LU87814A1 - COSMETIC COMPOSITION COMPRISING A DISPERSION OF LIPID VESICLES AS WELL AS MELANIC PIGMENTS, AND ITS USE - Google Patents

Abstract

The disclosed composition based on lipidic vesicles dispersed in an external phase is characterized in that it contains at least one melanic pigment in the aqueous external phase. The melanic pigments may be supported on fine particulate, mineral or polymer, or lamellar charges. The resulting composition is usable in the cosmetic field where it allows to obtain a very homogenous dispersion of the melanic pigment which may be uniformly distributed on the skin or hair; it increases the protection duration of keratinic material against noxious effects of ultraviolet radiations; it helps the sun tan of the skin and gives the skin a uniform colour and a better aspect; it gives coloration to grey hair; and it generates an improved storage of melanic pigment in the corneous layer.

Description

COSMETIC COMPOSITION COMPRISING A DISPERSION OF LIPID VESICLES AS WELL AS MELANIC PIGMENTS, AND ITS USE.

The present invention relates to a cosmetic composition based on lipid vesicles, said composition containing melanin pigments, as well as to its use, in particular for the protection of keratin materials, in particular of the skin and the hair, against ultraviolet radiation, and for »pigmentation of the skin and hair, in particular to color them with a color close to that of natural pigmentation.

Compositions based on lipid vesicles are already known, in particular in the aforementioned field. Lipid vesicles, generally in the form of aqueous dispersions, are characterized by a lamellar structure of sheets made up of at least one lipid bilayer, and encapsulating an aqueous phase which may include water-soluble active substances, which are thus protected from external conditions.

The vesicles can be obtained from ionic lipids and / or nonionic lipids: the term "vesicle" used in the present application encompasses all cases.

The natural protection of human skin against ultraviolet radiation is a function of the amount of melanin pigment present in the melanocytes, and this rate varies according to the different skin types, light to dark. This photoprotective role of melanin is well known. Thus, in individuals with type I, II, III skin, which does not produce sufficient melanin, prolonged exposure to the sun can lead to premature aging of the skin and skin cancers.

To overcome the insufficiency of this pigment in the epidermis, it has already been proposed to apply melanin to the skin. However, the topical application of melanin poses problems in terms of its use in the compositions, due to difficult dispersion and compatibility in the supports used in cosmetics. The complexity of these problems therefore limits its use.

Furthermore, still to compensate for the insufficiency of this pigment in the epidermis, it has also been proposed, in accordance with French patent applications FR-A-2 623 716 and FR-A-2 624 374, to be used in the compositions melanin precursors, such as L-tyrosine or water-soluble derivatives of L-tyrosine, which, by crossing the skin barrier, are transformed into metabolizable L-tyrosine and lead to the formation of melanin in the human skin. * The aforementioned patent applications thus propose compositions based on hydrated lipid lamellar phases or on liposomes containing tyrosine or a tyrosine derivative. The effectiveness of such compositions is nevertheless limited due to the use of a melanin pigment precursor.

According to the invention, it has now surprisingly been discovered that a composition based on vesicles of ionic and / or non-ionic amphiphilic lipids, containing at least one already formed melanin pigment, makes it possible to remedy the problems encountered up to here by constituting an advantageous cosmetic composition in several aspects: - it makes it possible to obtain a very homogeneous dispersion of the melanin pigment which can thus be distributed uniformly over the skin or the hair; it increases the duration of protection of keratin materials against the harmful effects of ultraviolet radiation and makes it possible to potentiate the protective effect; - it promotes the tanning of the skin and gives it a uniform color and a better appearance î it colors gray hair? and - it generates improved storage of the melanin pigment in the stratum corneum.

The present invention therefore relates to a cosmetic composition comprising, in aqueous dispersion, lipid vesicles with a lamellar structure encapsulating an aqueous phase, characterized in that it contains at least one melanin pigment, having a particle size of between approximately 500 nm and 50,000 nm, mixed with the vesicles in the continuous phase of the dispersion and / or in combination with the lipid sheets of the vesicles.

The melanin pigment (s) can be obtained (A) by oxidation of at least one indole compound, (B) by oxidative or enzymatic polymerization of melanin precursors, or (C) by extraction of melanin from substances containing it. (A) The melanin pigments can, first of all, be obtained by oxidation of at least one indolic compound chosen in particular from those corresponding to formula (I):

(I) in which: R1 and R3 represent, independently of each other, / · hydrogen or alkyl at 0, - (^; R2 represents hydrogen, C ^ -C ^ alkyl, carboxyl or (C alkoxy ,, - C4) -carbonyl; R4 and R7 represent, independently of one another, hydrogen, hydroxy, C alkyl, - ^, amino, alkoxy ((C2-C4 acyl) -oxy, (acyl C2-C4) -amino; R5 represents hydrogen, hydroxy, C ^ -C ^ alkoxy, C, alkyl, ^, halogen, amino, (C2-C14 acyl) -oxy, (C2-C4 acyl) - amino, trimethylsilyloxy; R6 represents hydrogen, hydroxy, C6 alkoxy, - C4, amino, (C2-C4 acyl) -oxy, (C2-C4 acyl) -amino, trimethylsilyloxy, (C2-C4 hydroxyalkyl) - amino; ·> R5 and R6 can also form, jointly with the carbon atoms to which they are attached, a methylenedioxy ring optionally substituted by a C 1 -C 4 alkyl or C 1 -C 4 alkoxy group, or else a carbonyldioxy ring : "At least one of the radicals R4 to R7 represents a

0 · A

OZ or NHR group with at most one of the radicals R to R7 representing NHR0; and at most two of the radicals R4 to R7 represent OZ and, in the case where Z represents hydrogen, the two OH are in positions 5 and 6; and at least one of the radicals R4 to R7 represents hydrogen, and in the case where only one of these radicals represents hydrogen, only one radical among R4 to R7 then represents NHR0 or OZ, the other radicals representing C 1 -C alkyl, - C4; the R ° of the NHR0 group denoting hydrogen, C2-C4 acyl, C2-C4 hydroxyalkyl, and the Z of the OZ group denoting hydrogen, C2-C14 acyl, C 1 -C 4 alkyl, or trimethylsilyl, and their salts of alkali, alkaline earth metals, ammonium or amines.

These indole compounds are preferably chosen from 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxy 5-methoxyindole, 4-hydroxy 5-ethoxyindole, 2-carboxyl 5-hydroxyindole, 5-hydroxy 6-methoxyindole, 6-hydroxy 7-methoxyindole, 5-methoxy 6-hydroxyindole, 5,6-dihydroxyindole, N-methyl 5,6-dihydroxyindole, 2-methyl 5 , 6-dihydroxyindole, 3-methyl 5,6-dihydro-xyindole, 2,3-dimethyl 5,6-dihydroxyindole, 2-carboxyl 5.6-dihydroxyindole, 4-hydroxy 5-methyl indole, 2-carboxyl 6-hydroxyindole, 6-hydroxy N-methylindole, 2-ethoxycarbonyl 5,6-dihydroxyindole, 4-hydroxy 7-xnethoxy 2,3-dimethylindole, 4-hydroxy 5-ethoxy N-methyl indole, 6- hydroxy 5-methoxy 2-methylindole, 6-hydroxy 5-methoxy 2,3-dimethylindole, 6-hydroxy 2- ethoxycarbonylindole, 7-hydroxy 3-methyl indole, le, / 5- hydroxy 6-methoxy 2,3 -dimethylindole, 5-hydroxy 3-methylindole, 5-acetoxy 6-hydroxyindole, 5-hydroxy 2-ethoxycarbonylindole, 6-hydroxy 2-carboxyl 5-methyl-indole, 6-hydroxy 2-ethoxycarbonyl 5-methoxyindole, 6- N- / 3-hydroxyethylamino indole, 4- aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, N-methyl 6/3-hydroxyethylaminoindole, 6-amino 2,3-dimethylindole, 6-amino 2,3,4,5-tetramethylindole , 6-amino 2,3,4-trimethylindole, 6-amino 2,3,5-tri-methylindole, 6-amino 2,3,6-trimethylindole, 5.6-diacetoxyindole ** 5-methoxy 6 -acetoxyindole, 5.6-dimethoxyindole, 5,6-methylenedioxyindole, 5,6-trimethylsilyloxyindole, the phosphoric ester of 5,6-dihydroxyindole and 5,6 dibenzyloxyindole, and the addition salts of these compounds.

5,6-dihydroxyindole and 6-hydroxy indole are particularly preferred. The oxidation of the indolic compound of formula (I) can be carried out in an aqueous medium or water-solvent (s), in air, in the presence or not of an alkaline agent and / or a metallic catalyst. such oxidation, for example the cupric ion.

The reaction medium is preferably made up of water and can, if necessary, be made up of a mixture of water and at least one solvent chosen in such a way that it will quickly dissolve the indole compound of formula (I). Among these solvents, there may be mentioned, by way of example, lower alcohols such as ethyl alcohol, propyl or isopropyl alcohol, tert.-butyl alcohol, alkylene glycols, such as ethylene glycol , propylene glycol, alkylene glycol alkyl ethers, such as mono-methyl, monoethyl and monobutyl ethers of ethylene glycol, monomethyl ethers of propylene glycol and dipropylene glycol, and methyl lactate. Oxidation can also be carried out using hydrogen peroxide in the presence of an alkaline agent, such as, preferably, ammonia, or in the presence of an iodide ion, iodide being, preferably, the iodide of an alkali, alkaline earth or ammonium metal.

Oxidation can also be carried out using periodic acid and its water-soluble salts and derivatives, permanganates and dichromates, such as sodium or potassium, sodium hypochlorite, potassium ferricyanide, ammonium persulfate. , silver oxide, lead oxide, ferric chloride, sodium nitrite, rare earth salts including, in particular, cerium, and organic oxidants chosen from ortho- and parabenzoquinones, ortho- and parabenzoquinones mono- or diimines, 1,2- and 1,4-naphthoquinones, 1,2- and 1,4-naphtoquinones mono- or diimines as defined in application EP-A-0 376 776.

The preferred periodic acid salt is sodium periodate.

Oxidizing agents can be activated by a pH modifier.

It is also possible to envisage an enzymatic oxidation.

The insoluble product is isolated by filtration, centrifugation, lyophilization or atomization; it is then ground or micronized to reach the desired particle size. (B) The melanin pigments according to the invention can also come from the oxidative or enzymatic polymerization of melanic precursors, such as L-tyrosine, L-dopa, catechol and their derivatives. (C) The melanin pigments according to the invention can finally come from the extraction of melanin from substances such as human hair, the ink of cephalopods (seich'ès, octopuses), also known under the name "sepiomelanin, in which case the pigment is ground and purified before use.

According to a particular implementation of the invention, the (or) melanin pigment (s) is (or are) associated (s) with at least one particulate filler to constitute a composite melanin pigment. In this case, the melanin pigment (s) can (or can) result from the oxidation of at least one indolic compound of formula (I), as defined above, in a mixture with the charge, in an essentially non-solvent medium for said charge, at a temperature which can range from ambient temperature to approximately 100 ° C., or alternatively by the oxidative polymerization of melanic precursors on the charge.

The general conditions for the oxidation of indole compounds of formula (I) are the same as those mentioned above.

According to a first embodiment, the particulate filler is an inert mineral filler with a particle size of less than 20,000 nm, in particular less than 10,000 nm and close to 5,000 nm, advantageously made up of particles of calcium carbonate, silica or titanium oxide. Such composite melanin pigments, deposited on a mineral filler, are described, as well as their preparation, in French patent application FR-A-2 618 069.

According to a second embodiment of the present invention, the particulate filler is a filler. inert polymer, with a particle size of less than 100,000 nm, in particular from 10 to 50,000 nm, advantageously chosen from natural or synthetic, organic or inorganic polymers, with a crosslinked, crystalline or amorphous network, having a molecular weight of between 5000 and 5000 000.

Composite melanin pigments with a polymeric charge and their preparation are described in the Luxembourg patent application LU-A-87 4 29.

The organic or synthetic polymers are / in particular chosen from polymers derived from keratin, chitin or cellulose, or from polyamides or homo- or copolymers resulting from the polymerization of mono- or polyethylenic, aliphatic monomers or aromatic, cross-linked, crystalline or amorphous.

The polymers derived from keratin are chosen from animal or human keratins. Other polymers derived from keratin which can be used are chemically modified keratins, having a molecular weight of between 10,000 and 250,000 and, in particular, partially hydrolyzed keratin (or keratin hydrolyzate), having a molecular weight of between 50,000 and 200,000; this hydrolyzate is preferably obtained by moderate alkaline hydrolysis; products of this type are, for example, sold under the name "KERASOL" by the company "CRODA". Other modified keratins are sulfonic keratins with a molecular weight of between 10,000 and 100,000, obtained by oxidation of all or part of the disulfide bonds of the cystine groups of keratin into cysteic acid groups. Mention may also be made, as keratin derivative, of silk fibroin.

The polymers derived from chitin first comprise chitin, which is a natural polymer, and the deacetylated derivative of chitin known under the name of chitosan, obtained by saponification of the acetyl groups of chitin. Chitosan, as commercially available, is partially acetylated and contains 70 to 90% by weight of chitosan.

It can also be used in the form of insoluble salts, such as sulfates and phosphates. Products of this type are sold, for example, under the name "KYTEX" by the company "HERCULES".

The cellulosic polymers are chosen / more particularly from microcrystalline celluloses, such as the products sold under the name "AVICEL" by the company "FMC CORPORATION".

Among the synthetic polymers, mention may be made particularly of polyethylene, polypropylene, polystyrene, poly (methyl methacrylate) sold under the names "MICROPEARL M" and "MICROPEARL M100" by the company "SEPPIC", poly (methacrylate of methyl) crosslinked, such as the product sold under the name "MICROPEARL M 305" by the company "SEPPIC". Other polymers are, in particular, chosen from cross-linked poly-jâ -alanine, as described in French patent 2,530,250, or advantageously presented in the form of microspheres having a very low size dispersity, 85% by weight having a particle size between 28,000 and 46,000 nm, and of which the tau ;. crosslinking is between 1 and 15 and preferably between 1 and 8%.

It is also possible to use, as polymers, products known by the name of micro-sponges, such as crosslinked polymers of styrene / divinylbenzene or of methyl methacrylate / ethylene glecol dimethacrylate or of vinyl stearate / divinylbenzene, such as described in patents WO-88/01164 and US-A-4 690 825. Such polymers are essentially constituted by beads of crosslinked polymers comprising an internal network of pores, capable of retaining the melanin pigment. Other polymers of this type are hollow microspheres of a copolymer of vinylidene chloride and acrylonitrile, sold under the name of "EXPANCEL" by the company "KEMA NORD"; or also porous polyamide 12 microspheres , polyamide 6 or copolyamide 6/12, sold under the name "ORGASOL" by the company "ATOCHEM"; these microspheres preferably have a particle size between 10,000 and 50,000 nm. /

It is also possible to use silicone powders which are gums, resins and, more particularly, organopolysiloxane elastomers.

According to a third embodiment, the particulate filler is a filler constituted by particles with a lamellar structure, organic or inorganic, having a dimension of less than 50,000 nm.

The particles of lamellar structure, consisting of sheets for which the ratio between the largest dimension and the thickness is in particular between 2 and 100, are chosen in particular from the following products: L-lauroyllysine, such as the product sold under the name of "AMIHOPE LL" by the company "AJIN0M0T0"; ceramic microparticles possibly coated with zirconium powder, such as the products sold under the names of "TORAYCERAM ZP 550" and "ZP 4000" by the company "TORAY"; lamellar titanium dioxide, such as the products sold under the names "LUXELEN SILK D" and "LUXELEN SS" by the company "SUMITOMO", lamellar talc, boron nitride, such as the products sold respectively under the names "Boron nitride SF" or "SHP" by the companies "WACKER" and "KAWASAKI"; lamellar mica, such as the product sold under the name "MICA CONCORD 1000" by the company "SCIAMA"; bismuth oxychloride, such as the product sold under the name "PEARL GLO" by the company "MALLINCKRODT". The size of the particles of lamellar structure used in accordance with the invention is preferably less than 50,000 nm and, in particular, less than 25,000 nm; their size is generally greater than 500 nm; it is, in particular, between 1,000 and 20,000 nm. These particles have a thickness generally greater than 10 nm. These lamellar particles can be in the form of a laminated structure. Details and additions i concerning the structure and the preparation of these melanin pigments on lamellar charges are described in the patent application FR 90-090 053 filed on July 16, 1990 in the name of the applicant Company.

The vesicles of the compositions according to the invention are prepared from a lipid phase comprising at least one ionic and / or nonionic amphiphilic lipid optionally associated with at least one stabilizing additive, said vesicles containing an encapsulated aqueous phase, which can contain cosmetically active products such as moisturizers or soothing agents.

Among the nonionic lipids that can be used, there may be mentioned (1) the polyglycerol ethers, linear or branched, of formula: R10O-f C3H5 (OH) O-tjpH in which: • -C3H5 (0H) 0 is represented by following structures taken in mixture or separately: -CH, CH0HCH? 0-? -CHp-CHO-; -CH-CH, 0-;

I I ch2oh ch2oh »n is an average statistical value between 2 and 6; • R10 represents: (a) an aliphatic chain, linear or branched, containing from 12 to 18 carbon atoms 5 (b) a residue R11CO, where R ^ 1 is an aliphatic radical, linear or branched, in C1l "C17 '( c) a residue R12 - [- OC2H3 (R13) where: R12 can take the meaning (a) or (b) given for R10; OC2H3 (R13) - is represented by the following structures, taken in 1 mixture or separately: '<-OCH-CH, - and -0-CH, -CH-

I I R13 R13 where R13 takes the meaning (a) given for R10; (2) polyoxyethylenated fatty alcohols; (3) esters of optionally polyoxyethylenated polyols; (4) cerebrosides; and (5) oxyethylenated polyglycerol stearate.

Among the ionic amphiphilic lipids which can be used, mention may be made of: phosphoaminolipids; glycolipids? natural phospholipids, such as egg or soy lecithin, sphingomyelin, phosphatidylserine, dipalmitoylphosphatidylcholine and hydrogenated lecithins. The stabilizing additive is intended, in known manner, to modify the permeability and / or the surface charge of the vesicles. It is preferably chosen from the group formed by sterols and anionic stabilizers. The sterol is advantageously cholesterol.

The anionic stabilizer is advantageously chosen, on the one hand, from the monosodium or disodium salts of (ac4 in C14 ~ C22) -glutamates, such as the monosodium salt of N-stearoylglutamic acid, the disodium salts with acyl radicals copra and tallow or the cocoyl and stearoyl radicals, and, on the other hand, among the phosphoric esters of C12-C22 fatty alcohols. In known manner, it is possible to add to the amphipile lipid (s) both a sterol and an anionic stabilizer.

The vesicles advantageously have an average diameter of between 10 and 1000 nm.

The lipid phase of the vesicles, consisting of the lipids and, where appropriate, the stabilizer (s) associated with them, advantageously represents from 0.1 to / / 16% and, preferably, from 0.1 to 10% of the total weight of the composition; the ionic and / or non-ionic amphiphilic lipid (s) advantageously represent (s) from 0.1 to 16% and, preferably, from 0.1 to 10% of the total weight of the composition; and the stabilizing additive advantageously represents less than 10% of the total weight of the composition.

According to the invention, the melanin pigment can be introduced into the lipid phase before the formation of the vesicles, that is to say into the lipid or the lipid phase melted at around 100 ° C. It can also be dispersed in an oil, such as petrolatum oil, to then be incorporated into the vesicles.

In the compositions according to the invention, the (or) melanin pigment (s), optionally on a charge, is (or are) present (s) in proportions ranging in particular between 0.01 to 5% by weight per relative to the total weight of the composition.

The vesicles are present in proportions of between 0.5 and 15% by weight relative to the total weight of the composition.

The composition according to the invention can be in the form of a more or less thick dispersion, gel, cream and milk.

The composition according to the invention may also contain, in addition to the melanin pigment (s) and the vesicles, cosmetically acceptable additives such as dihydroxyacetone, melanin precursors such as tyrosine; silicones, in particular silicone gums and mixtures formed from a hydroxylated polydimethyl-siloxane at the end of the chain (called dimethiconol according to the nomenclature of the CTFA dictionary) and a cyclic polydimethylsiloxane (called cyclomethicone according to the nomenclature of the CTFA dictionary ), such as the product sold under the name "02-1401" by the company "DOW CORNING"; thickening agents, such as crosslinked polyacrylic acids, in particular those sold under the trade names of "CARBOPOL" (pair example 934 and 940) by the company "GOODRICH", cellulose derivatives, such as more particularly hydroxyethyl cellulose such as that sold under the name of "NATR0S0L PLUS GRADE 330 CS" by the Company "AQUALON", a xanthan gum, bentonite, an emulsion of crosslinked ammonium acrylate / acrylamide copolymer, sold under the name of "PAS 5161" by the Company "HOECHST"; and adjuvants such as mineral and vegetable oils, fatty acid esters, fatty alcohols, ultraviolet filters, mineral pigments, such as titanium dioxide and ferric oxide, preservatives, perfumes, agents basifying agents, acidifying agents, stabilizing agents or colorants.

Finally, the invention relates to the use of the composition as defined above for the protection of the skin or the hair against ultraviolet radiation and for the pigmentation of the skin or the hair.

To better understand the object of the invention, we will now describe, by way of purely illustrative and non-limiting examples, several modes of implementation. EXAMPLE 1 Sunscreen

First step: Preparation of an aqueous dispersion of vesicles

A lipid phase formulated as follows is used:

Nonionic amphiphilic lipid of formula:

in which: • -C3H5 (0H) 0- is represented by the following structures, taken as a mixture or separately:

• n is an average statistical value equal to 3 ........................................ 3.8 g

Cholesterol .................................. 3.8 g

Diketylphosphate ............................. 0.4 g

The mixture, having a gentle stirring at a temperature of 100 ° C.-110 ° C., is melted, the mixture having the above formulation, and, into the molten mixture, 16 g of water brought to 95 eC are gradually introduced, with slow stirring. , after which it is stirred vigorously in a turbine fitted with blades, until an off-white gelled mass is obtained.

2 g of glycerin and 16.9 g of water at 90-95 ° C. are then added. The temperature and stirring are maintained for 10 minutes.

When the temperature reaches 25 ° C, the mixture is refined by passing it through a high pressure homogenizer at 500 bars of the "RANNIE" or "GAULIN" type.

2 g of water containing a preservative are then introduced, and then it is refined again with the high pressure homogenizer.

The vesicles have an average diameter of the order of 300 nm.

Second step: Preparation of the cream c To the aqueous dispersion of vesicles obtained * in the first step, the following ingredients are added: - Mineral oil .................... ......... 15 g 2-ethylhexyl p-methoxycinnamate marketed under the name "PARSOL MCX" by the company "GIVAUDAN" ---- 5 g

Melanic pigment obtained by oxidative polymerization of 5,6-dihydroxyindole in the presence of hydrogen peroxide in an ammoniacal medium ........ 0.1 g

Yellow iron oxide ......................... 0.04 g

Red iron oxide ......................... 0.05 g

Titanium oxide (anatase) .................. 3 g

Crosslinked polyacrylic acid (PM 4,000,000) sold under the name "CARBOPOL 940" by the company "GOODRICH" (thickening agent) ...................... 0.42 g

Triethanolamine ............................ 0.4 g

Water ........................................ 30 g - Perfume, preservatives ... ................... qs

Mineral oil, 2-ethylhexyl p-methoxycinnamate and perfume are introduced into the aqueous dispersion of vesicles obtained in the first step, at 35 ° C., and the mixture is stirred in a turbine. It is refined in a high pressure homogenizer at 500 bars. The melanin pigment is then added, then the mixture obtained is passed through a "FRYMA" or "DYNOMILL" type grinder. The metal oxides are then added and a new passage is carried out in the mill. We thicken in. last place the mixture in a paddle turbine, adding to it a very homogeneous aqueous gel constituted by the thickening agent dissolved with triethanolamine in water containing the preservatives and the perfume.

The composition thus obtained is applied by topical application at a rate of 2 mg / cm 2 on a skin area in a single application. The treated skin area is subjected to ultraviolet irradiation (OSRAM ULTRAVITALUX lamp) for 10 minutes at a rate of 1 m W / cm2. One notes that, one hour after the irradiation, “no erythema is visible on the zone of skin tested whereas the same irradiation on another zone of skin of the same subject leads to an erythema in the absence of any prior treatment . β EXAMPLE 2: Self-tanning cream

First step: Preparation of an aqueous dispersion of vesicles

A lipid phase formulated as follows is used:

Nonionic amphiphilic lipid of formula:

in which: * -C3H5 (0H) 0- is represented by the following structures, taken as a mixture or separately:

• n is an average statistical value equal to 3 ........................................ 3.8 g

Cholesterol .................................. 3.8 g

Glutamate monosodium salt of formula:

in which R is a mixture of alkenyl and / or C13-C21 alkyl radicals derived from tallow fatty acids, marketed under the name of ".ACYLGLUTAMATE HS 11" not by the company "AJINOMOTO" '........ ................................. 0.4 g

The mixture having the above formulation is melted, with gentle stirring at a temperature of 100 ° C.-110 ° C., and, into the molten mixture, 15 g of water brought to 95 ° C. are gradually introduced, with slow stirring, after which it is stirred vigorously in a turbine fitted with blades, until an off-white gelled mass is obtained.

5 g of glycerin and 13 g of water are then added to 90-95 * 0. The temperature and the stirring are maintained for 10 minutes.

Then the temperature is lowered to 60 ° C and 5 g of dihydroxyacetone dissolved in 3.8 g of water are introduced.

The mixture obtained is refined by passing it through a high pressure homogenizer at 500 bars of the "RANNIE" or "GAULIN" type. At 40 ° C., 0.8 g of water containing a preservative is introduced, then it is further refined with the high pressure homogenizer.

The vesicles have an average diameter of the order of 300 nm. /

Second step: Preparation of the cream To the aqueous dispersion of vesicles obtained in the first step, the following ingredients are added:

Mineral oil ............................. 12 g

Melanic pigment obtained by oxidative polymerization of 5,6-dihydroxyindole in the presence / of oxygenated water in an ammoniacal medium ........ 0.1 g

Yellow iron oxide ......................... 0.15 g - 'Red iron oxide .......... ............... 0.1 g

Titanium oxide (anatase) ...... · ............ 2.2 g "

Hydroxyethylcellulose sold under the name "NATR0S0L PLUS GRADE 330 CS" by the company "AQUALON" (thickening agent) ............. 0.5 g

Water ........................................ 30 g

Perfumes, preservative ...................... qs

Mineral oil and perfume are introduced into the aqueous dispersion of vesicles obtained in the first step, at 35 ° C., and the mixture is stirred in a turbine. It is refined in a high pressure homogenizer at 500 bars. The melanin pigment is then added; then the mixture obtained is passed through a "FRYMA" or "DYNOMILL" type mill. The metal oxides are then added and a new passage is carried out in the mill.

Finally, the mixture is thickened in a paddle turbine, adding to it a very homogeneous aqueous gel consisting of the thickening agent dissolved in water containing a preservative and perfume.

The composition thus obtained is applied by topical application at a rate of 2 mg / cm 2 on a skin area in a single application. After a few hours, the skin will color in a color close to that of natural tanning. EXAMPLE 3: Sun milk

A composition is prepared having the following formulation:

Nonionic amphiphilic lipid of formula:

in which: * -C3H5 (0H) 0- is constituted by a mixture of the radicals:

-OCgHjiR ') - consists of a mixture of radicals:

and

. n is an average statistical value equal to 6. R 'is a mixture of the radicals CUH29 and C16% ....................................... 1.9g

Dimyristylphosphate ........................ 0.1 g

Glycerin .................................. 1.5 g

Vaseline oil .......................... 15 g / - Melanin pigment obtained by oxidative polymerization of 5,6-dihydroxyindole in the presence of water oxygenated in an ammoniacal medium, on boron nitride sold under the name of "SH P2" by the company "KAWASAKI" ......................... ........ 0.5 g Mixture of a polydimethylsiloxane hydroxylated at the chain end and octamethylcyclo-tetrasiloxane (13:87 by weight), marketed under the name "Q2-1401" by the Company " DOW CORNING ”* ..... 3.4 g

Volatile silicones ........................ 1.6 g, / 2-Ethylhexyl monococoate .............. ..... 3 g

Crosslinked polyacrylic acid (PM 4,000,000) sold under the name "CARBOPOL 940" by the company "GOODRICH" ... 0.35 g

Triethanolamine ............................ 0.33 g

Water ..................... / .................. 76 g

Preservatives, perfume ...................... qs

Melting, gently stirring at a temperature of 85 ° C, a mixture of nonionic lipid and dimyristylphosphate. 4 g of water brought to 85 ° C. are gradually introduced into the molten mixture, with slow stirring, after which it is stirred vigorously in a turbine fitted with blades, until an off-white gelled mass is obtained.

Then glycerin and 42 g of water at 60 ° C. are added with rapid stirring. The temperature and the stirring are maintained for 10 minutes. Then add the petroleum jelly oil previously heated to 60 ° C.

When the temperature reaches 25 ° C., the mixture is refined by two passages in a high pressure homogenizer at 500 bars of the "RANNIE" or "GAULIN" type.

The melanin pigment is then added over boron nitride, followed by stirring for 5 minutes. The mixture of polysiloxanes, volatile silicones and 2-ethylhexyl monococoate is then added. Then stirred for 10 minutes.

The mixture is finally thickened in a paddle turbine, adding to it a very homogeneous aqueous gel constituted by the thickening agent dissolved with triethanolamine in 30 g of water containing preservatives and perfume.

The composition thus obtained is used as in Example 1. The same results are observed. EXAMPLE 4: After-sun cream ““

A composition is prepared according to the following formulation: ·· n

Non-ionic lipid of formula:

in which: • -C3H5 (0H) 0- is represented by the following structures, taken as a mixture or separately:

• Π is an average statistical value equal to 3 ....................................... 3 , 8 g cholesterol ................................ 3.8 g - Diketylphosphate ........ ................... 0.4 g

Glycerin .................................. 2 g

Vaseline oil .......................... 15 g

Melanic pigment obtained by oxidative polymerization of 5,6-dihydroxyindole in the presence of hydrogen peroxide in an ammoniacal medium, on bismuth oxychloride marketed under the name of "PEARL GLO UVR 1086" by the company "MALLINCKRODT" .... .......... 0.5 g Terpene derivative (bisabolol) sold under the name "DRAGOSANTOL" by the company "DRAGOCO" ................. ...... 0.5 g

Crosslinked polyacrylic acid (PM 4,000,000) sold under the name "CARBOPOL 940" by the company "GOODRICH" ... 0.42 g

Triethanolamine ............................ 0.4 g

Water ........................................ 88 g

Preservative, "perfume ....................... qs"

Melting, gently stirring at a temperature of 100 ° C-110 ° C, a mixture of non-ionic lipid, cholesterol and diketyl phosphate. Into the molten mixture, gradually introduced 16'g of water brought to 95eC, with slow stirring, after which it is stirred vigorously in a turbine fitted with blades, until an off-white gelled mass is obtained.

Glycerin and 42 g of water at 60 ° C. are then added. The temperature and the stirring are maintained for 10 minutes. Then add petroleum jelly oil.

The mixture obtained is refined by two passages in a high pressure homogenizer at 500 bars of the "RANNIE" OR "GAULIN" type.

The melanin pigment is then added to bismuth oxychloride, and the mixture is stirred for 5 minutes. The terpene derivative is then added.

The mixture is finally thickened in a paddle turbine, adding to it a very homogeneous aqueous gel consisting of the thickening agent dissolved in 30 g of water containing a preservative and perfume, and neutralized by triethanolamine.

The composition thus obtained is applied by topical application at a rate of 2 mg / cm 2 to an area of skin previously exposed to the sun. In addition to its soothing function, this cream gives a slight tan to the skin. EXAMPLE 5 Sunscreen

The following formulation is prepared:

Nonionic lipid of formula: ci6H33 ° -f ~ c3H5 (OH) ° - ^ r H in which ,: * -C3H5 (0H) 0- is represented by the following structures, taken as a mixture or separately:

and • n is an average statistical value equal to 3 ....................................... .. 3.8 g

Cholesterol .................................. 3.8 g

Diketylphosphate ............................. 0.4 g

Glycerin .................................... 2 g

Vaseline oil ............................ 14.4 g

Melanic pigment obtained by oxidative polymerization of 5,6-dihydroxyindole in the presence of hydrogen peroxide in an ammoniacal medium on mica sold under the name of "MICA CONCORD 1000" by the company "SCIAMA" .......... ........................... 0.5 g

Yellow iron oxide ........................... 0.04 g

Iron oxide sienna .......................... 0.05 g

Crosslinked polyacrylic acid (PM 4,000,000) sold under the name "CARBOPOL 940" by the company "GOODRICH" ..... 0.42 g

Triethanolamine .............................. 0.4 g

Water .......................................... 74 g

Preservative, fragrance ......................... qs

Melting, gently stirring at a temperature of 100 ° C-110 ° C, a mixture of nonionic lipid, cholesterol and diketylphosphate. Into the molten mixture, gradually introduced 16 g of water brought to 85 ° C, with slow stirring, after which it is stirred vigorously in a turbine fitted with blades, until an off-white gelled mass is obtained.

Glycerin and 28. g of water at 60 ° C. are then added. The temperature is maintained and the stirring is carried out for 10 minutes. Then the petrolatum oil previously heated to 60 ° C. is added.

The mixture obtained is refined by two passages in a high pressure homogenizer at 500 bars of the "RANNIE" OR "GAULIN" type.

The melanin pigment on mica is then added with stirring, then the iron oxides are added with stirring.

The mixture is finally thickened in a paddle turbine, adding to it a very homogeneous aqueous gel consisting of the thickening agent dissolved in 30 g of water containing a preservative and perfume, and neutralized by triethanolamine.

The composition thus obtained is used according to the method described in Example 1. The same results are observed.

Claims (26)

. CLAIMS 1 - Cosmetic composition comprising in aqueous dispersion lipid vesicles with a 'lamellar structure encapsulating an aqueous phase, characterized in that it contains at least one melanin pigment with a particle size between approximately 500 and 50,000 nm, mixed with the vesicles in the continuous phase of the dispersion and / or in association with the lipid sheets of the vesicles ^. " 2 - Composition according to claim 1, characterized in that the (or) melanin pigment (s) are obtained by oxidation of at least one indolic compound, by oxidative or enzymatic polymerization of melanic precursors, or by extracting melanin from substances containing it. 3 - Composition according to claim 2 characterized in that the indolic compound is chosen from those corresponding to formula (I):

(I) in which: R1 and R3 represent, independently of one another, hydrogen or C1-C4 alkyl; R2 represents hydrogen, C1-C4 alkyl / carboxyl or (C1-C4 alkoxy) -carbonyl; R4 and R7 represent, independently of each other, hydrogen, hydroxy, C 1 -C alkyl, amino, C 4 alkoxy, (C 1 -C 4 acyloxy, (C 2 -C 4 acyl) - amino; R5 represents hydrogen, hydroxy, C alkoxy, - ^, C ^ alkyl, CA, halogen, amino, (C2-Cu acyl) -oxy, (C2-C4 acyl) -amino, trimethylsilyloxy; R6 represents hydrogen, hydroxy, C1-C4-alkoxy, amino, (C2-C4 acyl) -oxy, (C2-C4 acyl) -amino, trimethylsilyloxy, (C2-C4 hydroxyalkyl) -amino; R5 and R6 can also form, jointly with the carbon atoms to which they are attached, a methylenedioxy ring optionally substituted by a C 1 -C 4 alkyl or C 1 -C 4 alkoxy group, or else a carbonyldioxy ring: at least one radicals R4 to R7 represent an OZ or NHR ° group with at most one of the radicals R4 to R7 representing NHR °; and at most two of the radicals R4 to R7 represent OZ and, in the case where Z represents hydrogen, the two OH are in positions 5 and 6; and at least one of the radicals R4 to R7 represents hydrogen, and in the case where only one of these radicals represents hydrogen, only one radical among R4 to R7 then represents NHR ° or OZ, the other radicals representing alkyl at 0, -C ^; the R ° of the NHR ° group designating hydrogen, C2-C4 acyl, hydroxy-C2-C4 alkyl, and the Z of the OZ group designating hydrogen, C2-C14 acyl, C., - C4 alkyl, or trimethylsilyl, and their alkali, alkaline earth, ammonium or amine salts. 4 - Composition according to claim 3, characterized in that the indole compound is chosen from the group formed by 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxy 5-methoxyindole , 4-hydroxy 5-ethoxyindole, 2-carboxyL 5-hydroxyindole, 5-hydroxy 6-methoxyindole, 6-hydroxy 7-methoxyindole, 5-methoxy 6-hydroxyindole, 5,6-dihydroxyindole, N -methyl 5,6-dihydroxyindole, 2-methyl 5,6 -dihydroxyindole, 3-methyl 5,6-diydroxyindole, 2,3-dimethyl 5,6-dihydroxyindole, 2-carboxyl 5.6-dihydroxyindole, 4 -hydroxy 5-methyl indole, 2-carboxyl 6-hydroxyindole, 6-hydroxy N-methylindole, 2-ethoxycarbonyl 5,6-dihydroxyindole, 4-hydroxy 7-methoxy 2,3-dimethylindole, 4-hydroxy 5-ethoxy N-methylindole, 6-hydroxy 5-methoxy 2-methylindole, 6-hydroxy 5-methoxy 2,3-dimethylindole, 6-hydroxy 2- ethoxycarbonylindole, 7-hydroxy 3-methylindole, 5- hydroxy 6-me thoxy 2,3-dimethylindole, 5-hydroxy 3-methylindole, 5-acetoxy 6-hydroxyindole, 5-hydroxy n 2-ethoxycarbonylindole, 6-hydroxy 2-carboxyl 5-methyl-indole, 6-hydroxy 2 -ethoxycarbonyl 5-methoxyindole, the 6- N - /? - hydroxyethylaminoindole, 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, N-methyl 6/3-hydroxyethylaminoindole, 6-amino 2,3-dimethylindole, 6-amino 2,3,4,5-tetramethylindole, 6-amino 2,3,4-trimethylindole, 6-amino 2,3,5-tri-methylindole, 6-amino 2,3,6-trimethylindole , 5.6-diacetoxyindole, 5-methoxy 6-acetoxyindole, 5.6- diraethoxyindole, 5,6-dibenzyloxyindole, 5,6-methylenedioxyindole, 5,6-trimethylsilyloxyindole, the phospboric ester of 5,6-dihydroxyindole and the addition salts of these compounds. 5 * Composition according to one of claims 1 to 4 characterized in that the (or) melanin pigment (s) is (or are) associated (s) with at least one particulate filler. 6 - Composition according to claim 5 characterized in that the (or) melanin pigment (s) result (s) from the oxidation of at least one indole compound of formula (X), as defined to one of claims 3 and 4 f in admixture with the filler in an essentially non-solvent medium of said filler, or of the oxidative polymerization of .aclanic precursors on the filler. 7 - Composition according to one of claims 5 ît 6 characterized in that the particulate filler is an inert mineral filler, of particle size less than 20,000 nm. ..8 - Composition according to one of claims 5 st "· 6 characterized by the fact that the particulate filler is an inert polymeric filler, of particle size less than 100,000 nm, chosen from natural or synthetic polymers, organic or inorganic, to crosslinked μ network, crystalline or amorphous, having a molecular weight of between 5,000 and 5,000,000. 9 - Composition according to claim 8 / characterized in that the polymers are chosen from the group formed by polymers derived from keratin, chitin, cellulose, polyamides and homo- or copolymers resulting from the polymerization of mono- or polyethylenic, aliphatic or aromatic monomers, with a crosslinked, crystalline or amorphous network. 10 ~ Composition according to claim 9 characterized in that the polymers derived from keratin are chosen from the group formed by animal or human keratins; chemically modified keratins, by hydrolysis or oxidation, having a molecular weight of between 10,000 and 250,000, and silk fibroin. 11 - Composition according to claim 9, characterized in that the polymers derived from chitin consist of chitin and / or its deacetylated derivative. 12 - Composition according to claim 9, characterized in that the cellulosic polymers are microcrystalline celluloses. 13 - Composition according to claim 9, characterized in that the synthetic polymers are chosen from the group formed by polyethylene, polypropylene, polystyrene, poly (methyl methacrylate) and crosslinked poly (methyl methacrylate). 14 - Composition according to claim ^ characterized in that the polymer is a crosslinked poly-β-alanine. 15 - Composition according to claim 3, characterized in that the polymers are constituted by hollow microspheres of copolymer of vinylidene chloride and acrylonitrile or by porous microspheres of polyamide 12, polyamide 6 or copolyamide 6/12. ·· » 16 - Composition according to claim β, characterized in that the polymers are micro-sponges consisting of crosslinked polymers of styrene / divinylbenzene, methyl methacrylate / ethylene glycol dimethacrylate, or vinyl stearate / divinylbenzene. 17 - Composition according to claim 8, characterized by * ie the fact that the polymers consist of silicone powders. 18 - Composition according to one of claims 5 and 6, characterized in that the particulate filler is a filler constituted by particles with a lamellar structure, organic or mineral, having a dimension of less than 50,000 nm. 19 - Composition according to claim 13 characterized in that the particles with a lamellar structure are chosen from L-lauroyllysine, ceramic microparticles optionally covered with zirconium powder, lamellar titanium dioxide, lamellar talc, boron nitride , lamellar mica, bismuth oxychloride. 20 ~ Composition according to one of claims 18 and 19, characterized in that the particles with a lamellar structure consist of sheets for which the ratio between the largest dimension and the thickness is between 2 and 100. 21 - Composition according to one of claims 1 to 20, characterized in that the (or) lipid (s) constituting (s) of the lipid phase of the vesicles is (or are) chosen (s) from the group formed by nonionic amphiphilic lipids, ionic amphiphilic lipids and their mixtures. 22. - Composition according to claim 21, characterized in that the nonionic amphiphilic lipids are chosen from the group formed by (1) the polyglycerol ethers, linear or branched, of formula: in which: t • -CjHj ( OH) O is represented by the following structures taken in mixture or separately:

• n is an average statistical value between 2 and 6; • R10 represents: (a) an aliphatic chain, linear or branched, containing from 12 to 18 carbon atoms; (b) a residue R11CO, where R11 is an aliphatic radical, linear or branched, in C11 "C17 '(c) a residue R12 - [- OC2H3 (R13) -] -, where:. R12 can take the meaning (a ) or (b) given for R10; OC2H3 (R13) - is represented by the following structures, taken in mixture or separately:

where R13 takes the meaning (a) given for R10; (2) polyoxyethylenated fatty alcohols; (3) esters of optionally polyoxyethylenated polyols; (4) cerebrosides; and (5) oxyethylenated polyglycerol stearate. 23 - Composition according to claim 21 characterized in that the ionic amphiphilic lipids are chosen from: phosphoamiholipids; i> glycolipids 7 - _ natural phospholipids, sphingomyelin, phosphatidylserine, dipalmitoylphosphatidyl-choline and hydrogenated lecithins. 24- Composition according to one of claims 21 to 23, characterized in that the lipids are associated with at least one stabilizing additive chosen from the group formed by sterols and anionic stabilizers. 2Fi - Composition according to one of claims 21 to 24 characterized in that the vesicles have an average diameter between 10 and 1000 nm. 26- Composition according to one of claims 1 to 25 characterized in that the lipid phase of the vesicles, consisting of (or) lipid (s) and (or) stabilizer (s) optionally associated (s) with these represent from 0.1 to 16% of the total weight of the composition, the proportion of the stabilizer (s) not exceeding 10% of the total weight of the composition. 27 - Composition according to one of claims 1 to 26 characterized in that the vesicles are present in proportions of between 0.5 and 15% by weight relative to the total weight of the composition. 28- Composition according to one of claims 1 to 27 characterized in that the (or) melanin pigment (s), optionally on charge, is (or are) present (s) in proportions of between 0 , 01 and 5% by weight relative to the total weight of the composition. 29 - Composition according to one of claims 1 to 2 & characterized in that it is in the form of lotion, gel, cream and milk. 30 "Composition according to one of claims 1 to '29 characterized in that it contains at least one cosmetically acceptable additive chosen from the group formed by dihydroxyacetone, silicones, thickening agents, mineral oils, vegetable oils , fatty acid esters, fatty alcohols, filters, ultraviolet, mineral pigments, preservatives, perfumes, basifying agents, acidifying agents, stabilizing agents and colorants. 31- Use of the composition according to one of claims 1 to 30 for the protection of the skin or hair against ultraviolet radiation, or for the pigmentation of the skin or hair.