WO2011004133A2

WO2011004133A2 - Composite material comprising uv filters and plasmonic particles, and use as sun screen

Info

Publication number: WO2011004133A2
Application number: PCT/FR2010/051456
Authority: WO
Inventors: Etienne Huguet; Benoit Muller; Philippe Barbarat
Original assignee: L'oreal
Priority date: 2009-07-10
Filing date: 2010-07-09
Publication date: 2011-01-13
Also published as: FR2947724A1; WO2011004133A3; FR2947724B1

Abstract

The present application relates to a composite material that screens out ultraviolet radiation and comprises at least one plasmonic particle formed from at least one metal and at least one organic agent that screens out ultraviolet radiation, said screening agent being located inside the plasmonic particle or outside the plasmonic particle, at a sufficiently short distance from the plasmonic particle so that the absorption of the ultraviolet radiation over at least one portion of the spectrum of the screening agent is increased. The present application also relates to a method for the cosmetic treatment of skin or hair in order to protect the same against the effects of UV rays, said method involving applying an effective amount of such a composite material to the skin or hair, and to a method for photostabilizing and/or for increasing the absorption of a photoprotective agent by means of at least one plasmonic particle.

Description

COMPOSITE MATERIAL COMPRISING UV FILTERS AND

PLASMONIC PARTICLES AND USE IN

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 organic 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 photostabilization of a 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 the rays.

UV-A on their skin. It is therefore desirable to also filter the UV-A radiation.

In order to ensure protection of the skin and keratin materials against UV radiation, antisolar compositions comprising organic screening agents active in the UV-A and active in the UV-B are generally used. Most of these filters are fat soluble.

In this respect, a particularly interesting family of UV-A filters currently consists of dibenzoylmethane derivatives, and in particular 4-tert-butyl-4'-methoxydibenzoyl methane, 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-0 14607; 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 concentration of UV filters 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 effective UV absorbers filters 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, that is to say, more precisely, that they present an unfortunate tendency to degrade more or less quickly 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 heart to allow an increase in emissions when excited by electromagnetic energy in the visible, which composition may optionally include an inorganic pigment.

There remains a need for UV sunscreen compositions which do not have the disadvantages 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 of the plasmonic particle or outside the plasmonic particle at a sufficiently small distance from the plasmonic particle, so that absorption of the 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 weak of the plasmonic particle, so that the absorption of ultraviolet radiation on at least a part 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.

For the purposes of this application, the term "composite material" is intended to mean a material formed of several distinct components.

For the purposes of this application, the term "plasmonic particle" is intended to mean a particle whose electrons oscillate collectively when they are excited by a suitable form of energy such as radiation, this oscillation being at the origin of an electromagnetic wave. 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, the absorption of UV radiation by the UV filter will more effectively protect the substrate. In addition, the absorption zone of the UV filter is substantially unaffected.

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 UVA _PPD sun protection factor (FP UVA _pp d) is mathematically expressed by the ratio of the UV-A radiation dose required to reach the UV filter pigmentation threshold (MPPDp) with the UV-A radiation dose. necessary to reach the threshold of pigmentation without UV filter (MPPD _np ).

MPPDp

FP PP UVA ₀ ₀ D _n = ^'

MPPDnp Increasing the 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 situated outside the plasmonic particle or inside the plasmonic particle.

The interactions between the coated particle (core particle) and the layer ("coating" in English) may be non-covalent interactions, which 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 the filtering agent (s) or formed from the filtering agent (s).

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 achieved 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).

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 agent.

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 1 μm, preferably from 0.5 to 5 μm, and the order of magnitude of the plasmonic particles is from 1 to 200 nm and more preferably from 1 to 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 at least one 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 from 0.1 to 1 μm, the dimension of the surface roughness or inclusions in the relief being less than 250 nm and more preferably less than 40 nm.

This embodiment is among the preferred.

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, can be stoichiometric or non-stoichiometric

The plasmonic particles may be of various shapes such as spherical, cylindrical, cubic, conical, platelet elliptical, 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 the 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 μm, 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 μm, 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 used as photoprotective agents in the composition according to the invention are chosen from active organic UV filters in the UVA and / or UVB. hydrophilic and / or hydrophobic.

The composition according to the invention may comprise a UV filter or a filtering system comprising a plurality of UV filters.

Preferably, the filtering system comprises several 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; β, β'-diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives especially those cited in 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- (hydroxyphenylbenzotriazole) derivatives as described in US5, 237,071, US 5, 166,355, GB2303549, DE 197 26 184 and EP8931 19; benzoxazole derivatives such as, for example, described in patent applications EP0832642, EP 1027883, EP 1300137 and DE 10162844; filter polymers and silicone filters such as those described in particular in the application WO-93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE 19855649; 4,4-diarylbutadienes as described in Applications EP0967200, DE 19746654, DE 19755649, EP-A-1008586, EP 133980 and EP 133981; merocyanine derivatives such as those described in applications 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:

2- (4-diethylamino-2-hydroxybenzoyl) benzoate of n-hexyl sold in particular under the trade name "UVINUL A +" by BASF;

Anthranilic derivatives:

Menthyl anthranilate sold in particular under the trade name "Neo Heliopan MA" by SYMRISE;

The 4,4-diarylbutadiene derivatives:

1,1-Dicarboxy (2,2'-dimethyl-propyl) -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 Acid Sulfonic Acid manufactured under the name "MEXORYL SX" by CHIMEX

the bis-benzoazolyl derivatives as described in the patents

EP 669 323, and US 2,463,264 and more particularly the compound

Disodium Phenyl Dibenzimidazole Tetrasulfonate 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 β, β'-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-Benzylidene camphor manufactured under the name "MEXORYL

SD "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 T 150 by BASF;

Diethylhexylbutamido 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) -s-triazine;

2,4-bis (dineopentyl 4'-amino benzalmalonate) -6- (n-butyl 4-aminobenzoate) -s-triazine;

2,4-bis (4-n-butyl benzoate) -6-

(aminopropyltrisiloxane) -s-triazine;

the symmetrical triazine filters described in US Pat. No. 6,225,467, WO 2004/085412 (see compounds 6 and 9) or the "Symetrical Triazine Derivatives" document IP.COM Journal,

In particular, 2,4,6-tris- (biphenyl) -1,3,5-triazines (especially 2,4,6-tris (biphenyl- 4-yl-1,3,5-triazine) and 2,4,6-tris (terphenyl) -1,3,5-triazine, the latter two filters being described in 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,

Derivatives of benzalmalonate:

Benzalmalonate-functional polyorganosiloxanes such as Polysilicone-sold in particular under the trademark "PARSOL SLX" by DSM Nutritional Products, Inc.;

Di-neopentyl 4'-methoxybenzalmalonate;

The preferred hydrophobic UVB filters are chosen from the following:

Ethylhexyl Salicylate

octocrylene

Ethylhexyl triazone

and their mixtures.

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

The preferred water-soluble UVB filter is Phenylbenzimidazole Sulfonic Acid

As UVA and UVB filters that can be used in the compositions according to the present invention, there are the following compounds: 1) UVA and UVB hydrophobic filters

Benzophenone derivatives

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 1 1" by Norquay;

Benzophenone-8 sold in particular under the trade name "Spectra-Sorb UV-24" by American Cyanamid;

Benzophenone-10;

Benzophenone-1 1;

Benzophenone-12;

Derivatives of phenyl benzotriazole:

Drometzole 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;

Bis-resorcinyl triazine derivatives

Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold in particular under the trade name "TINOSORB S" by CIBA GEIGY;

Benzoxazole derivatives:

2,4-bis [5- (1-dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine sold especially under the name 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 Drometzole Trisiloxane.

2) Water-soluble UVA and UVB filters

Benzophenone derivatives having at least one sulphonic radical 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, a filter system consisting of:

a) at least, as 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 chosen from Drometzole 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 filtering system consisting of:

a) at least as UVA filter: n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate and

b) at least one hydrophobic UVA and UVB filter selected from Drometzole Trisiloxane, Bis-Ethylhexyloxyphenol Methoxyphenyl

Triazine, methylene bis-benzotriazolyl tetramethylbutylphenol in micronized form or mixtures thereof. According to a preferred embodiment of the invention, a filtering system consisting of at least one organic UV filter and at least one inorganic UV filter is used.

Inorganic filters:

The inorganic UV filters that may be used in accordance with the present invention are coated or uncoated metal oxide pigments, for example titanium oxide pigments (amorphous or crystallized in rutile and / or anatase form), iron, zinc, zirconium or cerium.

Preferably, the inorganic UV filters are metal oxide particles having an average element particle size less than or equal to 0.5 μm, more preferably between 0.05 and 0.5 μm, and even more preferentially between 0.010 and 0, 1 micron, and even more particularly between 0.015 and 0.050 microns.

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), hydrocarbon radicals optionally substituted 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 coated titanium oxides:

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,

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 aluminum stearate such as the product MICROTITANIUM DIOXIDE MT 100 T, MT 100 TX, MT 100 Z,

MT-O l from the company TAYCA, the products "Solaveil CT-IOW" and "Solaveil CT 100" from the company UNIQEMA and the product "Eusolex T-AVO" from the company MERCK, silica, alumina and alginic acid such as the product "MT-100 AQ" from the company Tayca,

alumina and aluminum laurate 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 TITAN KOGYO,

silica and treated with a silicone such as the product "UV-TITAN X 195" from KEMIRA,

of alumina and treated with a silicone such as the products "TIPAQUE TTO-55 (S)" from ISHIHARA, or "UV TITAN M 262" from KEMIRA,

triethanolamine such as the product "STT-65-S" from TITAN KOGYO,

stearic acid such as the product "TIPAQUE TTO-55 (C)" from ISHIHARA,

- sodium hexametaphosphate such as the product

"MICROTITANIUM DIOXIDE MT 150 W" from the company 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 μm, such as that sold under the name commercial "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 TiO ₂ SD "by the company CARDRE, the TiO ₂ 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 MIYOSHI KASEI under the name "UFTR", by TOMEN under the name "ITS" and by the company TIOXIDE under the name "TIOVEIL AQ".

Uncoated zinc oxide pigments, for example, are

those marketed under the name "Z-cote" by the company Sunsmart;

Coated zinc oxide pigments are for example

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

those marketed under the name "DAITOPERSION ZN-30" and "DAITOPERSION Zn-50" by the company Daito (dispersions in cyclopolymethylsiloxane / polydimethylsiloxane oxyethylenated, containing 30% or 50% of zinc nano-oxides coated with silica and the polymethylhydrogenesiloxane; );

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-Z 1" by the company Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); those marketed under the name "Escalol Z 10 OO" 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 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 that the product "M 21 1" 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 make the combination physiologically acceptable. Preferably, the biodegradable or biocompatible materials will be chosen from polymers made from D- or L-lactide 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 SiO ₂ .

The additional coating may also contain stabilizers or free radical scavengers such as:

oils having in their structure at least one amide function: such as N-acetyl N-butylaminopropionate and N, N-diethyltoluamide (DEET), for example described in patent applications EP 717 982 and EP 815 834, Isopropyl N-lauroylsarcosinate (Eldew SL-205), especially described in application EP 1 269 980, the eutectic mixtures of n-butylphthalimide and of isopropylphthalimide, in particular described in application EP 1 430 881, the carboxylic pyrrolidinones, the amides or non-silicone arylalkyl esters, in particular described in applications EP 1618870, EP 191 1438, FR 2902652, amides or arylalkyl siloxane esters, compounds capable of accepting excited triplet level energy such as naphthalene derivatives (Corapan TQ), 4-hydroxy-benzylidene malonate derivatives (Oxynex ST), 4-hydroxy-cinnamate derivatives, derivatives thereof fluorene, piperidinol salts (TINOGUARD Q or TINOGUARD S-FX) especially described in application EP 1649900,

the siloxane phenol or bis-phenol compounds especially described in the application WO2007 / 080052,

the non-silicone phenol or bis-phenol compounds especially described in 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 the groups:

Cl, Br, F, -OSO3M, -OSO2 alkyl, -OSO2 aryl, -OSO2N (alkyl) 2, -OR1, SR2, -SOR2, -SO2R2, -S ⁺ R2R3, -SCN,

-SCOOR2, -NR2R3, N R2R3R4,

and

M represents a hydrogen atom, an alkali or alkaline earth metal or an ammonium residue,

R 1 represents a hydrogen atom, a C 1 -C 4 alkyl radical, a substituted or unsubstituted phenyl radical, the PO 3 H 2 radical and its salts or the acetyl radical. R 2, R 3 and R 4, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical or a substituted or unsubstituted phenyl radical.

Among the most known reactive groups, there may be mentioned in particular:

mono and dihalotriazines,

dihalogenoquinoxalines, dihalogeno pyrimidines,

vinylsulfones or their β-halogen or β-sulfatoethylsulphone precursors,

acrylates and methacrylates,

acrylamides and methacrylamides,

the maleimides and halogenomaleimides,

epoxides and aziridine derivatives,

the oxazolinium, imidazolium or thiazolidinium groups,

the halides of carboxylic or sulphonic acids,

the esters,

carbamates

anhydrides,

isothiocyanates and isocyanates,

- the lactones,

- azalactones of structure:

in which :

Rl 5 and Rl 6, which are identical or different, represent a hydrogen atom, a C 1 -C 12 alkyl radical, C 3 -C 12 cycloalkyl, C 5 -C 12 aryl, C 6 -C 26 arenyl radical having from 0 to 3 heteroatoms chosen from S, N and O, or R15 and R16 together form a carbocycle containing from 4 to 12 atoms and n is an integer from 0 to 3, etc. The cosmetic compositions according to the invention may, of course, contain one or more other sunscreens active in the UVA and / or UVB, hydrophilic or lipophilic in free form, that is to say not combined with the plasmonic particles.

According to a preferred embodiment, the composite material according to the present invention comprises one or more plasmonic particles formed of silver and titanium dioxide as an inorganic filter.

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, alkalinizing 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 in 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 not, isoparaffins, poly-α-olefins, fluorinated and perfluorinated oils. Similarly, the waxes can be chosen among 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 water-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

(W / O, W / O, O / W / H or W / O / W) such as 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 the protection of the human epidermis against the rays

UV, or as sunscreen, they can be in the form of suspension or dispersion in solvents or fatty substances, in the form of a nonionic vesicular dispersion or in the form of an emulsion, preferably of the oil-in-water type , such as cream or milk, in the form of ointment, gel, solid stick, stick, aerosol foam or 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 "Eldew SL-205" by the company Ajinomoto), fatty acids or esters such as benzoate C alcohols 12-C 15 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, the palmitate d octyl, 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 / C 10 -C 30 alkyl acrylate copolymer); polyacrylamides, for example crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide / C 13-14 isoparaffin / Laureth 7) or Simulgel 600 (C name: TFA: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by Seppic society; 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 trade name "Hostacerin AMPS" (name CTFA: 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 the SEPINOV

EMT 10 marketed by the company SEPPIC; cellulosic derivatives such as hydroxyethylcellulose; polysaccharides and especially gums such as Xanthan gum; and their mixtures.

Mention may be made, as lipophilic thickeners, of synthetic polymers such as the poly C 10 -C 30 alkyl acrylates sold under the name "INTELIMER IPA 13-1" and "INTELIMER IPA 13-6" by the company Landec, or the modified clays such as hectorite and its derivatives, such as products marketed under the name 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 such as 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 9 OR 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 P 135 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, examples of emulsifiers which may be mentioned include nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fatty acid and sorbitan esters; oxyalkylenated (oxyethylenated and / or oxypropylenated) fatty acid esters, such as PEG-100 Stearate / Glyceryl Stearate, sold 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; the fatty alcohol and sugar ethers, in particular the alkylpolyglucosides (APG) such as decylglucoside and laurylglucoside sold, for example, by Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearylglucoside optionally in admixture with alcohol; cetostearyl, marketed for example under the name Montanov 68 by the company Seppic, under the name Tegocare CG90 by the company Goldschmidt and under the name Emulgade KE3302 by Henkel, as well as 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 a particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition, as described, for example, in WO- A-92/06778.

Among the other stabilizers of emulsion, the polymers of isophthalic acid or of sulphoisophthalic acid, and in particular the phthalate / sulphoisophthalate / glycol copolymers, for example the copolymer of

Diethylene glycol / Phthalate / Isophthalate / 1,4-cyclohexanedimethanol (INCI name: Polyester-5) sold under the names "Eastman AQ polymer" (AQ35 S, AQ38S, AQ55 S, AQ48 Ultra) by the company Eastman Chemical.

In the case of an emulsion, the aqueous phase thereof may comprise a nonionic vesicular dispersion prepared by 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 a care product and / or protection sunscreen for the face and / or the body of liquid to semi-liquid consistency, such as milks, more or less creamy creams, gel creams, pastes. 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, additional cosmetic and dermatological active ingredients.

The additional active agents may in particular be chosen from moisturizing agents, desquamating agents, barrier-improving agents, depigmenting agents, antioxidants, dermodecontracting agents, anti-glycation agents, agents stimulating the synthesis of dermal macromolecules and 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, receptor antagonists benzodiazepines (PBR), the agents that increase the activity of the sebaceous gland, the agents stimulating the energy metabolism of cells, tensors, liporestructuring agents, slimming agents, skin microcirculation agents, soothing agents and / or anti-irritants, sebo-regulators 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, the hair, the eyelashes, the eyebrows, the 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 agents promoting cutaneous microcirculation 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.

The following examples serve to illustrate the invention without being limiting in nature. EXAMPLES

1 / Preparation of the composite material in a polymer obtained by precipitation of said polymer

The polymerization can be carried out in dispersion, that is by precipitation of the polymer being formed, with protection of formed particles containing the combination of one or more solar filtering agents with one or more plasmonic particles with a stabilizer.

We therefore prepare a mixture comprising

the initial monomers,

a radical initiator,

- filtering agents as well as

the plasmonic particles.

This mixture is dissolved in a solvent subsequently called "synthetic solvent". A synthetic solvent is chosen such that the initial monomers, the radical initiator, the filtering agents and the plasmonic particles are soluble therein, and the polymer particles obtained therein are insoluble, so that they precipitate during their formation.

When the composition comprises a non-volatile oil, as a fatty substance, the polymerization can be carried out in an apolar organic solvent (synthetic solvent) and then the oil is added non-volatile (which must be miscible with said synthesis solvent) and selectively distilling the synthesis solvent.

In particular, the synthesis solvent can be chosen from alkanes such as heptane or cyclohexane.

When the composition comprises a volatile oil, as a fatty substance, the polymerization can be carried out directly in the said oil, which thus also acts as a synthesis solvent.

The monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of 5-20% by weight. All of the monomers may be present in the solvent before the start of the reaction, or a portion of the monomers may be added as the polymerization reaction progresses.

The filtering agents and the plasmonic particles are preferably present in the synthesis solvent, before polymerization, in a proportion of 0.1 to 20% by weight.

The radical initiator may especially be azobisisobutyronitrile or tert-butylperoxy-2-ethylhexanoate.

The polymer particles are surface-stabilized when formed during the polymerization by virtue of a stabilizer which may be a block polymer, a graft polymer, and / or a random polymer, alone or in admixture.

The stabilization can be carried out by any known means, and in particular by direct addition of the block polymer, graft polymer and / or random polymer, during the polymerization.

The stabilizer is preferably also present in the mixture before polymerization. However, it is also possible to add it continuously, especially when the monomers are also added continuously. 2-30% by weight of stabilizer can be used in relation to the initial mixture of monomers, and preferably 5-20% by weight.

2 / Preparation of the composite material Ag _(OjTiO?. A) Embodiment N, N-dimethylformamide (DMF) is capable of reducing silver ions and thus leads to stable silver colloids in the presence of a stabilizer (for example 3-aminopropyltrimethoxysilane (APS)). On the other hand, the controlled hydrolysis and condensation of Ti (OC ₄ Hg) ₄ (TOB) on the surface of the silver cores can be carried out under reflux in the presence of a chelating agent such as acetylacetone, to slow down the hydrolysis. Thus, titanium barks of different particle sizes can be obtained. b) One pot summary

The initial reaction mixture is prepared from two solutions. All the reagents used for this synthesis come from Aldrich.

The first solution has an equimolar amount of

Ti (OC ₄ Hg) ₄ (TOB) and acetylacetone in ethanol at a concentration of 5.75 mM for each of the two components. The sonication in a standard ultrasonic bath for a few minutes allows to obtain a clear mixture.

The second solution comprises 3.8 mM of silver nitrate

(AgNO ₃ ) and 0.8 M water in DMF.

20 ml of the freshly prepared first solution and 5 ml of the second solution are mixed in a beaker and stirred at reflux. After 90 minutes, the colloid reaches a green-black color. This stable dispersion in DMF and ethanol can be diluted with water without any sign of disintegration for a period of at least one week at acidic pH or for one day at basic pH.

The prepared nanoparticles are characterized by high resolution electron transmission microscopy (HRTEM). Images

TEM are taken with a Phillips CM - 12 instrument with a 120 kV acceleration voltage, equipped with a high resolution lens and a 9800 EDAX analyzer. High resolution images are digitally recorded with a CCD camera. Two different populations are observed: a population of large silver particles having a mean diameter of about 20 nm, and smaller silver particles having a mean particle size of 4 nm, both of which are coated homogeneous by a thin bark of amorphous TiO ₂ identified by

EDAX. c) These nanoparticles can be formulated in solar compositions, intended to be applied to the skin or the hair.

3 / Preparation of Ag composite material (£ iSiO 2 + filter a) embodiment

Nanoscale spherical Ag / SiO ₂ composite particles having a narrow size distribution are obtained by silver reduction to inverse micelles followed by in situ hydrolysis and condensation in a microemulsion. When the cores of particles are formed by nucleation and homogeneous growth, the barks are formed by nucleation and heterogeneous growth.

Several methods have been developed for the coupling of filtering agents and Ag @ SiO ₂ core-bark.

One approach may be the coloration or doping of Ag @ SiO ₂ colloids. Another approach is the surface derivation and covalent conjugation of the filtering agent. b) Example

Inverse micelles are prepared using both ionic and nonionic surfactants, using procedures similar to those described in Osseo-Asare, K.; Arrigada, F. Ceram. Trans. 1990, 12, 3. The anionic surfactant is a sodium bis (2-ethylhexyl) sulfosuccinate (Aero OT or AOT, Aldrich Chemical) and the nonionic surfactant is a diethyl ether. polyoxyethylene nonylphenyl (Igepal CO-520, Aldrich Chemical Co.). Both surfactants are used without prior purification. Silver nitrate (AgNC> 3, Aldrich Chemical), tetraethoxysilane (TEOS, 99%), cyclohexane, isooctane and ammonium hydroxide (NH ₄ OH, 29%) (all obtained from Fisher Scientific ) are used.

Deionized water is used for all experiments.

Typically, microemulsions with a total volume of 20 mL are prepared at room temperature in 30 mL vials with rapid agitation. They are obtained by mixing 4 mL of polyoxyethylene nonylphenyl ether (Igepal), 10 mL of cyclohexane, 1.64 mL of a 10 ^-2 mol solution of silver nitrate (Αg (NO 3)) and Deionized water The ratio [water] / [surfactant] is set at 4. The microemulsion is mixed rapidly, and after 5 minutes equilibration, a drop (about 0.05 mL) of hydrazine hydrate (9 MN ₂ H ₄ XH ₂ O, Aldrich Chemical) is added as a reducing agent in the middle., To allow the condensation reaction, a base in the form of sodium hydroxide (NH ₄ (OH)) is added to the reaction mixture. microemulsion with stirring so as to obtain a ratio [NH ₄ (OH)] / [TEOS] equal to 1, and this in a stable suspension.The ratio makes it possible to obtain the appropriate consistency, the pH being measured independently in a After approximately 5 to 10 minutes of an equilibration period, the TEOS solution containing 50% TEOS and 50% by weight cyclo hexane is added to the microemulsion in order to obtain a [water] / [TEOS] ratio of 100 to obtain a thick SiO ₂ bark.

The final particle diameter is 35 nm for a silver core of about 15 nm. The size and morphology of the resulting composite particles are determined by electron transmission microscopy (TEM) (200CX, JEOL, Boston, MA).

Each Ag @ SiO ₂ suspension is washed, centrifuged (at 3500 rpm for 30 minutes) three times in a water-ethanol (5/4) mixture for 30 minutes, followed by resuspension in water. 500 μl of a solution of ethanol containing 1.6 mg / ml of 2- [3- [bis (2-ethylhexyl) amino] -2-cyclohexen-1-ylidene] propanedinitrile (WO2004 / 0068786) are added to 500 μl (0.2 mg) Ag @ SiO ₂ , the nanoparticles being suspended in a solution and being incubated overnight. The mixture is centrifuged, washed with 1.5 ml of water, and 1.2 ml of ethanol four times respectively.

The absorbance of the wash solution is measured to ensure that the unadsorbed UV filter is completely removed.

The absorbance of this system clearly shows an increase in the absorption of the UV filter (+ 25% average absorption in the UV for a fixed rate of fixing agent) for an equivalent quantity doped in silica particles of equivalent size. to Ag @ SiO ₂ particles as prepared above.

The measurement is carried out using the CARY 100 absorbimeter in double beam mode. c) These nanoparticles can be formulated in solar compositions, intended to be applied to the skin or the hair.

4 / Preparation of the composite material by the complex coacervation process a) Operating mode

The complex coacervation method is based on interactions between colloids versus charges, which are usually proteins and polysaccharides. The complex coacervation forms a coating around the target material to be encapsulated. b) Example In order to manufacture the microcapsules walls by complex coacervation, the gelatin (type B) used has a gel strength (bloom) of 300 and an isoelectric point of 5. The gum arabic comes from Sigma-Aldrich. Glutaraldehyde is obtained from Aldrich and citric acid and sodium hydroxide from Fluka. The silver nanoparticles functionalized with decanethiol are obtained from Sigma-Aldrich.

Complex coacervation is achieved by separating an oppositely charged polyion mixture in two distinct phases in specific pH ranges. An aqueous solution to

10% by weight of gelatin and a 10% by weight aqueous solution of gum arabic are prepared for the colloids.

The core material, which is the organic UV filter, namely 2- [3- [bis (2-ethylhexyl) amino] -2-cyclohexen-1-ylidene] -propane dinitrile at 1% by weight (WO 2004 / 006878) and plasmonic particles at 1% by weight (silver nanoparticles functionalized with decanethiol) are emulsified in the gelatin solution at 40 ^° C. The pH of the emulsion is fixed at 4 with the aid of citric acid.

The emulsion is then stirred for 150 minutes. 10% by weight of the gum arabic solution is added to the gelatin emulsion.

Then variable amounts of deionized hot water are slowly added dropwise in order to decrease the colloid concentration and to control that to glutaraldehyde which will be added later.

Glutaraldehyde is added at 11 ° C to solidify the walls around the core material, and microcapsules with thermally stable barks are formed at 55 ° C at a pH of 9.5.

Glutaraldehyde concentrations, after addition, are 0.015 M, 0.03 M and 0.06 M.

The pH of the colloidal solution is adjusted to 4 again with citric acid to keep the colloids stable.

The absorbance of this system clearly shows an increase in UV filter absorption (+ 25% absorption in average in the UV for a fixed rate of filtering agent) for an equivalent quantity doped in silica particles of size equivalent to the Ag (S) SiO ₂ particles as prepared above.

The measurement is carried out with the CARY 100 absorbimeter in double beam mode. c) These particles may be formulated in sunscreen compositions intended to be applied to the skin or the hair. 5 / Preparation of the composite material in microbeads a) Operating mode

It is possible to prepare copolymer beads in the form of perfect spheres using standard suspension polymerization techniques. The diameter of the beads can be controlled by varying the polymerization conditions such as agitation rate, slurry temperature, catalyst concentration, pH, monomer ratios in the suspended medium, and the concentration of the beads. suspending agents.

Microbeads having a mean diameter between 1 and 100 microns can be obtained from at least 1 monomer containing a polymerizable double bond and (as crosslinking agent) at least one monomer containing two or more double bonds.

Suitable monomers containing a polymerizable double bond may be selected from styrene, vinyl toluene, esters of acrylic acid and methacrylic acid, such as methyl, ethyl and butyl, and vinyl acetate ethers.

Suitable monomers containing two or more polymerizable double bonds may be selected from divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, divinyl ketone and divinyl oxalate. Suitable catalysts are those leading to free radicals by heating such as benzoyl peroxide, acetyl peroxide, cumene hydroperoxide and azobisisobutyronitrile.

Preferably, the monomers used are styrene and divinyl benzene (d.v.b.). b) Example

The following reagents are used:

- 80 mL of styrene, 80 mL of a styrene divinylbenzene mixture, containing 8% divinylbenzene; 20 mL of polyisobutylene (Oppanol B.3);

0.4 g of a wetting agent for non-aqueous systems;

1.7 mg of benzoyl peroxide as a catalyst,

200 mL of a solution of polyvinyl alcohol (a concentration of 1.75% in water);

20 g of 2- [3- [bis (2-ethylhexyl) amino] -2-cyclohexen-1-ylidene] propanedinitrile (WO 2004/006878);

5 g of silver nanoparticles functionalized with decanethiol from Sigma-Aldrich.

In this mixture, the polyvinyl alcohol acts as a stabilizer and its concentration is considerably higher than that required when the beads are of normal size (more than 100% ms).

In preparing the microbeads, all the constituents are dispersed and vigorously stirred to convert the monomers to fine particles. The mixture is then heated for at least 4 hours at 70 ^° C. with continuous stirring and the polymerization is complete by heating for at least one more hour at 90 ^° C. with continuous stirring. At least 95% of the microbeads have a diameter of between 3 and 15 μm. The absorbance of this system clearly shows an increase in the absorption of the filtering agent. c) These particles may be formulated in sunscreen compositions intended to be applied to the skin or the hair.

Claims

An ultraviolet radiation filtering composite material 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 plasmonic particle or outside the plasmonic particle at a sufficiently small distance from the plasmonic particle, so that 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, and their alloys, and preferably from among the group consisting of the following metals: aluminum, silver, chromium, zinc, rhodium, as well as their alloys.

3. 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; β, β'-diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives; p-aminobenzoic acid derivatives (PABA); methylene bis (hydroxyphenyl benzotriazole) derivatives; benzoxazole derivatives; filter polymers and silicone filters; dimers derived from α-alkylstyrene; 4,4-diarylbutadienes; merocyanine derivatives and mixtures thereof.

4. Composite material according to any one of the preceding claims, characterized in that the filtering agent is an inorganic UV filter chosen from metal oxide pigments. coated or not, for example titanium oxide pigments, iron, zinc, zirconium or cerium.

5. 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.

6. 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 bisphenol compounds.

7. 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 the filtering agent or agents or formed of the filtering agent or agents.

8. Composite material according to any one of claims 1 to 6, 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.

9. Composite material according to any one of claims 1 to 6, 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 filtering agent.

10. Composite material according to any one of claims 1 to 6 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 non-metallic matrix. metal further comprising at least one ultraviolet radiation filtering agent or being formed from said at least one ultraviolet radiation filtering agent.

1 1. Composite material according to any one of claims 1 to 6, characterized in that it comprises at least one plasmonic particle having inclusions in its relief and said at least one filtering agent placed in inclusions in the relief of the plasmonic particle.

12. Composite material according to any one of claims 1 to 6 characterized in that it consists of at least two composite materials as defined in claims 7 to

1 1.

13. Cosmetic composition for sun protection comprising, in a cosmetically acceptable medium, the composite material according to one of claims 1 to 12, said composition preferably further comprising one or more cosmetic adjuvants, chosen in particular from fats, solvents organic, ionic or nonionic thickeners, hydrophilic or lipophilic, softeners, humectants, opacifiers, antioxidants, stabilizers, emollients, silicones, α-hydroxy acids, antifoaming 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 .

14. Process for the cosmetic treatment of keratinous substances, in particular the skin or hair intended to protect them against the effects of UV rays, comprising applying to them an effective quantity of a cosmetic composition according to claim 13.

15. A method of photostabilizing a photosensitive agent that filters UV radiation, wherein said filtering agent is placed inside the plasmonic particle, or outside the plasmonic particle at a sufficiently small distance from the particle. plasmonic, so that the absorption of ultraviolet radiation on at least a portion of the spectrum of the filtering agent is increased.