FR2947724A1 - COMPOSITE MATERIAL COMPRISING UV FILTERS AND PLASMONIC PARTICLES AND USE IN SOLAR PROTECTION - Google Patents

Abstract

The present application relates to a composite material filtering ultraviolet radiation comprising at least one plasmonic particle formed of at least one metal and at least one ultraviolet radiation filtering agent, said filtering agent being located inside the particle. plasmonic or outside the plasmonic particle at a sufficiently small distance from the plasmonic particle, so that the absorption of ultraviolet radiation on at least a portion of the spectrum of the filtering agent is increased. The present application also relates to a method of cosmetic treatment of the skin or of the hair intended to protect them against the effects of UV rays consisting in applying thereon an effective quantity of a composite material and a process for photostabilization and / or increasing the absorption of a photoprotective agent with at least one plasmonic particle.

Description

B09-1406EN -SE / EVH OA 09289

Anonyme known as: L'OREAL MATERIAU COMPOSITE COMPRISING UV FILTERS AND PLASMONIC PARTICLES AND USE IN SOLAR PROTECTION Invention of:

COMPOSITE MATERIAL COMPRISING UV FILTERS AND PLASMONIC PARTICLES AND USE IN SOLAR PROTECTION The present application relates to the field of photoprotective agents. The present invention relates to ultraviolet radiation filtering materials and cosmetic compositions for topical use for the photo-protection of the skin and / or hair against ultraviolet (UV) radiation. These compositions are hereinafter referred to as antisolar compositions or sunscreen compositions and comprise, in a cosmetically acceptable medium, a combination of at least one UV solar filter and plasmonic particles. The present application also relates to the use of plasmonic particles to increase the absorption of a UV filter and / or to improve the photostabilisation of said UV filter. It is known that the luminous radiations of wavelengths between 280 nm and 400 nm allow the browning of the human epidermis, and that the wavelength rays more particularly between 280 and 320 nm, known under the name UV -B, cause erythema and skin burns that can affect the development of natural tanning. For these reasons as well as for aesthetic reasons, there is a constant demand for means of control of this natural tan to thereby control the color of the skin; it is therefore necessary to filter this UV-B radiation. It is also known that UV-A rays of wavelengths between 320 and 400 nm, which cause browning of the skin, are capable of inducing an alteration thereof, especially in the case of a skin sensitive or skin continuously exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature cutaneous aging. They promote the triggering of the erythematous reaction or amplify this reaction in some subjects and may even be the cause of photo-toxic or photo-allergic reactions. Thus, for aesthetic and cosmetic reasons such as the preservation of the natural elasticity of the skin for example, more and more people wish to control the effect of UV-A on their skin. It is therefore desirable to filter the UV-A radiation as well. In order to ensure protection of the skin and keratin materials against UV radiation, it is generally used antisolar compositions comprising organic filters, active in the UV-A and active in the UV-B. Most of these filters are fat soluble. In this respect, a particularly interesting family of UV-A filters currently consists of the dibenzoylmethane derivatives, and in particular 4-tert-butyl-4'-methoxydibenzoylmethane, which in fact have a high intrinsic absorption capacity. These dibenzoylmethane derivatives, which are now products that are well known per se as active filters in UV-A, are described in particular in French patent applications FR-A-2326405 and FR-A-2440933, as well as in European Patent Application EP-A-0114607; 4-tert-butyl-4'-methoxydibenzoyl methane (or avobenzone) is also currently offered for sale under the trade name PARSOL 1789 by DSM NUTRITIONAL PRODUCTS.

UV filters are however not completely satisfactory, they have the following disadvantages. To obtain an effective level of protection, it is often necessary to have formulations comprising a high concentration of UV filters, this UV filter concentration can be up to 20% by weight relative to the weight of the final composition. To ensure effective protection over the entire UV spectrum, it is necessary to combine several complementary filters each absorbing in a different area of the UV spectrum. However, despite these precautions, the area of very long UVA (between 360 and 400 nm) remains uncovered. There are indeed no UV absorbers filters effectively in this area, only some UV filters absorb a little in the area of very long UVA.

Some UV filters such as dibenzoylmethane derivatives (UVA filters) such as Butylmethoxy Dibenzoylmethane and cinnamate derivatives (UVB filters) such as Ethylhexylmethoxy Cinnamate are relatively sensitive to ultraviolet radiation (especially UV-A), that is to say that is to say, more precisely, that they present an unfortunate tendency to degrade more or less rapidly under the action of the latter. Thus, this substantial lack of photochemical stability (photostability) of the dibenzoylmethane derivatives and cinnamates against the ultraviolet radiation which they are intended to be subjected to, does not guarantee a constant protection during prolonged exposure to sunlight. Accordingly, repeated applications at regular and close time intervals must be performed by the user to achieve effective protection of the skin against UV rays.

The use of plasmonic particles in photostable filtering compositions is mentioned in application US 2005/0265935. In addition, the application US2009 / 0022766 relates to a composition of nanoparticles comprising a metal core covered with a layer, said layer comprising a molecule excitable by a radiation, the excitable molecule is positioned at a sufficient distance from the core to allow an increase in emissions when it is excited by electromagnetic energy in the visible, this composition may optionally include an inorganic pigment.

There remains a need for UV sunscreen compositions which do not have the drawbacks presented above and in particular which are photo-stable, effective over the entire UV spectrum, without the need to use high amounts of sunscreens.

Unexpectedly and advantageously, the inventors of the present application have shown that these disadvantages can be solved by means of the composite materials and compositions according to the present invention.

A first object of the present invention relates to a composite material filtering ultraviolet radiation comprising at least one plasmonic particle formed of at least one metal and at least one ultraviolet radiation filtering agent, said filtering agent being located at the inside the plasmonic particle or outside the plasmonic particle at a sufficiently small distance from the plasmonic particle, so that the absorption of ultraviolet radiation on at least a part of the spectrum of the filtering agent is increased. A second object of the present invention relates to a cosmetic composition for sun protection comprising, in a cosmetically acceptable medium, the composite material according to the present invention. A third object of the present application is a method for photostabilizing a photosensitive agent, filtering the UV radiation in which said filtering agent is placed inside the plasmonic particle or outside the plasmonic particle at a distance sufficiently low of the plasmonic particle, so that the absorption of ultraviolet radiation on at least a portion of the spectrum of the filtering agent is increased. For the purposes of the present application, the term "photosensitive agent" means an agent which degrades under the influence of UV radiation and thus filters out said UV radiation. A fourth subject of the present invention relates to the use of a plasmonic particle for photostabilizing a photosensitive agent, filtering the UV radiation of placing said filtering agent inside the plasmonic particle or outside the plasmonic particle to a sufficiently small distance from the plasmonic particle, so that the absorption of ultraviolet radiation on at least a part of the spectrum of the filtering agent is increased.

A fifth object of the present invention relates to a method of cosmetic treatment of the skin or hair for protecting them against the effects of UV rays consisting in applying thereon an effective amount of a cosmetic composition according to the present invention. By composite material, within the meaning of the present application, is meant a material formed of several distinct components. By plasmonic particle, within the meaning of the present application, is meant a particle whose electrons oscillate collectively when excited by a suitable form of energy such as radiation, this oscillation being at the origin of a wave. electromagnetic. The plasmonic particles generally consist of one or more metals of the same nature or of a different nature.

The inventors of the present application have demonstrated that the use of a filtering agent and a plasmonic particle at a sufficiently small distance makes it possible to significantly increase the absorption and light stabilization of said UV filter. Without wishing to be bound to any theory, in the composition according to the present invention, the plasmonic particles, subjected to radiation of wavelength corresponding to the solar radiation, oscillate to give rise to waves called plasmonic resonances which will allow increase the absorption of UV rays by the UV filter present near the plasmonic particle. Therefore, when the UV filter is applied to a substrate such as skin and / or hair, absorption of UV radiation by the UV filter will more effectively protect the substrate. In addition, the absorption zone of the UV filter is not substantially modified.

More effective sun protection is thus obtained with the known UV filters. The use of plasmonic particles and a given UV filter in a composite material according to the present invention makes it possible to amplify the absorption of the UV filter in its absorption range.

This use is particularly advantageous in the area of very long UVA because it will significantly increase the absorption of UV filters that absorbed this area very long UVA.

By combining several filters in a composite material according to the present invention, an increase in the effectiveness of the sunscreen compositions is obtained.

The effectiveness of the sunscreen compositions is generally expressed by the sun protection factor (SPF) expressed mathematically by the ratio of the dose of UV radiation necessary to reach the erythematogenic threshold with the UV filter with the dose of UV radiation. necessary to reach the erythematogenic threshold without UV filter. This factor therefore concerns the effectiveness of the protection against erythema, the biological spectrum of action of which is centered in the UVB and consequently, accounts for the protection with respect to this UV-B radiation.

To characterize protection against UV-A, the PPD (Persistent Pigment Darkening) method, which measures the skin color observed 2 to 4 hours after exposure of the skin to UV-A, is particularly recommended and used. This method has been adopted since 1996 by the Japanese Cosmetic Industry Association (JCIA) as the official testing procedure for UV-A labeling of products and is frequently used by testing laboratories in Europe and the United States; (Japan Cosmetic Industry Association Technical Bulletin, Measurement Standards for UVA protection efficacy, Issued November 21, 1995 and efective of January 1, 1996).

The UVAPPD sun protection factor (FP UVAppd) is mathematically expressed by the ratio of the UV-A radiation dose required to reach the UV filter pigmentation threshold (MPPDp) with the dose of UV-A radiation required to reach the threshold of pigmentation without UV filter (MPPDäp). MPPDp ', epD The increase in absorption over the entire UV spectrum will make it possible to prepare compositions as effective in terms of sun protection as the compositions of the prior art but containing a smaller amount of UV filters.

It has also been shown that the presence of plasmonic particles has a photostabilizing effect of the UV filters. Other objects, features, advantages of the present invention will appear on reading the description and examples which follow.

The composite material according to the present invention comprises at least one plasmonic particle formed of at least one metal, and at least one filtering agent disposed at a small distance from one another, said filtering agent being located outside the plasmonic particle or inside the plasmonic particle.

The interactions between the coated particle (core particle) and the layer (coating in English language) may be non-covalent interactions, these are then for example electrostatic, hydrophobic, steric interactions; or covalent interactions.

Embodiments of composite materials according to the present invention include the following modes. These embodiments do not constitute an exhaustive list of the composite materials covered by the invention. The composite material may comprise at least one plasmonic particle coated with a layer comprising particles of filtering agents or formed of at least one ultraviolet radiation filtering material. In a first embodiment shown in FIG. 1, the composite material consists of a plasmonic particle (1) covered with a layer (3) comprising particles and or molecules of filtering agents (2). Conventionally, the layer consists of a metal oxide, conventionally silica, or a polymeric material.

The plasmonic particle consists of one or more metals. This type of composite material can be produced by implementing a sol-gel process, for example by implementing the method described in the example of the application US2009 / 0022766. For this embodiment, the order of magnitude of the plasmonic particle or particles is from 1 to 200 nm and more preferably from 1 to 20 nm, the thickness of the layer is from 1 to 250 nm and more preferably from 1 to 40 nm.

In a second embodiment shown in Figure 2, the plasmonic particle (1) consisting of one or more metals is covered with a layer of filtering agents (2). For this embodiment, the order of magnitude of the plasmonic particle or particles is from 1 to 200 nm and more preferably from 1 to 20 nm, the thickness of the layer is from 1 to 250 nm and more preferably from 1 to 40 nm. This embodiment is among the preferred. The composite material may also comprise at least one plasmonic particle formed of a non-metallic matrix within which are disposed one or more metal particles, said non-metallic matrix further comprising at least one ultraviolet radiation filtering agent or being formed of at least one ultraviolet radiation filtering material. In a third embodiment shown in FIGS. 3 and 4, the composite material consists of a matrix (3) comprising plasmonic particles (1) and filtering agents (2). The matrix is conventionally made of silica, a polymeric material or latex. For this embodiment, the order of magnitude of the matrix is from 0.1 to 101 μm, preferably from 0.5 to 51 μm, and the order of magnitude of the plasmonic particles is from 1 to 200 nm and more preferably from 1 to 200 μm. 20 nm.

Advantageously, the distance between a plasmonic particle and the filtering agent ranges from 0 to 250 nm, preferably it is less than 40 nm. For these first three embodiments, it has been shown that the use of a coating or matrix having a low refractive index is particularly advantageous for improving the photoprotection. Preferably, the refractive index of the coating or of the matrix ranges from 1 to 3; preferably from 1.0 to 1.7.

Another criterion for the choice of the matrix is that it must be able to incorporate a large quantity of filtering agents. The composite material may also comprise at least one plasmonic particle comprising a non-metallic core and a metal shell around the core, said at least one filtering agent being in the core or forming the core. In the fourth and fifth embodiments described below, the lower diameter of the metal coating is less than 500 nm and more preferably less than 80 nm. In a fourth embodiment shown in FIG. 5, the composite material consists of a filtering agent (2) covered with a coating in which plasmonic resonances (1), that is to say a metallic coating, develop. or a metal alloy coating. In a fifth embodiment shown in FIG. 6, the composite material consists of a polymeric matrix or metal oxide (3) comprising filtering agents (2) covered with a coating in which plasmonic resonances ( 1) that is to say a metal coating or a metal alloy coating.

The composite material may also comprise at least one plasmonic particle having inclusions in its relief and a filtering agent placed in inclusions in the relief of the plasmonic particle.

In a sixth embodiment shown in FIG. 7, the composite material consists of a filtering agent (2) placed in inclusions of the plasmonic particle (1), that is to say that the inclusions are made in the mass of the plasmonic particle.

This embodiment is among the preferred. In a seventh embodiment shown in FIG. 8, the composite material consists of a filtering agent (2) placed in inclusions in the relief of the plasmonic particle (1). For this embodiment, the order of magnitude of the plasmonic particle is 0.1 to 101 μm, the size of the surface roughness or inclusions in the relief being less than 250 nm and more preferably less than 40 nm. among the favorites. The composite material according to the present invention may also consist of at least two composite materials as described in the various embodiments presented above, for example a metal particle with bulk inclusions and an outer coating composed of agents. filter. The plasmonic particles that can be used for the purposes of the present application are in particular chosen from the group consisting of the following metals: tungsten (W), aluminum (Al), palladium (Pd), platinum (Pt), silver (Ag), copper ( Cu), gold (Au), chromium (Cr), zinc (Zn), rhodium (Rh), nickel (Ni), tin (Sn), as well as their alloys. Preferably, the plasmonic particles are chosen from the metals according to silver, aluminum, chromium, zinc and rhodium, as well as their alloys. The alloys of several metals of the plasmonic particles may be stoichiometric or non-stoichiometric Plasmonic particles may be of various shapes such as spherical, cylindrical, cubic, conical, elliptical platelet, triangular, pyramidal, polyhedral. They can be hollow, smooth, rough or porous. They can be formed of one or more metals. When they are formed of several metals, it may be a continuous phase of metals such as an alloy that is to say a continuous phase in which the metals are no longer dissociable, or a discontinuous phase of metals for example consisting of a metal covered with a layer of another metal.

Within the composition according to the invention, the plasmonic particles may be free, aggregated or form a two-dimensional or three-dimensional network, for example a two-dimensional or three-dimensional matrix. The composition according to the present invention may comprise plasmonic particles of the same nature or of different natures. The formation of aggregates or networks of plasmonic particles makes it possible to further increase the effect of plasmonic particles with respect to the UV filter: the UV filter is in fact subjected to the plasmonic resonances of several plasmonic particles.

Advantageously, the size of the plasmonic particles is between 1 nm and 200 m, preferably less than 130 nm, preferably less than 100 nm, it is advantageously less than 50 nm and even more advantageously less than 20 nm. The inclusions in mass (resulting for example from aggregations of nanoparticles), surface roughness must have the same size parameters namely between 1 nm and 200 m, preferably less than 130 nm, preferably less than 100 nm, it is advantageously less than 50 nm and even more advantageously less than 20 nm.

The UV filters that can be used as photoprotective agents in the composition according to the invention are chosen from organic and / or inorganic UV filters active in UVA and / or UVB, which are hydrophilic and / or hydrophobic. The composition according to the invention may comprise a UV filter or a filtering system comprising several UV filters. Preferably, the filtering system comprises a plurality of UV filters making it possible to provide protection over the entire UVA and UVB spectrum.

Organic UV filters are especially chosen from cinnamic derivatives; anthranilates; salicylic derivatives, dibenzoylmethane derivatives, camphor derivatives; benzophenone derivatives; derivatives (3, (3'-diphenylacrylate, triazine derivatives, benzotriazole derivatives, benzalmalonate derivatives in particular those cited in patent US5624663, benzimidazole derivatives, imidazolines, bis-benzoazolyl derivatives such as for example described in patents EP669323 and US 2,463,264, p-aminobenzoic acid derivatives (PABA), methylene bis (hydroxyphenyl benzotriazole) derivatives as described in US5,237,071, US 5,166,355, GB2303549, DE 197 26 184 and EP893119, the benzoxazole derivatives such as, for example, described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844, the screening and screening silicone polymers such as those described in particular in the application WO-93/04665; α-alkylstyrene derivatives such as those described in patent application DE19855649; 4,4-diarylbutadienes as described in applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981; merocyanine derivatives such as those described in WO04 / 006878, WO05 / 058269 and WO06 / 032741 and mixtures thereof. As UV-A filters, the following compounds are counted. 1) Hydrophobic UV-A Filters Derivatives of dibenzoylmethane: Butyl Methoxydibenzoylmethane sold in particular under the trade name PARSOL 1789 by DSM Nutritional Products, Inc .; Isopropyl Dibenzoylmethane; Aminobenzophenones: n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate sold especially under the trade name UVINUL A + by BASF; Anthranilic derivatives: Menthyl anthranilate sold in particular under the trade name NEO HELIOPAN MA by SYMRISE; 4,4-diarylbutadiene derivatives: 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene; Merocyanine derivatives: Octyl-5-N, N-diethylamino-2-phenysulfonyl-2,4-pentadienoate; The preferred hydrophobic UVA filters are butyl methoxydibenzoylmethane and n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate. 2) Water-soluble UVA Filters - Terephthalylidene Dicamphor Sulfonic Acid Acid manufactured under the name "MEXORYL SX" by CHIMEX - bis-benzoazolyl derivatives as described in patents EP 669 323, and US 2,463,264 and more particularly the compound Disodium Phenyl Dibenzimidazole Tetra Sulfonate sold under the trade name "Neo Heliopan AP" by Haarmann and Reimer.

The preferred water-soluble UVA filter is Terephthalylidene Dicamphor Acid Sulfonic Acid. As UV-B filters, the following compounds are counted. 1) Hydrophobic UV-B Filters Para-aminobenzoates: ethyl PABA; Ethyl dihydroxypropyl PABA; Ethylhexyl Dimethyl PABA (ESCALOL 507 from ISP); salicylic derivatives: homosalate sold in particular under the name Eusolex HMS by Rona / EM Industries; Ethylhexyl salicylate sold in particular under the name NEO HELIOPAN OS by SYMRISE; Dipropylene glycol salicylate sold in particular under the name DIPSAL by SCHER; TEA Salicylate and under the name NEO HELIOPAN TS by SYMRISE; Cinnamates Ethylhexyl methoxycinnamate sold in particular under the trade name PARSOL MCX by DSM Nutritional Products, Inc.; Isopropyl methoxy cinnamate; Isoamyl methoxy cinnamate sold in particular under the trade name NEO HELIOPAN E 1000 by SYMRISE; Diisopropyl methylcinnamate; Cinnoxate; Glyceryl Ethylhexanoate Dimethoxycinnamate; derivatives of (3, (3'-diphenylacrylate: Octocrylene, sold in particular under the trade name UVINUL N539 by BASF; Etocrylene, sold in particular under the trade name UVINUL N35 by BASF; Derivatives of benzylidene camphor: 3-Benzylidenecamphor manufactured under the MEXORYL SD name by CHIMEX; Methylbenzylidene camphor sold in particular under the name EUSOLEX 6300 by MERCK; Polyacrylamidomethyl Benzylidene Camphor manufactured under the name MEXORYL SW by CHIMEX; Triazine derivatives: Ethylhexyl triazone sold in particular under the trade name UVINUL T150 by BASF; Diethylhexyl butamido Triazone sold in particular under the trade name UVASORB HEB by SIGMA 3V, 2,4,6-tris (4'-amino benzalmalonate dineopentyl) -s-triazine, 2,4,6-tris (4'-amino benzalmalonate diisobutyl) triazine; 2,4-bis (dineopentyl 4'-amino benzalmalonate) -6- (n-butyl 4'-aminobenzoate) -s-triazine; 2,4-bis (4'-amino benzoate); -butyl) -6- (aminopropyltrisiloxane The triazine symmetric filters described in US Pat. No. 6,225,467, WO 2004/085412 (see compounds 6 and 9) or the Symetrical Triazine Derivatives IP.COM Journal, IP.COM INC. WEST HENRIETTA, NY, US (September 20, 2004) including 2,4,6-tris- (biphenyl) -1,3,5-triazines (especially 2,4,6-tris (biphenyl-4-yl-1,3,5 triazin) and 2,4,6-tris (terphenyl) -1,3,5-triazine, these last two filters being described in the applications of BEIERSDORF WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007, WO 2006/034992, WO 2006/034985). Imidazoline derivatives Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate, Benzalmalonate derivatives: Benzalmalonate-functional polyorganosiloxanes such as Polysilicone-15 sold in particular under the trade name PARSOL SLX by DSM Nutritional Products, Inc.; Di-neopentyl 4'-methoxybenzalmalonate; Preferred hydrophobic UVB filters are selected from the following: Ethylhexyl Salicylate Octocrylene Ethylhexyl Triazone and mixtures thereof. 2) Water-soluble UVB Filters The following p-aminobenzoic acid (PABA) derivatives PABA, Glyceryl PABA, and PEG-25 PABA sold under the name "UVINUL P25" by BASF Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name "Eusolex 232" by MERCK, ferulic acid salicylic acid DEA methoxycinnamate benzylidene Camphor Sulfonic Acid manufactured under the name "MEXORYL SL" by CHIMEX, camphor Benzalkonium Methosulfate manufactured under the name "MEXORYL SO" by CHIMEX, and Water-soluble UVB filter Phenylbenzimidazole Sulfonic Acid As UVA and UVB filters that can be used in the compositions according to the present invention, the following compounds are counted: 1) UVA and UVB hydrophobic filters Derived from benzophenone Benzophenone-1 sold in particular under the trade name Uvinul 400 by BASF; Benzophenone-2 sold in particular under the trade name UVINUL D50 by BASF; Benzophenone-3 or Oxybenzone sold in particular under the trade name UVINUL M40 by BASF; Benzophenone-6 sold in particular under the trade name Helisorb 11 by Norquay; Benzophenone-8 sold in particular under the trade name Spectra-Sorb UV-24 by American Cyanamid; Benzophenone-10 Benzophenone-11 Benzophenone-12 Derivatives of phenyl benzotriazole: Drométrizole Trisiloxane sold in particular under the name Silatrizole by Rhodia Chimie or manufactured under the name Meroxyl XL by the company Chimex; Methylene bis-benzotriazolyl tetramethylbutylphenol, sold in solid form in particular under the trade name MIXXIM BB / 100 by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion, especially under the trade name TINOSORB M by CIBA SPECIALTY CHEMICALS; Derivatives bis-resorcinyl triazines Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold in particular under the trade name Tinosorb S by CIBA GEIGY; Derivatives of benzoxazole 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine sold in particular under the name of Uvasorb K2A by Sigma 3V; The preferred hydrophobic UVA and UVB filters are chosen from Drometzole Trisiloxane Methylene bis-Benzotriazolyl Tetramethylbutylphenol Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and mixtures thereof and even more preferably Drometrizole Trisiloxane. 2) Water-soluble UVA and UVB Filters Derivatives of benzophenone containing at least one sulphonic radical such as Benzophenone-4 sold under the trade name "UVINUL MS40" by BASF, Benzophenone-5 and Benzophenone-9. According to a particularly preferred form of the invention, use is made of a filter system consisting of: a) at least one UVA filter: butyl methoxydibenzoylmethane and preferably associated with Terephthalylidene Dicamphor Acid Sulfonic Acid and b) at least, as UVB filter Octocrylene and preferably associated with ethylhexyl salicylate.

More preferably, this filtering system will also comprise a hydrophobic UVA and UVB filter selected from Drometrizole Trisiloxane, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Methylene bis-Benzotriazolyl Tetramethylbutylphenol in micronized form or mixtures thereof.

According to a particularly preferred form of the invention, a filter system consisting of: a) at least, as UVA filter: n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate and b) at least a hydrophobic UVA and UVB filter selected from Drometrizole Trisiloxane, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Methylene bis-Benzotriazolyl Tetramethylbutylphenol in micronized form or mixtures thereof.

According to another particularly preferred form of the invention, a filtering system consisting of at least one organic UV filter and at least one inorganic UV filter will be used. Inorganic Filters: The inorganic UV filters used in accordance with the present invention are coated or uncoated metal oxide pigments such as, for example, titanium oxide pigments (amorphous or crystallized in rutile and / or anatase form), iron, zinc, zirconium or cerium. Preferably, the inorganic UV filters of the invention are metal oxide particles having an average element particle size less than or equal to 0.5 m, more preferably between 0.05 and 0.5 m, and even more preferentially between 0.010 and 0.1 m, and even more particularly between 0.015 and 0.050 m. The pigments can be coated or uncoated.

The coated pigments are pigments which have undergone one or more surface treatments of a chemical, electronic, mechanochemical and / or mechanical nature with compounds as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, p. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate. In a known manner, the silicones are organosilicon polymers or oligomers with a linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and / or polycondensation of suitably functionalized silanes, and essentially constituted by a repetition of main units in which the silicon atoms are connected to each other by oxygen atoms (siloxane bond), optionally substituted hydrocarbon radicals being directly bonded via a carbon atom to said silicon atoms. The term "silicones" also includes the silanes necessary for their preparation, in particular alkyl silanes. The silicones used for coating the pigments suitable for the present invention are preferably chosen from the group containing alkyl silanes, polydialkylsiloxanes, and polyalkylhydrogensiloxanes. Even more preferentially, the silicones are chosen from the group containing octyl trimethyl silane, polydimethylsiloxanes and polymethylhydrogensiloxanes.

Of course, the metal oxide pigments before their treatment with silicones, may have been treated with other surfactants, in particular with cerium oxide, alumina, silica, aluminum, silicon compounds, or mixtures thereof.

The coated pigments are more particularly titanium oxides coated with: - silica such as the product "Sunveil" from the company IKEDA, - silica and iron oxide such as the product "SUNVEIL F" from the company IKEDA, - silica and alumina, such as the products "MICROTITANIUM DIOXIDE MT 500 SA" and "MICROTITANIUM DIOXIDE MT 100 SA" from the company TAYCA, "TIOVEIL" from the company TIOXIDE, and Mirasun TiW 60 from the company Rhodia, - d ' 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 KEMIRA, - alumina and stearate of aluminum such as the product "MICROTITANIUM DIOXIDE MT 100 T, MT 100 TX, MT 100 Z, MT-01 from the company TAYCA, the products" Solaveil CT-10 W "and" Solaveil CT 100 "from the company UNIQEMA and the product "Eusolex TAVO" from MERCK, - silica, alumina and alginic acid such as the product "MT-100 AQ" from TAYCA, - alumina and laurate alu such as the product "MICROTITANIUM DIOXIDE MT 100 S" from TAYCA, - iron oxide and iron stearate such as the product "MICROTITANIUM DIOXIDE MT 100 F" from the company TAYCA, - zinc oxide and zinc stearate such as the product "BR351" from the company TAYCA, 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, silica, alumina, aluminum stearate and treated with a silicone such as the product" STT-30-DS "from the company TITAN KOGYO, silica and treated with a silicone such as the product "UV-TITAN X 195" from the company KEMIRA, - alumina and treated with a silicone such as the products "TIPAQUE TTO-55 (S)" ISHIHARA, or "UV TITAN M 262 "from KEMIRA, - triethanolamine such as the product" STT-65-S "from TITAN KOGYO, - stearic acid such as That the product "TIPAQUE TTO-55 (C)" of the company ISHIHARA - Sodium hexametaphosphate such as the product "MICROTITANIUM DIOXIDE MT 150 W" from TAYCA. Other titanium oxide pigments treated with a silicone are preferably TiO 2 treated with octyl trimethyl silane and whose average elementary particle size is between 0.025 and 0.04 m such as that sold under the trade name "T 805" by the company Degussa Silices, the TiO 2 treated with a polydimethylsiloxane and whose average elementary particle size is 21 nm, such as that sold under the trade name "70250 Cardre UF TiO2SI3" by CARDRE, TiO2 anatase / rutile treated with a polydimethylhydrogensiloxane and whose average elementary particle size is 25 nm such as that sold under the trade name "MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBIC" by the company COLOR TECHNIQUES. Uncoated titanium oxide pigments are for example sold by the company Tayca under the trade names "MICROTITANIUM DIOXIDE MT 500 B" or "MICROTITANIUM DIOXIDE MT600 B", by the company DEGUSSA under the name "P 25", by the WACKHER company 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" pigments d uncoated zinc oxide, for example are those marketed under the name "Z-cote" by the company Sunsmart; 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 marketed under the name "DAITOPERSION ZN-30" and "DAITOPERSION Zn-50" by Daito (dispersions in cyclopolymethylsiloxane / polydimethylsiloxane oxyethylenated, containing 30% or 50% of zinc nano-oxides coated with silica and polymethylhydrogeniloxane; ); those marketed under the name "NFD Ultrafine ZnO" by the company Daikin (ZnO coated with perfluoroalkyl phosphate and a copolymer based on perfluoroalkylethyl dispersed in cyclopentasiloxane); those marketed under the name "SPD-Z1" by Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); those marketed under the name "Escalol Z100" by the company ISP (ZnO treated with alumina and dispersed in the ethylhexyl methoxycinnamate / PVP-hexadecene / methicone copolymer mixture); those marketed under the name "Fuji ZnO-SMS-10" by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); Uncoated cerium oxide pigments are sold for example under the name "COLLOIDAL CERIUM OXIDE" by the company RHONE POULENC. Mention may also be made of mixtures of metal oxides, in particular titanium dioxide and cerium dioxide, including the titanium dioxide / silica-coated cerium-aluminum alloy mixture sold by the company IKEDA under the name "SUNVEIL A". ", as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as the product" M 261 "sold by the company KEMIRA or coated with alumina, silica and glycerin such as that the product "M 211" sold by KEMIRA. The photoprotective agents are generally present in the compositions of the invention in proportions ranging from 0.01% to 20% by weight relative to the total weight of the composition, and preferably ranging from 0.1% to 10% by weight relative to to the total weight of the composition. The composite material according to the present invention may also be covered by an additional coating, in particular chosen from biodegradable or biocompatible materials, lipidic materials such as surfactants or emulsifiers, polymers, and oxides. When the additional coating comprises a biodegradable or biocompatible material, this coating may in particular comprise any natural or synthetic molecule chosen in particular from lipids, carbohydrates, polysaccharides, proteins, polymers, glycoproteins, glycolipids which may be used to render the the physiologically acceptable combination.

Preferably, the biodegradable or biocompatible materials will be selected from polymers made from D- or Lucactide-type monomers, lactic acid, glycolic acid, hydroxybutyric acid or malic acid. When the additional coating comprises a lipid material, this coating may in particular comprise a lipid or a mixture of synthetic or natural lipid (s) possibly modified (s) by chemical or biological means. These lipids can be neutral or positively or negatively charged. When the additional coating comprises a polymer, this coating may in particular comprise at least one polymer chosen from polyesters, polyamides, polyethers, polythioethers, polyureas, polycarbonates, polycarbamides, proteins, polysaccharides and polyaryls, preferably with molar masses ranging from 100 g / mol at 100000 g / mol.

When the additional coating comprises an oxide, this coating may in particular comprise an oxide of an element chosen from Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Si, Sn, Sb, Ta, W, Pb. , Bi and Ce, preferably the oxide is SiO2. The additional coating may also contain stabilizers or scavengers of free radicals such as: - oils having in their structure at least one amide function: such as N-acetyl N-butylaminopropionate and N, N-diethyl-toluamide (DEET ) described especially in patent applications EP 717 982 and EP 815 834, isopropyl N-lauroylsarcosinate (Eldew SL-205), especially described in application EP 1 269 980, eutectic mixtures of n-butylphthalimide and isopropylphthalimide especially described in application EP 1 430 881, the non-silicone pyrrolidinones carboxylic acid, amides or arylalkyl esters, in particular described in applications EP1618870, EP1911438, FR 2902652, the amides or the arylalkyl siloxane esters, the compounds capable of accepting excited triplet level energy such as naphthalene derivatives (Corapan TQ), 4-hydroxy-benzylidene malonate derivatives (Oxynex ST), 4-hydroxy-cinnamon derivatives te, fluorene derivatives, piperidinol salts (TINOGUARD Q or TINOGUARD S-FX) especially described in the application EP1649900, - the phenol compounds or bis-phenols siloxane especially described in the application WO2007 / 080052, - the phenols compounds or non-silicone bis-phenols especially described in the application WO2007 / 080053. Advantageously, the composite material is functionalized in order to improve its affinity for the substrate: the skin and the hair.

This functionalization consists in introducing reactive functions on the surface of the composite material which will make it possible to produce covalent bonds between the composite material and the substrate. By reactive function is meant a known reactive group which allows the formation of a covalent bond (by reaction with nucleophilic functions, in this case sulfhydryl functions -SH) and which therefore comprises one or more nucleofuge (s) X or well one or more carbon (s) or link (s) activated (s). The usual nucleofuges are Cl, Br, F, -OSO3M, -OSO2 alkyl, -OSO2 aryl, -SOO2N (alkyl) 2, -OR1, SR2, -SOR2, -SO2R2, -S + R2R3, -SCN, N ~ + N / - SCOOR2, -NR2R3, N + R2R3R4, and M representing a hydrogen atom, an alkaline or alkaline earth metal or an ammonium residue, R1 represents a hydrogen atom, an alkyl radical or C1-C4, a substituted or unsubstituted phenyl radical, the PO3H2 radical and its salts or the acetyl radical. R2, R3 and R4, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical or a substituted or unsubstituted phenyl radical. Among the most well-known reactive groups, there may be mentioned in particular: mono and dihalotriazines, dihalogenoquinoxalines, dihalogeno pyrimidines, vinylsulfones or their precursors (3-halo or 13-sulphatoethylsulfones, acrylates and methacrylates, acrylamides and methacrylamides, maleimides and halogenomaleimides, epoxides and aziridine derivatives, oxazolinium, imidazolium or thiazolidinium groups, carboxylic or sulfonic acid halides, esters, carbamates, anhydrides, isothiocyanates and isocyanates, lactones, azalactones of structure R 15 N <(C): embedded image in which: R 15 and R 16, which may be identical or different, represent a hydrogen atom, a C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl or C 5 -C 12 aryl radical; , arenyl C6-C26 having from 0 to 3 heteroatoms selected from S, N and O, or R15 and R16 together form a carbocycle containing from 4 to 12 atoms and n is an integer between 0 and 3, etc. The cosmetic compositions according to the invention may, of course, contain one or more other active and / or UVB-active solar filters, hydrophilic or lipophilic in free form, that is to say not combined with plasmonic particles. The compositions of the invention may also comprise conventional cosmetic adjuvants chosen in particular from fatty substances, organic solvents, ionic or nonionic thickeners, hydrophilic or lipophilic, softeners, humectants, opacifiers, antioxidants, stabilizers, emollients, silicones, α-hydroxy acids, anti-foam agents, moisturizers, vitamins, perfumes, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, fillers, pigments ( inorganic or organic), sequestering agents, polymers, propellants, alkalizing or acidifying agents, dyes, or any other ingredient usually used in cosmetics and / or dermatology, in particular for the manufacture of sunscreen protection compositions. Of course, all the additional ingredients that may be introduced into the compositions in accordance with the invention must be such that they do not substantially disturb or alter the properties of these compositions, in particular in terms of light stabilization and increase of the sunscreen.

The fatty substances may be an oil or a wax or mixtures thereof, and they also include fatty acids, fatty alcohols and fatty acid esters. The oils may be chosen from animal, vegetable, mineral or synthetic oils and in particular from vaseline oil, paraffin oil, silicone oils, volatile or nonvolatile, isoparaffins, polyolefins, fluorinated and perfluorinated oils. Similarly, the waxes can be chosen from animal, fossil, vegetable, mineral or synthetic waxes known per se.

Among the organic solvents, mention may be made of lower alcohols and polyols. The thickeners may be chosen in particular from crosslinked polyacrylic acids, guar gums and modified or unmodified celluloses such as hydroxypropyl guar gum, methylhydroxyethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. The compositions of the invention may be prepared according to the techniques well known to those skilled in the art, in particular those intended for the preparation of oil-in-water or oil-in-oil type emulsions. The composition according to the present invention may be in the form of a solution, in emulsion form, simple or complex (O / W, W / O, W / E / H or W / O / W) such that cream, milk or gel, cream gel; in the form of an aqueous gel; in the form of a lotion or a powder. It can optionally be packaged in an aerosol and be in the form of foam or spray. In the case of an emulsion, the aqueous phase thereof may comprise a nonionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins, J. Mol Biol 13, 238 (1965)). FR 2 315 991 and FR 2 416 008). The cosmetic compositions according to the invention can be used as protective compositions for the human epidermis or the hair against ultraviolet rays, as sunscreen compositions or as make-up products. When the cosmetic compositions according to the invention are used for protecting the human epidermis against UV rays, or as an antisolar composition, they may be in the form of a suspension or dispersion in solvents or fatty substances, in the form of nonionic vesicular dispersion or in the form of an emulsion, preferably of the oil-in-water type, such as a cream or a milk, in the form of an ointment, a gel, a solid stick, a stick, an aerosol foam or of spray.

When the cosmetic compositions according to the invention are used for the protection of the hair, they may be in the form of shampoo, lotion, gel, emulsion, non-ionic vesicular dispersion, hairspray and constitute, for example, a hair composition for rinsing, for applying before or after shampooing, before or after coloring or bleaching, before, during or after permanent or straightening, a lotion or gel for styling or treating, a lotion or a gel for blow-drying or setting the hair, a composition of permanent or straightening, coloring or discoloration of the hair. The fatty substances may consist of an oil or a wax or mixtures thereof. By oil is meant a liquid compound at room temperature. By wax is meant a compound that is solid or substantially solid at room temperature and whose melting point is generally greater than 35 ° C. As oils, mention may be made of mineral oils (paraffin); vegetable (sweet almond oil, macadamia oil, blackcurrant seed oil, jojoba oil); synthetic such as perhydrosqualene, alcohols, fatty amides (such as isopropyl lauroyl sarcosinate sold under the name of Eldew SL-205 by Ajinomoto), fatty acids or esters, such as C12-C15 alcohols benzoate; sold under the trade name Finsolv TN or Witconol TN by the company WITCO, 2-ethylphenyl benzoate as the commercial product sold under the name X-TEND 226 by the company ISP, octyl palmitate, isopropyl lanolate, triglycerides, including those of capric / caprylic acids, dicaprylyl carbonate sold under the name Cetiol CC by Cognis), oxyethylenated or oxypropylenated esters and fatty ethers; silicone oils (cyclomethicone, polydimethylsiloxane or PDMS) or fluorinated oils, polyalkylenes, trialkyl trimellitates such as tridecyl trimellitate. As waxy compounds, mention may be made of carnauba wax, beeswax, hydrogenated castor oil, polyethylene waxes and polymethylene waxes, such as that sold under the name Cirebelle 303 by the company SASOL. Among the organic solvents, mention may be made of lower alcohols and polyols. These can be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol. As hydrophilic thickeners, mention may be made of carboxyvinyl polymers such as Carbopols (Carbomers) and Pemulen (acrylate / C10-C30-alkylacrylate copolymer); polyacrylamides, for example crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide / C13-14 isoparaffin / Laureth 7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by the company Seppic ; polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally cross-linked and / or neutralized, such as poly (2-acrylamido-2-methylpropanesulphonic acid) marketed by Hoechst under the trademark Hostacerin AMPS (CTFA name: ammonium polyacryloyldimethyl taurate or SIMULGEL 800 sold by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate / polysorbate 80 / sorbitan oleate); copolymers of 2-acrylamido-2-methylpropanesulphonic acid and hydroxyethyl acrylate such as SIMULGEL NS and SEPINOV EMT 10 sold by the company SEPPIC, cellulosic derivatives such as hydroxyethylcellulose, polysaccharides and especially gums such as Xanthan gum, and mixtures thereof, As lipophilic thickeners, mention may be made of synthetic polymers such as poly C10 -C30 alkyl acrylates sold under the name INTELIMER IPA 13-1 and INTELIME R IPA 13-6 by Landec or modified clays such as hectorite and its derivatives, such as products sold under the name of Bentone.

Of course, those skilled in the art will take care to choose the optional additional compound (s) mentioned above and / or their amounts in such a way that the advantageous properties intrinsically attached to the compositions in accordance with the invention are not, or substantially, not, altered by the addition or additions envisaged, in particular the improvement of the photostability of the derivative of dibenzoylmethane. The compositions according to the invention can be prepared according to the techniques well known to those skilled in the art. They may be in particular in the form of an emulsion, simple or complex (O / W, W / O, O / W / H or W / O / W) such as cream, milk or cream gel ; in the form of an aqueous gel; in the form of a lotion. They may optionally be packaged in aerosol and be in the form of foam or spray.

Preferably, the compositions according to the invention are in the form of an oil-in-water or water-in-oil emulsion. The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The emulsifiers are suitably selected according to the emulsion to be obtained (W / O or O / W). The emulsions may also contain other types of stabilizers, for example fillers, gelling or thickening polymers. As emulsifying surfactants that may be used for the preparation of W / O emulsions, mention may be made, for example, of alkyl esters or ethers of sorbitan, of glycerol or of sugars; silicone surfactants such as dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name DC 5225 C by Dow Corning, and alkyl dimethicone copolyols such as Laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid "by Dow Corning; cetyl dimethicone copolyol such as the product sold under the name Abil EM 90R by Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the name ABIL WE 09 by the company Goldschmidt. One or more coemulsifiers may also be added, which advantageously may be selected from the group consisting of alkylated polyol esters. Polyol alkyl esters that may especially be mentioned include polyethylene glycol esters such as 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 are polyglycerol isostearate, such as the product sold under the name Isolan GI 34 by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company ICI; sorbitan isostearate and glycerol, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof. For O / W emulsions, mention may be made, for example, as emulsifiers, of nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fatty acid and sorbitan esters; oxyalkylenated fatty acid esters (oxyethylenated and / or oxypropylenated) such as the PEG-100 Stearate / Glyceryl Stearate mixture marketed for example by the company ICI under the name Arlacel 165; oxyalkylenated fatty alcohol ethers (oxyethylenated and / or oxypropylenated); sugar esters such as sucrose stearate; fatty alcohol and sugar ethers, in particular alkylpolyglucosides (APG) such as decylglucoside and laurylglucoside sold, for example, by Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearylglucoside optionally mixed with cetostearyl alcohol; , marketed for example under the name Montanov 68 by the company Seppic, under the name Tegocare CG90 by Goldschmidt and under the name Emulgade KE3302 by Henkel, and arachidyl glucoside, for example in the form of a mixture of arachidic and behenic alcohols and arachidylglucoside 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, as described, for example, in WO- A-92/06778. Among the other emulsion stabilizers, the polymers of isophthalic acid or sulfoisophthalic acid, and in particular the phthalate / sulphoisophthalate / glycol copolymers, for example the diethylene glycol / phthalate / isophthalate / 1,4-diol copolymer, will be used more particularly. cyclohexane-dimethanol (INCI name: Polyester-5) sold under the names "Eastman AQ polymer" (AQ35S, AQ38S, AQ55S, AQ48 Ultra) by the company Eastman Chemical. In the case of an emulsion, the aqueous phase thereof may comprise a nonionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins, J. Mol Biol 13, 238 (1965)). FR 2 315 991 and FR 2 416 008).

The compositions according to the invention find their application in a large number of treatments, in particular cosmetics, of the skin, lips and hair, including the scalp, in particular for the protection and / or care of the skin, lips and / or hair.

Another object of the present invention is constituted by the use of the compositions according to the invention as defined above for the manufacture of products for the cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyebrows and / or scalp, including skincare products, sunscreen products. The cosmetic compositions according to the invention may, for example, be used as skincare and / or sun protection products for the face and / or body of liquid semiliquid consistency, such as milks, more or less unctuous creams, creams, pasta. They may optionally be packaged in aerosol and be in the form of foam or spray. The compositions according to the invention in the form of vaporizable fluid lotions according to the invention are applied to the skin or the hair in the form of fine particles by means of pressurizing devices. The devices according to the invention are well known to those skilled in the art and include non-aerosol pumps or "atomizers", aerosol containers comprising a propellant and aerosol pumps using compressed air as a propellant. These are described in US Pat. Nos. 4,077,441 and 4,850,517. The aerosol-conditioned compositions in accordance with the invention generally contain conventional propellants such as, for example, hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane and trichlorofluoromethane. They are present preferably in amounts ranging from 15 to 50% by weight relative to the total weight of the composition. The compositions according to the invention may also comprise, in addition to additional cosmetic and dermatological active agents. The additional active agents may in particular be chosen from moisturizing agents, desquamating agents, barrier-improving agents, depigmenting agents, antioxidant agents, dermodecontracting agents, anti-glycation agents and agents stimulating the synthesis of dermal macromolecules. and / or epidermal and / or preventing their degradation, agents stimulating the proliferation of fibroblasts or keratinocytes and / or differentiation of keratinocytes, agents promoting the maturation of the horny envelope, inhibitors of NO-synthases, antagonists peripheral benzodiazepine receptors (PBR), agents increasing the activity of the sebaceous gland, agents stimulating the energy metabolism of cells, tensors, liporestructuring agents, slimming agents, agents promoting cutaneous microcirculation, agents soothing and / or anti-irritating, the sebo-regulat or anti-seborrhoeic agents, astringent agents, healing agents, anti-inflammatory agents and anti-acne agents. The skilled person will choose the active agent (s) depending on the desired effect on the skin, hair, eyelashes, eyebrows, nails. For the care of aged skin, it will preferably choose at least one active ingredient chosen from hydrating agents, desquamating agents, barrier-improving agents, depigmenting agents, antioxidants, dermodecontracting agents, anti-glycation agents, agents stimulating the synthesis of dermal and / or epidermal macromolecules and / or preventing their degradation, agents stimulating the proliferation of fibroblasts or keratinocytes and / or differentiation of keratinocytes, agents promoting the maturation of the horny envelope, inhibitors NO-synthases, peripheral benzodiazepine receptor antagonists (PBRs), agents increasing sebaceous gland activity, agents stimulating energy metabolism of cells, liporestructuring agents and cutaneous microcirculatory agents for the contour eyes. For the care of oily skin, those skilled in the art will preferably choose at least one active agent selected from desquamating agents, sebo-regulating or anti-seborrhoeic agents, astringent agents. When the compositions are used as a makeup product for eyelashes, eyebrows or skin, such as epidermis cream, foundation, lipstick stick, eyeshadow, blush, mascara or liner also called "eyeliner", they can be in solid or pasty, anhydrous or aqueous, such as oil-in-water or water-in-oil emulsions, nonionic vesicular dispersions or suspensions.

As indicated at the beginning of the description, another object of the present invention resides in a method of cosmetic treatment of the skin or of the hair intended to protect them against the effects of UV rays consisting in applying to them an effective amount of a photostable cosmetic composition as defined above.

Claims (17)

REVENDICATIONS1. An ultraviolet radiation filtering composite material comprising at least one plasmonic particle formed from at least one metal and at least one ultraviolet radiation filtering agent, said filtering agent being located within the plasmonic particle or at least one outside the plasmonic particle at a sufficiently low distance from the plasmonic particle, so that the absorption of ultraviolet radiation on at least a portion of the spectrum of the filtering agent is increased. 2. Composite material according to claim 1, characterized in that said at least one metal is selected from the group consisting of the following metals: tungsten, aluminum, palladium, platinum, silver, copper, gold, chromium, zinc, rhodium, nickel , tin, as well as their alloys. 3. Composite material according to claim 2, characterized in that said at least one metal is selected from the group consisting of the following metals: aluminum, silver, chromium, zinc, rhodium, as well as their alloys. 4. Composite material according to any one of the preceding claims, characterized in that the filtering agent is an organic UV filter selected from cinnamic derivatives; anthranilates; salicylic derivatives, dibenzoylmethane derivatives, camphor derivatives; benzophenone derivatives; derivatives (3, 3'-diphenylacrylate, triazine derivatives, benzotriazole derivatives, benzalmalonate derivatives, benzimidazole derivatives, imidazolines, bisbenzoazolyl derivatives, p-aminobenzoic acid derivatives (PABA)) methylene bis (hydroxyphenyl benzotriazole) derivatives, benzoxazole derivatives, screening and screening silicone polymers, α-alkylstyrene derived dimers, 4,4-diarylbutadienes, merocyanine derivatives and mixtures thereof. 5. Composite material according to any one of the preceding claims, characterized in that the filtering agent is an inorganic UV filter selected from coated or uncoated metal oxide pigments such as, for example, titanium oxide and iron pigments. , zinc, zirconium or cerium. 6. Composite material according to any one of the preceding claims, characterized in that it is covered by an additional coating selected from biodegradable or biocompatible materials, lipid materials such as surfactants or emulsifiers, polymers, the oxides. 7. Composite material according to any one of the preceding claims, characterized in that it contains or is covered with an additional coating containing stabilizers or scavengers of free radicals such as oils having in their structure at least one amide function compounds capable of accepting triplet excited level energy, siloxane phenol or bisphenol compounds, non-silicone phenol or bis-phenol compounds. 8. Composite material according to any one of the preceding claims, characterized in that it comprises at least one plasmonic particle coated with a layer comprising particles of filtering agents or formed of at least one ultraviolet radiation filtering material. purple. 9. Composite material according to any one of claims 1 to 7, characterized in that it comprises at least one plasmonic particle comprising a non-metallic core and a metal shell around the core, said at least one filtering agent being in the core. or forming the nucleus. 10. Composite material according to any one of claims 1 to 7, characterized in that it comprises at least one plasmonic particle formed of a metal particle comprising one or more inclusions containing said at least one filter material. 11. composite material according to any one of claims 1 to 7 characterized in that it comprises at least one plasmonic particle formed of a non-metallic matrix within which are arranged one or more metal particles, said matrix not metal further comprising at least one ultraviolet radiation filtering agent or being formed of at least one ultraviolet radiation filtering material. 12. composite material according to any one of claims 1 to 7, characterized in that it comprises at least one plasmonic particle having inclusions in its relief and a filtering agent placed in inclusions in the relief of the plasmonic particle. 13. Composite material according to any one of claims 1 to 7 characterized in that it consists of at least two composite materials as defined in claims 8 to 12. 14. A cosmetic composition for sun protection comprising, in a cosmetically acceptable medium, the composite material according to one of claims 1 to 13. 15. Cosmetic composition according to any one of the preceding claims, characterized in that it contains one or more cosmetic adjuvants, especially chosen from fatty substances, organic solvents, ionic or nonionic thickeners, hydrophilic or lipophilic, softeners, humectants, opacifiers, antioxidants, stabilizers, emollients, silicones, α-hydroxy acids, antifoaming agents, moisturizers, vitamins, perfumes, preservatives, anionic surfactants, cationic, ionic, zwitterionic or amphoteric, fillers, pigments (inorganic or organic), sequestering agents, polymers, propellants, alkalinizing or acidifying agents, dyes. 16. Process for the cosmetic treatment of keratinous substances, in particular the skin or hair intended to protect them against the effects of UV rays, consisting in applying to them an effective quantity of a cosmetic composition according to any one of Claims 14 or 15. . 17. A process for photostabilizing a photosensitive agent, filtering the UV radiation in which said filtering agent is placed outside the plasmonic particle, or inside the plasmonic particle at a sufficiently small distance from the plasmonic particle, so that the absorption of ultraviolet radiation on at least a portion of the spectrum of the filtering agent is increased.