen, sulfur and/or phosphorus atoms, for example in the form of hydroxyl, amine, amide, ester, ether or acid groups, and in particular in the form of hydroxyl, ester, ether or acid groups.

The oily phase generally comprises, in addition to the lipophilic UV-screening agent(s), at least one volatile or non-volatile hydrocarbon-based oil and/or one volatile and/or non-volatile silicone oil.

For the purposes of the invention, the term "volatile oil" is intended to mean an oil that is capable of evaporating on contact with the skin or the keratin fibre 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 which have a non-zero vapour pressure, at ambient temperature and atmospheric pressure, ranging 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).

The term "non-volatile oil" is intended to mean an oil that remains on the skin or the keratin fibre at ambient temperature and atmospheric pressure for at least several hours, and that in particular has a vapour pressure of less than 10^"3 mmHg (0.13 Pa).

Hydrocarbon-based oils Mention may in particular be made, as non-volatile hydrocarbon-based oils which can be used according to the invention, of:

(i) hydrocarbon-based oils of plant origin, such as glyceride triesters, which are generally triesters of fatty acids and of glycerol, the fatty acids of which can have varied chain lengths from C₄ to C2₄, it being possible for these chains to be saturated or unsaturated and linear or branched; these oils are in particular wheatgerm oil, sunflower oil, grape seed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soyabean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil and musk rose oil; or also caprylic/capric acid triglycerides, such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel;

(ii) synthetic ethers containing 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, and squalane, and mixtures thereof; (iv) synthetic esters, for instance oils of formula RCOOR' in which R represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R' represents a hydrocarbon-based chain that is in particular branched, containing from 1 to 40 carbon atoms, on condition that R + R' is >10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoate, such as the product sold under the trade name Finsolv TN® or Witconol TN® by the company Witco or Tegosoft TN® by the company Evonik Goldschmidt, 2-ethylphenyl benzoate, such 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, such as the product sold under the name Dub Dis by the company Stearinerie Dubois, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, such as propylene glycol dioctanoate; hydroxylated esters, such as isostearyl lactate or diisostearyl malate; and pentaerythritol esters; citrates or tartrates, such as di(linear C12-C13 alkyl) tartrates, such as those sold under the name Cosmacol ETI® by the company Enichem Augusta Industriale, and also di(linear C14-C15 alkyl) tartrates, such as those sold under the name Cosmacol ETL® by the same company; or acetates; (v) fatty alcohols that are liquid at ambient temperature, containing a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2- butyloctanol or 2-undecylpentadecanol; (vi) higher fatty acids such as oleic acid, linoleic acid or 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 SL205® from Ajinomoto;

and mixtures thereof. Among the non-volatile hydrocarbon-based oils that may be used according to the invention, preference will be given more particularly to glyceride triesters and in particular to caprylic/capric acid triglycerides, synthetic esters and in particular isononyl isononanoate, oleyl erucate, C12-C15 alkyl benzoate, 2- ethylphenyl benzoate and fatty alcohols, in particular octyldodecanol.

As volatile hydrocarbon-based oils that may be used according to the invention, mention may be made in particular of hydrocarbon-based oils having from 8 to 16 carbon atoms and in particular of branched Cs-Ci6 alkanes, such as Cs-Ci6 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane or isohexadecane, the oils sold under the Isopar or Permethyl trade names, branched Cs-Ci6 esters, isohexyl neopentanoate, and mixtures thereof.

Mention may also be made of the alkanes described in the Cognis patent applications WO 2007/068 371 or WO 2008/155 059 (mixtures of distinct alkanes differing by at least one carbon). These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut or palm oil. Mention may be made of the mixtures of n-undecane (Cn ) and n-tridecane (C13) obtained in Examples 1 and 2 of application WO 2008/155 059 from the company Cognis. Mention may also be made of n-dodecane (C12) and n-tetradecane (Ci₄) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97®, and also mixtures thereof.

Other volatile hydrocarbon-based oils, for instance petroleum distillates, in particular those sold under the name Shell Solt® by the company Shell, may also be used. According to one embodiment, the volatile solvent is chosen from volatile hydrocarbon-based oils containing from 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 (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups which are pendent and/or at the end of the silicone chain, which groups each contain from 2 to 24 carbon atoms, or phenyl silicones, such as phenyl trimethicones, phenyl dimethicones, phenyl(trimethylsiloxy)diphenylsiloxanes, diphenyl dimethicones, diphenyl(methyldiphenyl)trisiloxanes or (2-phenylethyl)trimethylsiloxysilicates.

Examples of volatile silicone oils that may be mentioned include volatile linear or cyclic silicone oils, in particular those with a viscosity≤ 8 centistokes (8 10^"6 m²/s) and in particular containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made in particular of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

Mention may also be made of the volatile linear alkyltrisiloxane oils of general formula (IV):

in which R represents an alkyl group comprising from 2 to 4 carbon atoms, one or more hydrogen atoms of which may be replaced with a fluorine or chlorine atom.

Among the oils of general formula (IV) that may be mentioned are:

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 an ethyl group. Fluoro oils

Use may also be made of volatile fluoro oils, such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures thereof.

An oily phase according to the invention may also comprise other fatty substances, mixed with or dissolved in the oil. Another fatty substance that may be present in the oily phase may be, for example:

- a fatty acid chosen from fatty acids comprising from 8 to 30 carbon atoms, such as stearic acid, lauric acid, palmitic acid and oleic acid;

- a wax chosen from waxes such as lanolin, beeswax, carnauba or candelilla wax, paraffin waxes, lignite waxes, microcrystalline waxes, ceresin or ozokerite, or synthetic waxes, such as polyethylene waxes or Fischer-Tropsch waxes;

- a gum chosen from silicone gums (dimethiconol);

- a pasty compound, such as polymeric or non-polymeric silicone compounds, esters of a glycerol oligomer, arachidyl propionate, fatty acid triglycerides and derivatives thereof;

- and mixtures thereof.

These fatty substances can be chosen in a varied way by those skilled in the art in order to prepare a composition having the desired properties, for example of consistency or texture.

Preferentially, the overall oily phase, including all the lipophilic substances of the composition capable of being dissolved in this same phase, represents from 5% to 95% by weight and preferentially from 10% to 80% by weight relative to the total weight of the composition.

According to one 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 may be used are of the paddle or impeller, rotor-stator and HPH type. In order to obtain stable emulsions with a low content of polymer (oil/polymer ratio > 25), it is possible to prepare the dispersion in concentrated phase and then to dilute the dispersion with the remainder of the aqueous phase.

It is also possible, by means of an HPH (between 50 and 800 bar), to obtain stable dispersions with drop sizes that may be as low as 100 nm.

The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic and non-ionic emulsifiers, used alone or as a mixture, and optionally a coemulsifier. The emulsifiers are appropriately chosen according to the emulsion to be obtained (W/O or O/W).

The emulsifier and the coemulsifier 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 also contain lipid vesicles.

Examples of W/O emulsifying surfactants that may be mentioned include alkyl esters or ethers of sorbitan, of glycerol, of polyol or of sugars; silicone surfactants, for instance dimethicone copolyols, such as the mixture of cyclomethicone and of dimethicone copolyol, sold under the name DC 5225 C® by the company Dow Corning, and alkyldimethicone copolyols such as laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by the company Dow Corning; cetyldimethicone copolyol, such as the product sold under the name Abil EM 90R® by the company Goldschmidt, and the mixture of cetyldimethicone copolyol, of polyglyceryl isostearate (4 mol) and of hexyl laurate, sold under the name Abil WE O9® by the company Goldschmidt. One or more coemulsifiers may also be added thereto, which coemulsifiers may be chosen advantageously from the group comprising polyol alkyl esters.

Mention may also be made of non-silicone emulsifying surfactants, in particular alkyl esters or ethers of sorbitan, of glycerol, of polyol or of sugars. Polyol alkyl esters that may in particular be mentioned include polyethylene glycol esters, for instance PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135® by the company ICI. Examples of glycerol and/or sorbitan esters that may be mentioned include polyglyceryl isostearate, such as the product sold under the name Isolan Gl 34® by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987® by the company ICI; sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986® by the company ICI, and mixtures thereof.

For the O/W emulsions, examples of non-ionic emulsifying surfactants that may be mentioned include polyoxyalkylenated (more particularly polyoxyethylenated and/or polyoxypropylenated) esters of fatty acids and of glycerol; oxyalkylenated esters of fatty acids and of sorbitan; polyoxyalkylenated (in particular polyoxyethylenated and/or polyoxypropylenated) esters of fatty acids, optionally in combination with an ester of fatty acid and of glycerol, such as the PEG-100 stearate/glyceryl stearate mixture sold, for example, by the company ICI under the name Arlacel 165; oxyalkylenated (oxyethylenated and/or oxypropylenated) ethers of fatty alcohols; esters of sugars, such as sucrose stearate; or ethers of fatty alcohol and of sugar, in particular alkyl polyglucosides (APGs), such as decyl glucoside and lauryl glucoside, sold, for example, by the company Henkel under the respective names Plantaren 2000® and Plantaren 1200®, cetostearyl glucoside, optionally as a mixture with cetostearyl alcohol, sold, for example, under the name Montanov 68® by the company SEPPIC, under the name Tegocare CG90® by the company Goldschmidt and under the name Emulgade KE3302® by the company Henkel, and arachidyl glucoside, for example in the form of the mixture of arachidyl and behenyl alcohols and of arachidyl glucoside sold under the name Montanov 202® by the company SEPPIC. According to one 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, for example as described in document WO-A-92/06778. The compositions according to the invention may also comprise at least one aqueous phase. The aqueous phase contains water and optionally other water-soluble or water- miscible organic solvents.

An aqueous phase that is suitable for use in the invention may comprise, for example, a water chosen from a natural spring water, such as water from La Roche-Posay, water from Vittel or waters from Vichy, or a floral water.

The water-soluble or water-miscible solvents that are suitable for use in the invention comprise 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, use may more particularly be made of ethanol, propylene glycol, glycerol, and mixtures thereof. According to one particular form of the invention, the overall aqueous phase, including all the hydrophilic substances of the composition capable of being dissolved in this same phase, represents from 5% to 95% by weight and preferentially from 10% to 80% by weight relative to the total weight of the composition.

The compositions according to the invention may also contain adjuvants that are standard in the cosmetics or dermatological field, such as hydrophilic or lipophilic gelling agents, preservatives, antioxidants, solvents, fragrances, fillers, odour absorbers, colorants or salts. Depending on their nature, these adjuvants may be introduced into the fatty phase, into the aqueous phase and/or into 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 non-ionic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoams, fragrances, preserving agents, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active agents, fillers, polymers, propellants, basifying or acidifying agents or any other ingredient commonly used in the cosmetics and/or dermatological field. Mention may be made, among organic solvents, of alcohols other than Ci-C₄ monoalkanols as defined above and in particular short-chain C2-C8 polyols, such as glycerol or diols, such as caprylyl glycol, 1 ,2-pentanediol, propanediol, butanediol, glycols and glycol ethers, such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.

Mention may be made, as thickeners, of carboxyvinyl polymers, such as the Carbopols® (Carbomers) and the Pemulens, such as Pemulen TR1® and Pemulen TR2® (acrylate/C 10-C30 alkyl acrylate copolymer); polyacrylamides, for instance the 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; 2- acrylamido-2-methylpropanesulfonic acid polymers and copolymers, optionally crosslinked and/or neutralized, for instance poly(2-acrylamido-2- methylpropanesulfonic acid) sold by the company Hoechst under the trade name Hostacerin AMPS® (CTFA name: ammonium polyacryloyldimethyl taurate or Simulgel 800® sold by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate/polysorbate 80/sorbitan oleate); copolymers of 2- acrylamido-2-methylpropanesulfonic acid and of hydroxyethyl acrylate, for instance Simulgel NS® and Sepinov EMT 10® sold by the company SEPPIC; cellulose derivatives such as hydroxyethyl cellulose; polysaccharides and in particular gums such as xanthan gum; water-soluble or water-dispersible silicone derivatives, for instance acrylic silicones, polyether silicones and cationic silicones, and mixtures thereof.

Among the acidifying agents, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.

Among the basifying agents, examples that may be mentioned include aqueous ammonia, alkali metal carbonates, alkanolamines, such as mono-, di- and triethanolamines and derivatives thereof, sodium hydroxide or potassium hydroxide.

Preferably, the cosmetic composition comprises one or more basifying agents chosen from alkanolamines, in particular triethanolamine, and sodium hydroxide. In the case of a direct emulsion, the pH of the composition in accordance with the invention is generally between 3 and 12 approximately, preferably between 5 and 1 1 approximately and even more particularly from 6 to 8.5. According to one 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- screening agents and/or one or more mineral pigments. It will preferentially consist of at least one hydrophilic, lipophilic or insoluble organic UV-screening agent.

The term "hydrophilic UV-screening agent" is intended to mean any cosmetic or dermatological organic or mineral compound for screening out UV radiation, which can be fully dissolved in molecular form in a liquid aqueous phase or which can be dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.

The term "lipophilic screening agent" is intended to mean any cosmetic or dermatological organic or mineral compound for screening out UV radiation, which can be fully dissolved in molecular form in a liquid fatty phase or which can be dissolved in colloidal form (for example in micellar form) in a liquid fatty phase.

The term "insoluble UV-screening agent" is intended to mean any cosmetic or dermatological organic or mineral compound for screening out UV radiation which has a solubility in water of less than 0.5% by weight and a solubility of less than 0.5% by weight in the majority of organic solvents such as liquid paraffin, fatty alcohol benzoates and fatty acid triglycerides, for example Miglyol 812® sold by the company Dynamit Nobel. This solubility, determined at 70°C, is defined as the amount of product in solution in the solvent at equilibrium with an excess of solid in suspension after returning to ambient temperature. It may be readily evaluated in the laboratory.

The organic UV-screening agents are chosen in particular from cinnamic compounds; anthranilate compounds; salicylic compounds; dibenzoylmethane compounds; benzylidenecamphor compounds; benzophenone compounds; β,β- diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds, in particular those cited in patent US 5 624 663; benzimidazole derivatives; imidazoline compounds; bis-benzazolyl compounds, as described in patents EP 669 323 and US 2 463 264; p-aminobenzoic (PABA) compounds; methylenebis(hydroxyphenylbenzotriazole) compounds, as described in applications US 5 237 071 , US 5 166 355, GB 2 303 549, DE 197 26 184 and EP 893 1 19; benzoxazole compounds, as described in patent applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 101 62 844; screening polymers and screening silicones, such as those described in particular in application WO 93/04665; a-alkylstyrene-based dimers, such as those described in patent application DE 198 55 649; 4,4-diarylbutadiene compounds, as described in applications EP 0 967 200, DE 197 46 654, DE 197 55 649, EP-A-1 008 586, EP 1 133 980 and EP 133 981 , and mixtures thereof.

As examples of organic photoprotective agents, mention may be made of those denoted hereinbelow under their INCI name:

Cinnamic compounds:

Ethylhexyl methoxycinnamate sold in particular under the trade name Parsol MCX® by DSM Nutritional 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 BASF. 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. β,β-Diphenylacrylate compounds:

2-Ethylhexyl cyano-3,3-diphenylacrylate 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:

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 1 1® by Norquay,

Benzophenone-8 sold under the trade name Spectra-Sorb UV-24® by American Cyanamid,

Benzophenone-9, sold under the trade name Uvinul DS 49® by BASF,

Benzophenone-12,

n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, sold under the trade name Uvinul A Plus® or, as a mixture with octyl methoxycinnamate, under the trade name Uvinul A Plus B® by the company BASF,

1 ,1 '-(1 ,4-Piperazinediyl)bis[1 -[2-[4-(diethylamino)-2- hydroxybenzoyl]phenyl]methanone] (CAS 919803-06-8), as described in application WO 2007/071 584; this compound advantageously being used in micronized form (mean size of 0.02 to 2 μιτι), which may be obtained, for example, according to the micronization process described in applications GB- A-2 303 549 and EP-A-893 1 19, and in particular in the form of an aqueous dispersion.

Benzylidenecamphor compounds:

3- Benzylidenecamphor, manufactured under the name Mexoryl SD® by Chimex,

4- Methylbenzylidenecamphor, sold under the name Eusolex 6300® by Merck, Benzylidenecamphorsulfonic acid, manufactured under the name Mexoryl SL® by Chimex,

Camphor benzalkonium methosulfate, manufactured under the name Mexoryl SO® by Chimex,

Terephthalylidenedicamphorsulfonic acid, manufactured under the name Mexoryl SX® by Chimex,

Polyacrylamidomethylbenzylidenecamphor, manufactured under the name Mexoryl SW® by Chimex. Phenylbenzimidazole compounds:

Phenylbenzimidazolesulfonic acid, sold in particular under the trade name Eusolex 232® by Merck.

Bis-benzazolyl compounds:

Disodium phenyl dibenzimidazole tetrasulfonate, sold under the trade name Neo Heliopan AP® by Haarmann and Reimer.

Phenylbenzotriazole compounds:

Drometrizole trisiloxane, sold under the name Silatrizole® by Rhodia Chimie.

Methylenebis(hvdroxyphenylbenzotriazole) compounds:

Methylene bis-benzotriazolyl tetramethylbutylphenol, in particular in solid form, such as the product sold under the trade name Mixxim BB/100® by Fairmount Chemical, or in the form of an aqueous dispersion of micronized particles with a mean particle size ranging from 0.01 to 5 μιτι, more preferentially from 0.01 to 2 μιτι and more particularly from 0.020 to 2 μιτι, with at least one alkylpolyglycoside surfactant having the structure C_nH₂n+iO(C6HioO₅)xH, in which n is an integer from 8 to 16 and x is the mean degree of polymerization of the (C6H10O₅) unit and ranges from 1 .4 to 1 .6, as described in patent GB-A-2 303 549, sold in particular under the trade name Tinosorb M® by the company BASF, or in the form of an aqueous dispersion of micronized particles with a mean particle size ranging from 0.02 to 2 μιτι, more preferentially from 0.01 to 1 .5 μιτι and more particularly from 0.02 to 1 μιτι, in the presence of at least one polyglyceryl mono(C8-C2o)alkyl ester with a degree of glycerol polymerization of at least 5, such as the aqueous dispersions described in application WO 2009/063 392.

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,

- Diethylhexyl butamido triazone, sold under the trade name Uvasorb HEB® by Sigma 3V,

- 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-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,

- symmetrical triazine screening agents substituted with naphthalenyl groups or polyphenyl groups described in patent US 6 225 467, application WO 2004/085 412 (see compounds 6 and 9) or the document "Symmetrical Triazine Derivatives", IP.COM IPCOM000031257 Journal, INC, West Henrietta, NY, US (20 September 2004), in particular 2,4,6-tris(diphenyl)triazine and 2,4,6- tris(terphenyl)triazine, which is also mentioned in patent applications WO 06/035 000, WO 06/034 982, WO 06/034 991 , WO 06/035 007, WO 2006/034 992 and WO 2006/034 985, these compounds advantageously being used in micronized form (mean particle size of 0.02 to 3 μιτι), which may be obtained, for example, according to the micronization process described in applications GB-A-2 303 549 and EP-A-893 1 19, and in particular in aqueous dispersion;

- silicone triazines substituted with two aminobenzoate groups, as described in patent EP 0 841 341 , in particular 2,4-bis(n-butyl 4'-aminobenzalmalonate)-6- [(3-{1 ,3,3,3-tetramethyl-1 -[(trimethylsilyl)oxy]disiloxanyl}propyl)amino]-s-triazine.

Anthranilic compounds:

Menthyl anthranilate, sold under the trade name Neo Heliopan MA® by Symrise.

Imidazoline compounds:

Ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.

Benzalmalonate compounds:

Polyorganosiloxane comprising benzalmalonate functional groups, such as Polysilicone-15, sold under the trade name Parsol SLX® by Hoffmann- LaRoche. 4,4-Diarylbutadiene compounds:

1 ,1 -Dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene. Benzoxazole compounds:

2,4-bis[5-(1 ,1 -dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2- ethylhexyl)imino-1 ,3,5-triazine, sold under the name Uvasorb K2A® by Sigma 3V. Carbon-bearing merocvanine derivatives:

These compounds are described in the patent US 4 195 999, application WO

2004/006878 and document IP COM Journal 4 (4), 16 N°IPCOM00001 1 179D published on 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 the company Merck,

Isopropyldibenzoylmethane. The preferred organic screening agents are chosen from:

Ethylhexyl methoxycinnamate,

Ethylhexyl salicylate,

Homosalate,

Octocrylene,

Phenylbenzimidazolesulfonic acid,

Benzophenone-3,

Benzophenone-4,

Benzophenone-5,

n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,

4-Methylbenzylidenecamphor,

Terephthalylidenedicamphorsulfonic acid,

Disodium phenyl dibenzimidazole tetrasulfonate,

Methylene bis-benzotriazolyl tetramethylbutylphenol,

Bis(ethylhexyloxyphenol)methoxyphenyltriazine,

Ethylhexyl triazone,

Diethylhexyl butamido triazone,

2,4,6-Tris(dineopentyl 4'-aminobenzalmalonate)-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'-aminobenzalnnalonate)-6-(n-butyl 4'-aminobenzoate)-s- triazine,

2,4-Bis(n-butyl 4'-aminobenzalmalonate)-6-[(3-{1 ,3,3,3-tetramethyl-l -

[(trimethylsilyl)oxy]disiloxanyl}propyl)amino]-s-tnazine,

2,4,6-Tris(diphenyl)triazine,

2,4,6-Tris(terphenyl)triazine,

Drometrizole Trisiloxane,

Polysilicone-15,

1 ,1 -Dicarboxy(2,2'-dinnethylpropyl)-4,4-diphenylbutadiene,

2,4-Bis[4-[5-(1 ,1 -dimethylpropyl)benzoxazol-2-yl]phenylimino]-6-[(2- ethylhexyl)imino]-1 ,3,5-triazine,

Butyl methoxy dibenzoylmethane, and mixtures thereof.

The particularly preferred organic screening agents are chosen from:

Ethylhexyl salicylate,

Homosalate,

Octocrylene,

n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,

Terephthalylidenedicamphorsulfonic acid,

Bis(ethylhexyloxyphenol)methoxyphenyltriazine,

Ethylhexyl triazone,

Diethylhexyl butamido triazone,

2,4-Bis(n-butyl 4'-aminobenzalmalonate)-6-[(3-{1 ,3,3,3-tetramethyl-l -

[(trimethylsilyl)oxy]disiloxanyl}propyl)amino]-s-triazine,

Drometrizole trisiloxane,

Butyl methoxy dibenzoylmethane,

and mixtures thereof.

The inorganic UV-screening agents used in accordance with the present invention are metal oxide pigments. More preferentially, the inorganic UV- screening agents of the invention are metal oxide particles with a mean elementary particle size of less than or equal to 0.5 μιτι, more preferentially between 0.005 and 0.5 μητι, even more preferentially between 0.01 and 0.2 μιτι, better still between 0.01 and 0.1 μιτι and more particularly between 0.015 and 0.05 pm. They may be chosen in particular from titanium oxide, zinc oxide, iron oxide, zirconium oxide and cerium oxide, or mixtures thereof.

Such coated or uncoated metal oxide pigments are described in particular in patent application EP-A-0 518 773. Commercial pigments that may be mentioned include the products sold by the companies Sachtleben Pigments, Tayca, Merck and Degussa.

The metal oxide pigments may be coated or uncoated. The coated pigments are pigments that have undergone one or more surface treatments of 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 aluminium salts of fatty acids, metal alkoxides (of titanium or aluminium), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

The coated pigments are more particularly titanium oxides that have been coated:

- with silica, such as the product Sunveil® from the company Ikeda,

- with silica and iron oxide, such as the product Sunveil F® from the company Ikeda,

- with silica and alumina, such as the products Microtitanium Dioxide MT 500 SA® and Microtitanium Dioxide MT 100 SA from the company Tayca and Tioveil from the company Tioxide,

- with alumina, such as the products Tipaque TTO-55 (B)® and Tipaque TTO- 55 (A)® from the company Ishihara and UVT 14/4 from the company Sachtleben Pigments,

- with alumina and aluminium stearate, such as the products Microtitanium Dioxide MT 100 T®, MT 100 TX®, MT 100 Z® and MT-01® from the company Tayca, the products Solaveil CT-10 W® and Solaveil CT 100® from the company Uniqema and the product Eusolex T-AVO® from the company Merck, - with silica, alumina and alginic acid, such as the product MT-100 AQ® from the company Tayca,

- with alumina and aluminium laurate, such as the product Microtitanium Dioxide MT 100 S® from the company Tayca,

- with iron oxide and iron stearate, such as the product Microtitanium Dioxide MT 100 F® from the company Tayca,

- with zinc oxide and zinc stearate, such as the product BR 351® from the company Tayca,

- with silica and alumina and treated with a silicone, such as the products Microtitanium Dioxide MT 600 SAS®, Microtitanium Dioxide MT 500 SAS® or

Microtitanium Dioxide MT 100 SAS® from the company Tayca,

- with silica, alumina and aluminium stearate and treated with a silicone, such as the product STT-30-DS® from the company Titan Kogyo,

- with silica and treated with a silicone, such as the product UV-Titan X 195® from the company Sachtleben Pigments,

- with alumina and treated with a silicone, such as the products Tipaque TTO-55 (S)® from the company Ishihara or UV Titan M 262® from the company Sachtleben Pigments,

- with triethanolamine, such as the product STT-65-S from the company Titan Kogyo,

- with stearic acid, such as the product Tipaque TTO-55 (C)® from the company Ishihara,

- with sodium hexametaphosphate, such as the product Microtitanium Dioxide MT 150 W® from the company Tayca,

- T1O2 treated with octyltrimethylsilane, sold under the trade name T 805® by the company Degussa Silices,

- T1O2 treated with a polydimethylsiloxane, sold under the trade name 70250 Cardre UF TiO2SI3® by the company Cardre,

- anatase/rutile T1O2 treated with a polydimethylhydrosiloxane, sold under the trade name Microtitanium Dioxide USP Grade Hydrophobic® by the company

Color Techniques.

Mention may also be made of T1O2 pigments doped with at least one transition metal such as iron, zinc or 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 also comprise one or more dispersants, for instance a sorbitan ester, for instance sorbitan isostearate, or a polyoxyalkylenated fatty acid ester of glycerol, for instance TRI-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate. Preferably, the oily dispersion of titanium oxide particles comprises at least one dispersant chosen from polyoxyalkylenated fatty acid esters of glycerol. Mention may be made more particularly of the oily dispersion of T1O2 particles doped with manganese in capric/caprylic acid triglyceride in the presence of TRI-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate and sorbitan isostearate having the INCI name: titanium dioxide (and) TRI-PPG- 3 myristyl ether citrate (and) polyglyceryl-3 ricinoleate (and) sorbitan isostearate, for instance the product sold under the trade name Optisol TD50® by the company Croda.

The uncoated titanium oxide pigments are sold, for example, by the company Tayca under the trade names Microtitanium Dioxide MT 500 B or Microtitanium Dioxide MT 600 B®, by the company Degussa under the name P 25, by the company Wackherr 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 sold under the name Z-Cote by the company Sunsmart;

- those sold under the name Nanox® by the company Elementis;

- those sold under the name Nanogard WCD 2025® by the company Nanophase Technologies.

The coated zinc oxide pigments are for example:

- those sold under the name Zinc Oxide CS-5® by the company Toshibi (ZnO coated with polymethylhydrogenosiloxane);

- those sold under the name Nanogard Zinc Oxide FN® by the company Nanophase Technologies (as a 40% dispersion in Finsolv TN®, C12-C15 alkyl benzoate);

- those sold under the name Daitopersion Zn-30® and Daitopersion Zn-50® by the company Daito (dispersions in cyclopolymethylsiloxane/oxyethylenated polydimethylsiloxane, containing 30% or 50% of zinc oxides coated with silica and polymethylhydrogenosiloxane); - those sold under the name NFD Ultrafine ZnO® by the company Daikin (ZnO coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl as a dispersion in cyclopentasiloxane);

- those sold under the name SPD-Z1 ® by the company Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane);

- those sold under the name Escalol Z100® by the company ISP (alumina- treated ZnO dispersed in the ethylhexyl methoxycinnamate/PVP-hexadecene copolymer/methicone mixture);

- those sold under the name Fuji ZnO-SMS-10® by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane);

- those sold under the name Nanox Gel TN® by the company Elementis (ZnO dispersed at a concentration of 55% in C12-C15 alkyl benzoate with hydroxystearic acid polycondensate).

The uncoated cerium oxide pigments may be, for example, those sold under the name Colloidal Cerium Oxide® by the company Rhone-Poulenc.

The uncoated iron oxide pigments are sold, for example, by the company Arnaud under the names Nanogard WCD 2002® (FE 45B®), Nanogard Iron FE 45 BL AQ, Nanogard FE 45R AQ® and Nanogard WCD 2006® (FE 45R®) or by the company Mitsubishi under the name TY-220®.

The coated iron oxide pigments are sold, for example, by the company Arnaud under the names Nanogard WCD 2008 (FE 45B FN)®, Nanogard WCD 2009® (FE 45B 556®), Nanogard FE 45 BL 345® and Nanogard FE 45 BL® or by the company BASF under the name Transparent Iron Oxide®.

Mention may also be made of mixtures of metal oxides, in particular of titanium dioxide and of cerium dioxide, including the equal-weight mixture of titanium dioxide and cerium dioxide coated with silica, sold by the company Ikeda under the name Sunveil A®, and also the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone, such as the product M 261® sold by the company Sachtleben Pigments, or coated with alumina, silica and glycerol, such as the product M 21 1® sold by the company Sachtleben Pigments. According to the invention, coated or uncoated titanium oxide pigments are particularly preferred. The amount of UV-screening agents depends on the desired final use. The UV- screening agents according to the invention are preferably present in the compositions according to the invention in a content ranging from 0.1 % to 45% by weight and in particular from 5% to 30% by weight relative to the total weight of the composition.

A subject of the present invention is also the cosmetic use of a composition according to the invention as defined above, for colouring and/or pigmenting keratin materials, and/or promoting the pigmentation of keratin materials.

More particularly, a subject of the present invention is the cosmetic use of a composition according to the invention as defined above, for colouring and/or pigmenting the skin and/or promoting the pigmentation of the skin.

A subject of the present invention is also the cosmetic use of a composition according to the invention as defined above, for browning the skin and/or giving the skin a tan and/or for strengthening the tan, and/or for making the skin complexion uniform.

Preferably, the cosmetic use according to the invention is characterized in that said composition is applied to the skin.

A subject of the present invention is also a cosmetic treatment process for colouring and/or pigmenting keratin materials, and/or promoting the pigmentation of keratin materials, characterized in that a composition according to the invention as defined above is applied to said keratin materials.

More particularly, a subject of the present invention is also a cosmetic treatment process for colouring and/or pigmenting the skin, and/or promoting the pigmentation of the skin, characterized in that a composition according to the invention as defined above is applied to the skin.

A subject of the present invention is also a cosmetic treatment process for browning the skin and/or giving the skin a tan and/or for strengthening the tan, and/or for making the skin complexion uniform.

The cosmetic compositions according to the invention may be used, for example, as care products and/or antisun products for keratin materials, in particular for the skin of the face and/or the body, with a liquid to semi-liquid consistency, such as milks, more or less smooth creams, cream gels or pastes. They may optionally be packaged in aerosol form and may be in the form of a foam or a 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 pressurization devices. The devices in accordance with the invention are well known to those skilled in the art and comprise non-aerosol pumps or "atomizers", aerosol containers comprising a propellant and aerosol pumps using compressed air as propellant. These devices are described in patents US 4 077 441 and US 4 850 517. The compositions packaged in aerosol form in accordance with the invention generally contain conventional propellants, for instance hydrofluoro compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane or 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 term "comprising a" should be understood as being synonymous with "comprising at least one", unless otherwise specified.

The terms "between... and..." and "ranging from... to..." should be understood as being limits inclusive, unless otherwise specified. The examples that follow serve to illustrate the invention without, however, being limiting in nature. The names are, as appropriate, given as chemical names or CTFA names (International Cosmetic Ingredient Dictionary and Handbook) and the amounts as percentage by weight unless otherwise mentioned.

Example 1 : demonstration of the modulatory effect on melanogenesis MATERIAL AND METHOD:

Pigmented epidermises were reconstructed by seeding normal human melanocytes and normal human keratinocytes onto a collagen substrate, according to the protocol of the company Episkin.

The following controls are performed:

- negative control: untreated;

- positive control for stimulation of melanogenesis: 10 nM of alpha- MSH.

The products tested are as follows:

- the acetyl hexapeptide-1 peptide (Melitane® GL 200 from Unipex Innovations, the main active agent being at 200 ppm). Alone at 10 nM;

- the acetyl hexapeptide-1 peptide (Melitane® GL 200) at 10 nM with the active agent N-acetyl-L-tyrosine (N ac Tyrosine® sold by the company Sigma, code

A2513) at 700 μΜ;

- the acetyl hexapeptide-1 peptide (Melitane® GL 200) at 10 nM with the active agent caffeine (Caffeine® sold by the company Sigma, code 27600 Fulka) at 50 μΜ;

- the acetyl hexapeptide-1 peptide (Melitane® GL 200) at 10 nM with the two active agents N-acetyl-L-tyrosine (N ac Tyrosine® from Sigma, code A2513) at 700 μΜ and caffeine (Caffeine® from Sigma, code 27600 Fulka) at 50 μΜ.

The treatment with the active agents was carried out systemically, and was repeated every day except for the weekend, starting from dO (day on which the cells are seeded) and up to d9 (9^th day).

The histological quality of the epidermises after treatment is evaluated on histological sections after HES staining in order to determine the impact of the treatment on the epidermises. Also, the physiology of the melanocytes is studied in order to detect any melano-cytotoxicity. If no histological modification nor any melanotoxic effect of the products evaluated is noted, the pigmentation is quantified by quantifying the melanin on histological sections by image analysis (Fontana Masson staining) using the Histolab software. RESULTS:

The reconstructed epidermidises treated with 10 nM alpha-MSH and 10 nM acetyl hexapeptide-1 optionally combined with 50 μΜ caffeine and/or 700 μΜ N- acetyl-L-tyrosine exhibit a good histological quality, comfortable to that of the untreated control epidermises. There is no visible cytotoxic effect. The physiological aspect of the melanocytes also remains unchanged after these various treatments, showing the absence of cytotoxic effect of the products and of the various combinations of active agents on the melanocytes.

Histological sections stained using the Fontana Masson method were prepared in order to visualise the melanin granules. Between 45 and 60 images corresponding to an identical epidermis length were acquired per experimental condition. The area occupied by the melanin was quantified in each image. The mean pixel number per image is compared.

The results show a very significant pro-pigmenting effect of acetyl hexapeptide- 1 in comparison with the untreated control (p-value <0.05).

The pro-pigmenting effect obtained with the combination of the three active agents, acetyl hexapeptide-1 , N-acetyl-L-tyrosine and caffeine, is very significantly greater than the effect of acetyl hexapeptide-1 alone, very significantly greater 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 demonstrate an activation of skin pigmentation by the combination of acetyl hexapeptide-1 /N-acetyl-L-tyrosine/caffeine (+690%) which is greater than the accumulation of the activations obtained with the compounds alone (+538%), thus demonstrating an unexpected synergistic effect.

These results show that a composition comprising acetyl hexapeptide-1 , N- acetyl-L-tyrosine and caffeine is significantly more effective in terms of the pro- pigmenting response than the addition of the effects of acetyl hexapeptide-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 that is conventional for those skilled in the art: In these examples, the amounts of the ingredients of the compositions are given as % by weight of starting material, relative to the total weight of the composition.

Example 2A: fluidic direct emulsion with screening system

The aqueous phase A and the oily phase B were prepared by mixing the starting materials, with mechanical stirring, at 80°C.

Once the aqueous solution A and the oily solution B were macroscopically homogeneous, the emulsion was prepared by introducing phase B into phase A with stirring using a rotor-stator homogenizer at a stirring speed of 4500 rpm for 20 minutes.

Phases C1 , C2 and C3 and then D were subsequently introduced and the emulsion was cooled to ambient temperature.

After addition of phases E, F and G, the stirring was maintained for 10 min.

The final emulsion is characterized by drops of between 1 mm and 20 mm in size. phase Ingredients %

WATER qs 100

GLYCEROL 5.00

Disodium salt of ethylenediaminetetraacetic acid 0.10

A

ACETYL HEXAPEPTIDE-1 ; 200 ppm (MELITANE®

GL 200 from UNIPEX INNOVATIONS (ATRIUM 5.00

BIOTECHNOLOGIES) )

CAFFEINE (CAFEINE ANHYDRE POUDRE® sold by

1 .00 the company BASF)

N-ACETYL-L- TYROSINE ( N -AC ETYLTYROS I N E ®

0.50 from PHARMAZELL)

DISODIUM STEAROYL GLUTAMATE (MISOFT HS

0.50 21 P® from AJINOMOTO)

TROCOPHERYL ACETATE (DL -ALPHA- TOCOPHERYL ACETATE® sold by the company 0.20 DSM NUTRITIONAL PRODUCTS)

CETYL ALCOHOL 0.50

B MIXTURE OF LINEAR ALCOHOLS (C18/C20/C22)

1 .00 (NAFOL 1822 C® sold by the company SASOL)

POLYETHYLENE GLYCOL MONOSTEARATE (100

0.30 EO) (MYRJ S100-PA-(SG) ® from CRODA)

MIXTURE OF CETYLSTEARYL GLUCOSIDE AND OF CETYL AND STEARYL ALCOHOLS (12/46/42) 0.32 (MONTANOV 68® sold by the company SEPPIC)

ISOPROPYL ISOSTEARATE 1 .50

2-ethylhexyl cyano-3,3-diphenylacrylate

3.00 (OCTOCRYLENE® sold by the company MFCI)

BUTYL METHOXYDIBENZOYLMETHANE (EUSOLEX

3.00 9020® sold by the company Merck)

ETHYLHEXYL SALICYLATE (NEO HELIOPAN OS/H®

5.00 sold by the company Symrise) PRESERVATIVE 1 .00

ETHOXYLATED AMPS / C16/C18 ALKYL

C1 METHACRYLATE COPOLYMER (8 MOL EO) 80 / 20 0.50

(ARISTOFLEX SNC® from CLARIANT)

C2 Carboxyvinyl polymer (Synthalen K® from 3V) 0.07

Acrylamide/sodium acrylamido-2- methylpropanesulfonate copolymer as an inverse

C3 1 .30 emulsion at 40% in isoparaffin/water (Sepigel 305®

from Seppic)

PTFE (FLUOROPURE 103 C® sold by the company

D 2.00

Shamrock Technologies)

Mixture of α,ω-dihydroxylated

polydimethylsiloxane/polydimethylsiloxane 5 cSt; Dow

2.50 Corning 1503 Fluid® sold by the company DOW

E CORNING

FRAGRANCE 0.20

DIMETHICONEA/INYL DIMETHICONE COPOLYMER

(DOW CORNING 9506 POWDER® sold by the 0.50 company Dow Corning)

Mixture of crosslinked polydimethylsiloxane and of

F polydimethylsiloxane (6 cSt) (24/76) (KSG16® from 1 .50

Shin-Etsu)

G DENATURED ALCOHOL 2.00

This cosmetic composition can be used as a care product, such as a daily care product, with a sunscreen agent.

Example 2B: Emulsified gel

The aqueous phase A was prepared by mixing the starting materials, with mechanical stirring, at 80°C. While allowing the mixture to cool to ambient temperature, preparations B and then C (macroscopically homogeneous) were introduced with stirring using a rotor-stator homogenizer at a stirring speed of 4000 rpm for 20 minutes.

Phases C1 , C2 and C3 and then D were subsequently introduced and the emulsion was cooled to ambient temperature.

After addition of phases D and E, the stirring was maintained for 10 min.

The final emulsified gel is characterized by drops of between 1 mm and 20 mm in size. phase Ingredients %

WATER 24.64

Polyethylene glycol (20 EO) (CARBOWAX SENTRY

POLYETHYLENE GLYCOL 1000 NF,FCC GRADE® 3.00

A

from Dow Chemical)

Oxyethylenated dimethylsiloxane (16 EO) with

methoxy end group

5.00 (DOW CORNING 2501 COSMETIC WAX® from Dow

Corning)

GLYCEROL 5.00

DIPROPYLENE GLYCOL 8.00

PRESERVATIVE 0.00

ADENOSINE 0.04

Disodium salt of ethylenediaminetetraacetic acid 0.10

Carboxyvinyl polymer (Synthalen K® from 3V) 0.40

Polyacrylamidomethylpropanesulfonic acid

B partially neutralized with aqueous ammonia and highly

crossl inked 0.20 (Hostacerin AMPS^® from Clariant)

Xanthan gum (RHODICARE XC® from Rhodia) 0.05

C WATER qs 100

ACETYL HEXAPEPTIDE-1 ; 200 ppm (MELITANE® GL

5.00 200 from UNIPEX INNOVATIONS (ATRIUM BIOTECHNOLOGIES) )

CAFFEINE (CAFEINE ANHYDRE POUDRE® sold by

1 .00 the company BASF)

N-ACETYL-L- TYROSINE (N-ACETYLTYROSINE ®

0.50 from PHARMAZELL)

CROSSLINKED POLYDIMETHYLSILOXANE GUM

D BEADS COATED WITH SILSESQUIOXANE RESIN 2.00

(92/8) (KSP 100® from SHIN ETSU)

E WATER 1 .00

TRIETHANOLAMINE 0.40

This cosmetic composition can be used as a care product, such as a daily care product.

Example 2C: Photoprotective composition

The aqueous phase A and the oily phase B were prepared by mixing the starting materials, with mechanical stirring, at 80°C.

Once the aqueous solution A and the oily solution B were macroscopically homogeneous, the emulsion was prepared by introducing phase B into phase A with stirring using a rotor-stator homogenizer at a stirring speed of 4500 rpm for 20 minutes.

After returning to ambient temperature, phases B2 and C, D and E (macroscopically homogeneous) were then introduced with stirring.

After the addition of G, the final emulsion is characterized by drops of between 1 mm and 20 mm in size.

Phase Ingredients %

A WATER qs 100

Disodium salt of ethylenediaminetetraacetic acid 0.20

PROPYLENE GLYCOL 6.00 GLYCEROL 6.00

XANTHAN GUM (RHODICARE XC® from Rhodia) 0.50

CETEARYL ALCOHOL (MINACARE OCTIOL® from

1 .50 MINASOLVE)

OXYPROPYLENATED MYRISTYL ALCOHOL PROPIONATE (2 PO) (CRODAMOL PMP-LQ-(MH) ® 3.00 from CRODA)

PROTECTED OXYPROPYLENATED STEARYL ALCOHOL (15 PO) (ARLAMOL PS15E-LQ-(RB) ® 3.00 from CRODA)

MIXTURE OF OXYETHYLENATED STEARYL ALCOHOL / GLYCERYL STEARATE / PEG

STEARATE (75 MOL) / CETYL AND STEARYL 4.50 ALCOHOLS (20 EO) (EMULIUM DELTA® from

GATTE FOSSE)

C12/C15 alkyl benzoate (TEGOSOFT TN® from

5.00 Goldschmidt)

DIISOPROPYL SEBACATE 5.00

BIS-ETHYLHEXYLOXYPHENOL METHOXYPHENYL

1 .00 TRIAZINE (TINOSORB S® from BASF)

DROMETRIZOLE TRISILOXANE (SILATRIZOLE®

3.00 from RHODIA CHIMIE)

DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE (UVINUL A PLUS GRANULAR® from 1 .00

BASF)

BUTYL METHOXYDIBENZOYLMETHANE

3.00 (EUSOLEX 9020® sold by the company Merck)

ETHYLHEXYL SALICYLATE (NEO HELIOPAN

5.00 OS/H® sold by the company Symrise)

2-Ethylhexyl cyano-3,3-diphenylacrylate

3.50 (OCTOCRYLENE® sold by the company MFCI)

ETHYLHEXYL TRIAZONE (UVINUL T 150® sold by 2.30 the company BASF)

PRESERVATIVE 1 .1

Mixture of α,ω-dihydroxylated

polydimethylsiloxane/polydimethylsiloxane 5 cSt; Dow

B2 2.00

Corning 1503 Fluid® sold by the company DOW

CORNING

C ALCOHOL 3.00

Corn starch esterified with octenylsuccinic anhydride,

D 3.00 aluminium salt (Dry Flo Plus® from National Starch)

SILICA (SILICA BEAD SB 150® from MIYOSHI

E 2.00

KASEI)

WATER 4.40

ACETYL HEXAPEPTIDE-1 ; 200 ppm (MELITANE®

GL 200 from UNIPEX INNOVATIONS (ATRIUM 5

BIOTECHNOLOGIES) )

F

CAFFEINE (CAFEINE ANHYDRE POUDRE® sold by

1 the company BASF)

N-ACETYL-L- TYROSINE ( N -AC ETYLTYROS I N E ®

0.5 from PHARMAZELL)

G CITRIC ACID 0.12

This cosmetic composition can be used as an anti-sun product, such as a suntan cream.

These compositions according to the invention, applied to the skin, make it possible to colour and/or pigment keratin materials, and/or 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 brown the skin and/or give the skin a tan and/or to strengthen the tan, and/or to make the skin complexion uniform.

Claims

1 . Composition comprising, in a physiologically acceptable medium, at least a) one peptide corresponding to formula (I)

R-V¹-Ala²-His³-X⁴-Y⁵-Trp⁶-NH₂ (I) in which:

- R represents a hydrogen atom or a protective group which can be chosen from an acetyl group, a benzoyl group, a tosyl group, a benzenesulfonyl group, a benzyloxycarbonyl group or a pyridinepropionyl group,

- V represents a natural or unnatural amino acid, of L configuration, chosen from norleucine, norvaline and 2-N-Me-norleucine,

- X represents a natural or unnatural amino acid, of L or D configuration, which is aromatic in nature, chosen from phenylalanine, 1 -naphthylalanine, 2- naphthylalanine, phenylglycine, benzothienylalanine, 4,4'-biphenylalanine, 3,3- diphenylalanine, homophenylalanine, indanylglycine, 4-methylphenylalanine, thienylalanine, p-nitrophenylalanine, and halophenylalanine, where the halogen is chosen from a chlorine, bromine, iodine or fluorine atom in the meta, ortho or para position with respect to the phenyl group,

- Y represents a natural amino acid of L configuration, which is basic in nature, chosen from arginine, lysine or ornithine,

and also optical isomers thereof,

the Ala, His and Trp amino acids respectively in positions 2, 3 and 6 being of L configuration; b) one xanthine base chosen from the group consisting of 3,7- dimethylxanthine, 1 ,3,7-trimethylxanthine and 1 ,7-dimethylxanthine; and c) one compound corresponding to formula (III)

(III) in which:

- R₄ represents a hydrogen atom, a hydroxyl or a -CO-Rs group,

- R₅ represents a hydroxyl radical or an -Si(OH)₂R9 group,

- R6 represents a hydrogen atom or a hydroxyl radical,

- R₇ represents an -O-M radical,

- M represents a hydrogen atom; a linear or branched Ci-C₄ alkyl radical; or a metal cation which is an alkali metal, an alkaline-earth metal or a transition metal,

- Rs represents a linear or branched, saturated C1-C20 alkyl; a linear or branched C2-C20 alkylene; a -CH₂NH₂ group; a hydroxyl radical; or a linear or branched C2-C20 ketone group,

- R9 represents a linear or branched Ci-C₄ alkyl radical,

and also optical isomers thereof.

2. Composition according to Claim 1 , characterized in that the peptide corresponds to formula (I) in which:

- R represents a protective group which can be chosen from an acetyl group, a benzenesulfonyl group, a tosyl group or a pyridinepropionyl group,

- V represents a natural or unnatural amino acid chosen from norleucine and 2N-Me-norleucine, of L configuration,

- X represents a natural or unnatural amino acid, which is aromatic in nature, chosen from phenylalanine, 2-naphthylalanine, homophenylalanine, thienylalanine or p-nitrophenylalanine, of D or L configuration,

- Y represents a natural amino acid of L configuration, which is basic in nature, chosen from arginine or lysine,

- the alanine, histidine and tryptophan, respectively in positions 2, 3 and 6 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 is 1 ,3,7-trimethylxanthine.

5. Composition according to any one of Claims 1 to 4, characterized in that the compound corresponds to formula (III) in which:

- R₄ represents a hydrogen atom, a hydroxyl or a -CO-Rs group, - R₅ represents a hydroxyl radical or an -Si(OH)₂R9 group,

- R6 represents a hydrogen atom,

- R₇ represents an -O-M radical,

- M represents a hydrogen atom; a methyl group; or a metal cation which is an alkali metal such as sodium or potassium, an alkaline-earth metal such as calcium or magnesium, or a transition metal such as copper,

- Rs represents an alkyl which is chosen from a methyl group; a saturated linear C5-C10 alkyl; a linear C15-C20 alkylene; a -CH₂NH₂ group; or a -(CH₂)6-CO(CH₂)6-CH3 group,

- R₉ represents a methyl radical.

6. Composition according to any one of Claims 1 to 5, characterized in that the compound corresponding to formula (III) is chosen from the group consisting of N-acetyl-L-tyrosine, N-hydroxy-L-tyrosine, N-ethanoyltyrosine, tyrosine, glycine- tyrosine, caproyl tyrosine, capryloyi tyrosine, oleoyl acetyl tyrosine, glycyl-L- tyrosine, N-acetyl methylsilanol-tyrosine, copper N-acetyl tyrosinate methylsilanol, oleyl acetyl tyrosine, potassium N-caproyl tyrosinate, methyl capryloyi tyrosinate, L-3,4-dihydroxyphenylalanine, and hexyldioxodecyl methyl tyrosinate.

7. Composition according to any one of Claims 1 to 6, characterized in that the compound corresponding to formula (III) is N-acetyl-L-tyrosine.

8. Composition according to any one of Claims 1 to 7, characterized in that the peptide corresponding to formula (I) is Ac-Nle-Ala-His-DPhe-Arg-Trp-NH₂, the xanthine base is 1 ,3,7-trimethylxanthine, and the compound corresponding to formula (III) is N-acetyl-L-tyrosine.

9. Composition according to any one of Claims 1 to 8, characterized in that said peptide corresponding to formula (I) is present in the composition in 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 in 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 in a content of 0.001 % by weight relative to the total weight of the composition.

10. Composition according to any one of Claims 1 to 9, characterized in that said xanthine base is present in the composition in 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 in a content of between 0.1 % and 3% by weight relative to the total weight of the composition, more particularly the xanthine base is present in the composition in a content of 1 % by weight relative to the total weight of the composition.

1 1 . Composition according to any one of Claims 1 to 10, characterized in that said compound corresponding to formula (III) is present in the composition in 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 in a content of between 0.1 % and 3% by weight relative to the total weight of the composition, more particularly the compound of formula (III) is present in the composition in a content of 0.5% by weight relative to the total weight of the composition.

12. Cosmetic use of a composition as defined according to any one of Claims 1 to 1 1 , for colouring and/or pigmenting keratin materials, and/or promoting the pigmentation of keratin materials.

13. Cosmetic treatment process for colouring 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 a composition as defined according to any one of Claims 1 to 12 is applied to said keratin materials.