FR3061000A1 - AQUEOUS PHOTOPROTECTIVE COMPOSITION CONTAINING POLYACRYLATE CONCENTRATED PARTICLES AND AT LEAST ONE ORGANIC OR INORGANIC INSOLUBLE UV FILTER - Google Patents

Abstract

The present invention relates to an aqueous composition comprising in a physiologically acceptable medium: a) at least one aqueous phase b) concave particles of polyacrylate, in particular in the form of portions of hollow spheres; c) at least one insoluble organic or inorganic UV filter. The present invention also relates to the use of polyacrylate particles, especially in the form of portions of hollow spheres in an aqueous composition comprising in a physiologically acceptable medium at least one aqueous phase and at least one insoluble organic or inorganic UV filter, for the purpose to increase the sun protection factor (SPF). The present invention also relates to the use of concave particles of polyacrylate, in particular in the form of portions of hollow spheres in an aqueous composition comprising in a physiologically acceptable medium at least one aqueous phase and at least one insoluble organic or inorganic UV filter, in order to reduce the gloss after application.

Description

Holder (s):

Agent (s):

L'OREAL Public limited company.

L'OREAL Public limited company.

FR 3 061 000 - A1 ® AQUEOUS PHOTOPROCTOR COMPOSITION CONTAINING CONCAVED POLYACRYLATE PARTICLES AND AT LEAST ONE ORGANIC OR INORGANIC INSOLUBLE UV FILTER.

(57) The present invention relates to an aqueous composition comprising, in a physiologically acceptable medium:

a) at least one aqueous phase

b) concave polyacrylate particles, in particular in the form of portions of hollow spheres;

c) at least one insoluble organic or inorganic UV filter.

The present invention also relates to the use of polyacrylate particles, in particular in the form of portions of hollow spheres in an aqueous composition comprising in a physiologically acceptable medium at least one aqueous phase and at least one insoluble organic or inorganic UV filter, for the purpose increase the sun protection factor (SPF).

The present invention also relates to the use of concave polyacrylate particles, in particular in the form of portions of hollow spheres in an aqueous composition comprising in a physiologically acceptable medium at least one aqueous phase and at least one insoluble organic or inorganic UV filter, in order to reduce the gloss after application.

AQUEOUS PHOTOPROTECTOR COMPOSITION CONTAINING

CONCAVATED POLYACRYLATE PARTICLES AND AT LEAST ONE FILTER

UV ORGANIC OR INORGANIC INSOLUBLE

The present application relates to an aqueous composition comprising, in a physiologically acceptable medium:

a) at least one aqueous phase

b) concave polyacrylate particles, in particular in the form of portions of hollow spheres;

c) at least one insoluble organic or inorganic UV filter.

It is well known that light radiations of wavelengths between 280 nm and 400 nm allow the browning of the human epidermis and that rays of wavelengths between 280 and 320 nm, known under the name of UV-B, cause erythema and skin burns which can affect the development of natural tanning; this UV-B radiation must therefore be filtered.

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, in particular in the case of skin sensitive or skin continuously exposed to solar radiation. UV-A rays cause in particular a loss of elasticity in the skin and the appearance of wrinkles, leading to premature aging. They promote the triggering of the erythematous reaction or amplify this reaction in certain subjects and can even be the cause of photo-toxic or photo-allergic reactions. It is therefore desirable to also filter UV-A radiation.

UVA and UVB rays must therefore be filtered and there are currently cosmetic compositions protecting the human epidermis containing UVA and / or UVB filters in the context of daily and sun photoprotection.

However, one of the major objectives of these applications is, for reasons of cosmetic approval, of tolerance but also for reasons of formulation to limit as much as possible the rate of sunscreens in the composition.

In addition, we are looking for light products, without residue on the skin, which can be easily applied to the skin, especially by spraying.

In patent application US-2015-0064224, solar formulations have already been proposed comprising organic UV filters and spherical polymer particles to increase the level of protection. These particles do not make it possible to obtain both an improvement in the sun protection factor of the compositions as well as softfocus properties or to reduce the shine of the skin after application.

We will therefore look for materials, which introduced into the composition not only make it possible to significantly improve the effectiveness of insoluble sunscreens but without the drawbacks stated above, in particular making it possible to obtain a soft feel after application, a soft focus effect and a tanned skin.

The Applicant has surprisingly and unexpectedly discovered that this objective can be achieved by using concave polyacrylate particles in an aqueous composition comprising at least one insoluble organic or inorganic UV filter.

Furthermore, the Applicant has found that these concave polyacrylate particles in an aqueous composition comprising at least one insoluble organic or inorganic UV filter, also made it possible to significantly reduce the gloss, after application. They also bring softness to the application as well as a soft-focus effect.

These particles allow the reduction or even elimination of the tacky feel, the optimization of the sliding properties, of spreading, and of comfort of the composition according to the invention.

Thus, the subject of the present invention is an aqueous composition comprising in a physiologically acceptable medium:

a) at least one aqueous phase

b) concave polyacrylate particles, in particular in the form of portions of hollow spheres;

c) at least one insoluble organic or inorganic UV filter.

The present invention also relates to the use of concave polyacrylate particles, in particular in the form of portions of hollow spheres in an aqueous composition comprising in a physiologically acceptable medium at least one aqueous phase and at least one insoluble organic or inorganic UV filter, in order to increase the effectiveness of protection against UV radiation and in particular the sun protection factor (SPF).

The present invention also relates to the use of concave polyacrylate particles, in particular in the form of portions of hollow spheres in an aqueous composition comprising in a physiologically acceptable medium at least one aqueous phase and at least one insoluble organic or inorganic UV filter, in order to reduce the gloss after application.

The present invention also relates to the use of concave polyacrylate particles, in particular in the form of portions of hollow spheres in an aqueous composition comprising in a physiologically acceptable medium at least one aqueous phase and at least one insoluble organic or inorganic UV filter, in order to bring softness to the application on the skin.

The term "physiologically acceptable medium" means a non-toxic medium capable of being applied to the skin, the lips, the hair, the eyelashes, the eyebrows, the nails. The composition of the invention may especially constitute a cosmetic or dermatological composition.

The sun protection factor (SPF) is 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.

The term "aqueous composition" means a composition comprising at least

2% by weight of water relative to the weight of the composition.

Polyacrylate concave particles

The concave particles present in the composition according to the invention are solid polyacrylate particles.

These particles are in particular in the form of portions of hollow spheres and in particular are hemispherical hollow particles.

Said particles preferably have an average diameter less than or equal to 30 μm, in particular ranging from 0.5 μm to 25 μm, preferably from 1 to 20 μm, more preferably ranging from 3 to 18 μm, and more preferably ranging from 5 to 15 pm.

By mean diameter is meant the largest dimension of the particle.

Advantageously, these particles have a density greater than 1.

Preferably, the hemispherical hollow particles comprise or consist of homopolymers or copolymers of (meth) acrylic acid or their C1-C4 esters, such as C1-C4 alkyl acrylate or C1-C4 alkyl methacrylate, in particular acrylate or methyl or ethyl methacrylate, preferably crosslinked.

The particles according to the invention are generally obtained by radical polymerization.

By “radical polymerization” is meant a polymerization of at least one ethylenic monomer such as (meth) acrylic acid or their C1-C4 esters, such as C1-C4 alkyl acrylate or methacrylate, in particular acrylate or methacrylate of methyl or ethyl.

The particles comprise at least a concave part and at least a convex part, more particularly the particles have a hollow hemispherical shape, that is to say of the "bowls" type.

The particles in the form of “bowls” can comprise or consist of PMMA.

Particles in the form of “crosslinked polymethyl methacrylate (PMMA) bowls are in particular the MICROPEARL® M310 sold by the company SEPPIC.

The concave particles according to the invention may be present in the composition according to the invention in a content ranging from 0.1 to 20% by weight, preferably ranging from 0.25 to 10% by weight, and preferably ranging from 0, 5 to 5% by weight relative to the total weight of the composition.

Insoluble organic UV filters and inorganic UV filters

The compositions according to the invention contain one or more UV filters chosen from insoluble organic UV filters and / or inorganic UV filters.

By “insoluble organic UV filter” is meant any organic compound screening for UV radiation having a solubility in water of less than 0.5% by weight and a solubility of less than 0.5% by weight in most organic solvents such as paraffin oil, fatty alcohol benzoates and fatty acid triglycerides, for example Miglyol 812® sold by the company DYNAMIT NOBEL. This solubility, carried out at 70 ° C. is defined as the amount of product in solution in the solvent at equilibrium with an excess of solid in suspension after returning to ambient temperature. It can easily be evaluated in the laboratory.

The insoluble organic UV filters according to the invention preferably have an average particle size which varies from 0.01 to 5 μm and more preferably from 0.01 to 2 μm and more particularly from 0.02 to 1.8 μm.

The average particle diameter being measured by a Culter N4 PLUS type particle size distribution analyzer manufactured by Bechman Coulter INC.

The insoluble organic filters according to the invention can be brought into the desired particulate form by any ad-hoc means such as in particular dry grinding or in solvent medium, sieving, atomization, micronization, spraying.

The insoluble organic filters according to the invention in micronized form can in particular be obtained by a process of grinding an insoluble organic UV filter in the form of coarse-sized particles in the presence of an appropriate surfactant making it possible to improve the dispersion particles thus obtained in cosmetic formulations.

An example of a process for micronizing insoluble organic filters is described in applications GB-A-2 303 549 and EP-A-893119. The grinding apparatus used according to these documents can be a jet, ball, vibration or hammer mill and preferably a high agitation mill or an impact mill and more particularly a rotary ball mill, a vibrating mill, tube mill or rod mill.

According to this particular process, alkylpolyglucosides with the structure C _n H ₂ n + i O (C6Hi ₀ O5) _x H in which n is an integer from 8 to 16 and x are used as surfactants for the grinding of said filters. is the average degree of polymerization of the unit (C6H10O5) and varies from 1.4 to 1.6. They can be chosen from Ci-Ci ₂ esters of a compound of structure C _n H _{2n +} i O (C6Hi ₀ O5) _x H and more precisely an ester obtained by reaction of a Ci-Ci ₂ carboxylic acid such as formic, acetic, propionic, butyric, sulfosuccinic, citric or tartaric acid with one or more free OH functions on the glucoside unit (ΟβΗ-ιοΟδ). As alkylpolyglucoside, mention may in particular be made of decylglucoside.

Said surfactants are generally used at a concentration ranging from 1 to 50% by weight and more preferably from 5 to 40% by weight relative to the insoluble filter in its micronized form.

The insoluble organic UV filters in accordance with the invention can be chosen in particular from organic UV filters of the oxalanilide type, of the triazine type, of the benzotriazole type; vinyl amide type; cinnamide type; of the type comprising one or more benzazole and / or benzofuran, benzothiophenene groups or of the indole type; of the aryl vinylene ketone type; of the phenylene bis-benzoxazinone derivative type, of the amide, sulfonamide or acrylonitrile carbamate derivative type or mixtures thereof.

As used in the present invention, the term benzazole includes both benzothiazoles, benzoxazoles and benzimidazoles.

A / Oxalanides

Among the UV filters of the oxalanilide type in accordance with the invention, mention may be made of those corresponding to the structure:

in which Ti, T'i, T ₂ and T ' ₂ denote, identical and different, a C1-Cs alkyl radical or a C1-Cs alkoxy radical. These compounds are described in patent application WO95 / 22959.

By way of examples, mention may be made of the commercial products TINUVIN 315® and TINUVIN 312® sold by the company BASF and respectively of structure:

B / Triazines

Among the insoluble UV filters of the triazine type in accordance with the invention, mention may also be made of those corresponding to the following formula (II):

(II) in which T ₃ , T ₄ , T ₅ , independently, are phenyle, phenoxy, pyrrolo, in which the phenyle, phenoxy, pyrrolo unsubstituted or substituted by one, two or three substituents chosen from OH, CiC-isalkyle or CiC-isalkoxy, CiC-iscarboxyalkyl, Cs-Cscycloalkyle, a methylbenzylidenecamphor group, a group - (CH = CH) _n (CO) -OT ₆ , with T ₆ either Ci-Cisalkyl or cinnamyl.

These compounds are described in WO 97/03642, GB 2286774, EP-743309, WO 98/22447, GB 2319523.

Among the UV filters of the triazine type in accordance with the invention, mention may also be made of insoluble s-triazine derivatives carrying benzalmalonate and / or phenylcyanoacrylate groups such as those described in application EP-A-0790243 (forming an integral part of the content of the description).

Among these insoluble UV filters of type e, the following compounds will be mentioned more particularly:

- 2,4,6-tris (4'-amino diethyl benzalmalonate) -s-triazine,

- 2,4,6-tris (4'-amino benzalmalonate diisopropyl) -s-triazine,

- 2,4,6-tris (dimethyl 4’-amino benzalmalonate) -s-triazine,

- 2,4,6-tns (ethyl a-cyano-4-aminocinnamate) -s-triazine.

Among the UV filters of the triazine type in accordance with the invention, there may also be mentioned the insoluble derivatives of s-triazine carrying benzotriazole and / or benzothiazole groups such as those described in application WO98 / 25922 (forming an integral part of the content of the description).

Among these compounds, there may be mentioned more particularly:

- 2,4,6-tris [(3'-benzotnazol-2-yl-2'-hydroxy-5'-methyl) phenylamino] -s-triazine,

- 2,4,6-tris [(3’-benzotnazol-2-yl-2’-hydroxy-5’-ter-octyl) phenylamino] -s-triazine.

Mention may also be made of symmetrical triazines substituted by naphthalenyl groups or polyphenyl groups described in patent US 6,225,467, application W02004 / 085412 (see compounds 6 and 9) or the document "Symetrical Triazine Dérivatives" IP.COM Journal, IP .COM INC WEST HENRIETTA, NY, US (September 20, 2004) notably 2,4,6-tris (di-phenyl) -tnazine and 2,4,6-tris (ter-phenyl) -triazine which is included in patent applications W006 / 035000, WO06 / 034982, W006 / 034991, W006 / 035007, W02006 / 034992, W02006 / 034985. It is more particularly possible to use an aqueous dispersion

2,4,6-tris (di-phenyl) -tnazine such as in particular TINOSORB A2B® from BASF which is an aqueous dispersion comprising decylglucoside, xanthan gum and propylene glycol (INCI name: Tris-Biphenyl Triazine (and ) Aqua (and) Decyl Glucoside (and) Butylene Glycol (and) Disodium Phosphate (and)

Xanthan Gum)

C / Benzotriazoles

Among the insoluble organic UV filters of the benzotriazole type in accordance with the invention, mention may be made of those of the following formula (III) as described in application WO95 / 22959 (forming an integral part of the content of the description):

in which T ₇ denotes a hydrogen atom or a C1-C6 alkyl radical; T ₈ and T ₉ , identical or different, denote a C1-C6 alkyl radical optionally substituted by a phenyl.

By way of example of compounds of formula (III), mention may be made of the commercial products TINUVIN 328, 320, 234 and 350 from the company BASF with the following structure:

C (CH ₃ ) ₂ CH ₂ CH ₃

Among the insoluble organic UV filters of the benzotriazole type in accordance with the invention, mention may be made of the compounds as described in patents US Pat. No. 5,687,521, US Pat. No. 5,373,037, US Pat. No. 5,362,881 and in particular [2,4'-dihydroxy -3- (2H-benzotriazol-2-yl) -5- (1,1,3,3-tetramethylbutyl) -2'-n-octoxy-5'-benzoyl] diphenylmethane sold under the name MIXXIM PB30® by the company FAIRMOUNT CHEMICAL structure:

Among the insoluble organic UV filters of the benzotriazole type in accordance with the invention, mention may be made of methylene bis- (hydroxyphenyl benzotriazole) derivatives with the following structure:

(IV) in which the radicals T10 and Tu, which are identical or different, denote a C-i-C-is alkyl radical which may be substituted by one or more radicals chosen from C1-C4 alkyl, C5-C12 cycloalkyl or an aryl residue. These compounds are known per se and described in applications 5 US 5237 071, US 5 166 355, GB-A-2 303 549, DE 197 26 184 and EP-A-893 119 (forming an integral part of the description).

In the formula (I) defined above: the C1-C6 alkyl groups can be linear or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, nbutyl, isobutyl, tert-butyl, tert-octyl, n -amyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, tetradecyl, hexydecyl, or octadecyl; C5-C12 cycloalkyl groups are, for example, cyclopentyl, cyclohexyl, cyclooctyl; aryl groups are, for example phenyl, benzyl.

Among the compounds of formula (IV), there may be mentioned those of following structure:

compound (b) compound (a)

compound (c)

The compound (a) with the nomenclature 2,2'-methylene-bis- [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] is sold in particular under the name commercial MIXXIM BB / 200® by FAIRMOUNT CHEMICAL.

The compound (c) with the nomenclature 2,2'-methylene-bis- [6- (2H-benzotriazol-2-yl) -4- (methyl) phenol] is especially sold in solid form under the trade name MIXXIM BB / 200 ® by FAIRMOUNT CHEMICAL.

According to a particularly preferred embodiment of the invention, the methylene bis- (hydroxyphenyl benzotriazole) compounds of formula (IV) are in the form of an aqueous dispersion of particles having an average particle size which varies from 0.01 to 5 μm and more preferably from 0 , 01 to 2 pm and more particularly 0.020 to 2 pm with at least one surfactant of structure C _n H ₂ n + i O (C6Hi ₀ O5) _x H in which n is an integer from 8 to 16 and x is the degree means of polymerization of the unit (ΟβΗ-ιοΟδ) and varies from 1.4 to 1.6 as defined above. Said surfactant is preferably used at a concentration ranging from 1 to 50% by weight and more preferably from 5 to 40% by weight relative to the benzotriazole filter and the amount of benzotriazole filter of formula (I) in the aqueous dispersion varies from preferably from 10 to 50% by weight and more preferably from 30 to 50% by weight relative to the total weight of the dispersion.

The average particle diameter being measured by a Culter N4 PLUS® type particle size distribution analyzer manufactured by Bechman Coulter INC.

According to a particularly preferred form of the invention, the methylene bis- (hydroxyphenyl benzotriazole) compounds of formula (IV) may be in the form of an aqueous dispersion of particles having an average particle size which varies from 0.02 to 2 μm and more preferably from 0.01 to 1.5 pm and more particularly from 0.02 to 1 pm in the presence of at least one mono- (Cs-C2o) alkyl-ester of polyglycerol having a degree of polymerization of glycerol of at least 5 such as the aqueous dispersions described in application WO2009 / 063392.

As an example of polyglycerol mono- (C8-C2o) alkyl esters, there may be mentioned decaglyceryl caprate, decaglyceryl laurate, decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate, decaglyceryl isostearate, hexaglyceryl caprate, hexaglyceryl laurate, hexaglyceryl myristate, hexaglyceryl oleate, hexaglyceryl stearate, hexaglyceryl isostearate, pentaglyceryl caprate, pentaglyceryl laurate, pentaglyceryl laurate pentaglyceryl, pentaglyceryl oleate, pentaglyceryl stearate, pentaglyceryl isostearate.

We will use more in particular

- decaglyceryl caprate such as the products sold under the following trade names SUNSOFT Q10Y®, SUNSOFT Q10S®, SUNSOFT Q12Y®, SUNSOFT Q12S®, SUNSOFT M12J® by the company Taiyo Kagaku Co. Ltd., NIKKOL Decaglyn 1-L by Nikko Chemicals Co. Ltd, RYOTO-Polyglycerylester L-10D® and L-7D® by Mitsubishi-Kagaku Co. Ltd.,

- decaglyceryl laurate such as the products sold under the following commercial names SUNSOFT Q14Y®, SUNSOFT Q14S®, SUNSOFT Q12Y®, SUNSOFT Q12S®, SUNSOFT M12J® by the company Taiyo Kagaku Co. Ltd., NIKKOL Decaglyn 1-M ® by the company Nikko Chemicals Co. Ltd, RYOTO-Polyglycerylester M-10D and M-7D by the company Mitsubishi-Kagaku Co. Ltd.,

- decaglyceryl stearate such as the products sold under the following commercial names SUNSOFT Q18Y®, SUNSOFT Q18S®, SUNSOFT Q12Y®, SUNSOFT Q12S®, SUNSOFT M12J® by the company Taiyo Kagaku Co. Ltd., NIKKOL Decaglyn 1-SV by Nikko Chemicals Co. Ltd, RYOTO-Polyglycerylester S-15D® by Mitsubishi-Kagaku Co. Ltd.,

- Hexagleryl caprate such as the products sold under the following trade names NIKKOL Hexaglyn 1-L® by the company Nikko Chemicals Co. Ltd, GLYSURF 6ML by the company Aoki Oil Industrial Co. Ltd., UNIGLY GL-106® by Nippon Oil & Fats Co. Ltd.,

- Hexaglyceryl myristate such as the products sold under the following trade names NIKKOL Hexaglyn 1-M®, NIKKOL Hexaglyn 1-OV® by the company Nikko Chemicals Co. Ltd, GLYSURF 6ML® by the company Aoki Oil Industrial Co. Ltd ., UNIGLY GL-106 by Nippon Oil & Fats Co. Ltd.,

- Hexaglyceryl stearate such as the products sold under the following trade names NIKKOL Hexaglyn 1-M®, NIKKOL Hexaglyn 1-SV® by the company Nikko Chemicals Co. Ltd, EMALEXMSG-6K® by the company

Nihon-Emulsion Co. Ltd., UNIGLY GL-106 by Nippon Oil & Fats

Co. Ltd.,

- Hexaglyceryl isostearate such as the products sold under the following commercial names MATS U MATE MI-610® by the company Matsumoto Fine Chemical Co. Ltd,

- pentaglyceryl caprate such as the products sold under the following commercial names SUNSOFT A10E®, by the company Taiyo Kagaku Co. Ltd.,

- pentaglyceryl laurate such as the products sold under the following commercial names SUNSOFT A12E®, SUNSOFT A121E®, by the company Taiyo Kagaku Co. Ltd.,

- pentaglyceryl myristate such as the products sold under the following trade names SUNSOFT A14E®, SUNSOFT A141E®, by the company Taiyo Kagaku Co. Ltd.,

- pentaglyceryl oleate such as the products sold under the following commercial names SUNSOFT A17E®, SUNSOFT A171E®, by the company Taiyo Kagaku Co. Ltd.,

- pentaglyceryl stearate such as the products sold under the following commercial names SUNSOFT A18E®, SUNSOFT A181E®, by the company Taiyo Kagaku Co. Ltd.,

Among these surfactants, it is preferred to use those having an HLB greater than or equal to

14.5 and more preferably greater than or equal to 15. As examples of polyglycerol mono- (C8-C2o) alkylesters having a degree of polymerization having a degree of glycerol polymerization of at least 5 having an HLB greater than or equal to 14.5, there may be mentioned decaglyceryl caprate, decaglyceryl laurate, decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate, decaglyceryl isostearate, hexaglyceryl laurate, pentaglyceryl caprate, pentaglyceryl laurate, pentaglyceryl myristate, pentaglyceryl oleate, pentaglyceryl stearate. As examples of polyglycerol mono- (C8-C2o) alkyl esters having a degree of polymerization having a degree of glycerol polymerization of at least 5 having an HLB greater than or equal to 15, there may be mentioned decaglyceryl caprate, laurate decaglyceryl.

The amount of methylene bis- (hydroxyphenyl benzotriazole) compound of formula (IV) in the aqueous dispersion preferably varies from 10 to 50% by weight and more preferably from 30 to 50% by weight relative to the total weight of the dispersion.

Preferably, the weight ratio of methylene bis- (hydroxyphenyl benzotriazole) / mono- (C8-C2o) alkyl ester of polyglycerol varies from 0.05 to 0.5 and more preferably from 0.1 to 0.3.

More preferably in these aqueous dispersions, as the methylene bis- (hydroxyphenyl benzotriazole) compound of formula (IV), the compound 2,2'-methylene-bis- [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3tetramethylbutyl) phenol] of structure:

compound (a) such as the commercial product sold under the name TINOSORB M® by BASF which is an aqueous dispersion comprising decylglucoside, xanthan gum and propylene glycol (INCI name: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (and) Aqua (and ) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum).

One can also use 2,2’-methylene-bis- [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] of structure:

compound (a) in aqueous dispersion of particles having an average particle size which varies from 0.02 to 2 pm and more preferably from 0.01 to 1.5 pm and more particularly from 0.02 to 1 pm in the presence of at at least one mono- (C8-C2o) alkyl ester of polyglycerol having a degree of polymerization of glycerol of at least 5 such as polyglyceryl-10 laurate These aqueous dispersions are in particular described in application WO2009 / 063392.

D / Vinyl amides

Among the insoluble organic filters of the vinyl amide type, there may be mentioned, for example, the compounds of the following formulas which are described in application WO95 / 22959 (forming an integral part of the content of the description):

Ti ₂ - (Y) rC (= O) -C (T ₁₃ ) = C (T ₁₄ ) -N (T ₁₅ ) (T ₁ 6) (V) in which Τ _Ί2 is a C1-C6 alkyl radical, preferably C1-C5 or a phenyl group optionally substituted by one, two or three radicals chosen from OH, C1-C18 alkyl, C1-C6 alkoxy, or a group -C (= O) -OTi ₇ where Τ _Ί7 is C1-C18 alkyl; Τη, T14, T15 and Ti _{6, which are} identical or different, denote a C1-C5, preferably C1-C5 alkyl radical or a hydrogen atom; Is there

N or O and r is 0 or 1.

Among these compounds, more particularly:

- 4-octylamino-3-penten-2-one;

- ethyl-3-octylamino-2-butenoate;

- 3-octylamino-1-phenyl-2-buten-1-one

- 3-dodecylamino-1-phenyl-2-buten-1-one.

E / Cinnamamides

Among the insoluble organic filters of the cinnamamide type in accordance with the invention, mention may also be made of the compounds as described in application WO95 / 22959 (forming an integral part of the content of the description) and corresponding to the following structure:

o

in which OTi ₈ is a hydroxy or C1-C4 alkoxy radical, preferably methoxy or ethoxy; T19 is hydrogen, C1-C4 alkyl, preferably methyl or ethyl; T ₂ o is a group - (CONH) _s -phenyl or s is 0 or 1 and the phenyl group may be substituted by one, two or three groups chosen from OH, C1-C6 alkyl, C1-C6 alkoxy, or a group -C (= O) -OT ₂ i where T ₂ i is a C1-C18 alkyl and more preferably T ₂ i is a phenyl, 4-methoxyphenyl or phenylaminocarbonyl group.

Mention may also be made of cinnamamide dimers such as those described in US Pat. No. 5,888,481, for example the compound of structure:

Among the insoluble organic filters of the benzazole type, mention may be made of those corresponding to one of the following formulas:

in which each of the symbols X independently represents an oxygen or sulfur atom or a group NR ₂ , each of the symbols Z independently represents a nitrogen atom or a group CH, each of the symbols Ri independently represents an OH group, an atom of halogen, a C1-E alkyl group, linear or branched, optionally containing a silicon atom, or a C1-E alkoxy group, linear or branched, each of the numbers m is independently 0, 1 or 2, ίο n represents an integer between 1 and 4 inclusive, p is equal to 0 or 1, each of the numbers q is independently equal to 0 or 1, each of the symbols R2 independently represents a hydrogen atom, a benzyl or C1-alkyl group -e, linear or branched, optionally containing a silicon atom,

A represents a radical of valence n chosen from those of formulas:

in which each of the symbols R ₃ independently represents a halogen atom or a C1-4 alkyl or alkoxy group, linear or branched, or hydroxy, R ₄ represents a hydrogen atom or a C1-4 alkyl group, linear or branched, c = 0 - 4, d = 0 - 3, e = 0 or 1, and f = 0 - 2.

These compounds are described in particular in patents DE 676 103 and CH 350 763, US patent 5,501,850, US patent 5,961,960, patent application EP0669323, US patent 5,518,713, US patent 2,463,264, the article by J. Am. Chem. Soc., 79, 5706 - 5708, 1957, article by J. Am. Chem. Soc., 82, 609 - 5,611, 1960, patent application EP0921126, patent application EP712855.

As examples of preferred compounds of formula (VII) of the family of 2-arylbenzazoles, mention may be made of 2-benzoxazol-2-yl-4-methylphenol, 2- (1 H-benzimidazol-2-yl) -4-methoxyphenol or 2-benzothiazol-2-ylphenol, these compounds being able to be prepared for example according to the methods described in patent CH 350 763.

As examples of preferred compounds of formula (VII) of the family of benzimidazolylbenzazoles, mention will be made of 2,2'-bis-benzimidazole, 5.5 ', 6,6'-tetramethyl-2,2'-bis -benzimidazole, 5,5'-dimethyl-2,2'-bis-benzimidazole, 6-methoxy-2,2'-bis-benzimidazole, 2- (1 H-benzimidazol-2-yl) -benzothiazole, 2- (1 H-benzimidazol-2-yl) -benzoxazole and N, N'-dimethyl-2,2'-bis-benzimidazole, these compounds can be prepared according to the procedures described in US Patents 5,961,960 and US 2,463,264.

By way of examples of preferred compounds of formula (VII) from the family of phenylene benzazoles, mention will be made of 1,4-phenylene-bis- (2-benzoxazolyl), 1,415 phenylene-bis- (2-benzimidazolyl), 1,3-phenylene-bis- (2-benzoxazolyl), 1,2-phenylene-bis- (2-benzoxazolyl), 1,2-phenylene-bis- (benzimidazolyl), 1,4-phenylene- bis- (N-2-ethylhexyl-2-benzimidazolyle) and 1,4-phenylene-bis- (Ntrimethylsilylmethyl-2-benzimidazolyle), these compounds can be prepared according to the procedures described in US Pat. No. 2,463,264 and in the publications J. Am. Chem. Soc., 82, 609 (1960) and J. Am. Chem. Soc., 79, 5706-5708 (1957).

As examples of preferred compounds of formula (VII) of the family of benzofuranyl-benzoxazoles, mention will be made of 2- (2-benzofuranyl) -benzoxazole, 2- (benzofuranyl) -5-methylbenzoxazole and 2- (3 -methyl-2-benzofuranyl) -benzoxazole, these compounds can be prepared according to the procedures described in US Patent 5,518,713.

As preferred compounds of formula (VIII), mention may, for example, be made of 2,6-diphenyl-1,7-dihydro-benzo [1,2-d; 4,5-d '] - di-imidazole corresponding to the formula

or 2,6-distyryl-1,7-dihydro-benzo [1,2-d; 4,5-d '] - di-imidazole or 2,6-di (p-tert-butylstyryl) -1,7-dihydrobenzo [1,2-d; 4,5-d '] - di-imidazole, which can be prepared according to application EP 0 669 323.

As preferred compound of formula (IX), mention may be made of 5,5′-bis - [(2-phenyl) -benzimidazole] of formula:

whose preparation is described in J. Chim. Phys., 64, 1602 (1967).

Among these insoluble organic compounds filtering UV radiation, very particularly preferred is 2- (1 H-benzimidazol-2-yl) benzoxazole, 5 goose, 6-methoxy-2,2'-bis-benzimidazole, 2- ( 1 H-benzimidazol-2-yl) -benzothiazole, 1,4-phenylenebis- (2-benzoxazolyle), 1,4-phenylene-bis- (2-benzimidazolyle), 1,3-phenylenebis- (2- benzoxazolyle), 1,2-phenylene-bis- (2-benzoxazolyl), 1,2-phenylenebis- (2-benzimidazolyle) and 1,4-phenylene-bis- (N-methylethylsilylmethyl-2-benzimidazolyl).

G / Aryl vinylene ketones

Among the insoluble organic filters of the aryl vinylene ketone type, mention may be made of those corresponding to one of the following formulas (X) and (XI):

(X)

r ₅ or ₅ (XI) in which:

n ’= 1 or 2,

B, in formula (X) when n '= 1 or in formula (XI), is an aryl radical chosen from the following formulas (a') to (d '), or in formula (X) when n' = 2, is a radical chosen from the following formulas (e ') to (h'):

in which :

each R ₈ is independently OH, a halogen atom, an alkyl group Ci-e straight or branched and optionally containing a silicon atom, an alkoxy group -C ₈ linear or branched and optionally containing a silicon atom, a C1-5 alkoxycarbonyl group, linear or branched, or a C1-β alkylsulfonamide group, linear or branched and optionally containing a silicon atom or an amino acid function, p 'represents an integer between 0 and 4 inclusive, q 'represents 0 or 1,

R ₅ represents hydrogen or an OH group,

R ₆ represents hydrogen, a C1-E alkyl group, linear or branched and optionally containing a silicon atom, a cyano group, a C1-E alkylsulfonyl group, a phenylsulfonyl group,

R ₇ represents a Ci-e alkyl group, linear or branched and optionally containing a silicon atom or a phenyl group which can form a unicycle and optionally substituted by one or two radicals R ₄ , or R ₆ and R ₇ together form a hydrocarbon residue C2-10 monocyclic, bicyclic or tricyclic, optionally interrupted by one or more nitrogen, sulfur and oxygen, and possibly containing another carbonyl, and optionally substituted with a alkylsulfonamide group Ci-C ₈ linear or branched , and optionally containing a silicon atom or an amino acid function; provided that when n '= 1, R ₆ and R ₇ do not form a camphor nucleus.

As examples of compounds of formula (X) in which n ’= 1, insoluble, filtering UV radiation, having an average particle size of between 10 nm and 5 nm, the following families can be mentioned:

the compounds of the styryl ketone type as described in application JP 04 134 042 such as 1- (3,4-dimethoxy-phenyl) -4,4-dimethyl-pent-1-en-3-one:

- compounds of the benzylidene cineole type such as those described in the article by E. Mariani et al, 16th IFSCC Congress, New York (1990)) such as 1,3,3-trimethyl-5- (4-methoxy-benzylidene ) -2-oxa-bicyclo [2.2.2] octan-6-one:

- Benzylidene chromanone type compounds such as those described in application JP 04 134 043 such as 3- (4-methoxy-benzylidene) 2,3,4a, 8atetrahydro-chromen-4-one:

- Benzylidene thiochromanone type compounds such as those described in application JP 04 134 043 such as 3- (4-methoxy-benzylidene) 2,3,4a, 8atétrahydro-chromèn-4-thione:

- Benzylidene quinuclidinone type compounds such as those described in application EP 0 576 974 such as 4-methoxy benzylidene-1azabicyclo [2.2.2] octan-3-one:

- compounds of the benzylidene cycloalkanone type such as those described in application FR 2 395 023 such as 2- (4-methoxy-benzylidene) -cyclopentanone and

2- (4-methoxy-benzyl-idene) -cyclohexanone:

- compounds of the benzylidene hydantoin type such as those described in application JP 01 158 090 such as 5- (3,4-dimethoxy-benzylidene) -imidazolidine-

2,4-dione:

- Benzylidene indanone type compounds such as those described in application JP 04 134 043 such as 2- (4-methoxy-benzylidene) -indan-1-one:

compounds of the benzylidene tetralone type such as those described in application JP 04 134 043 such as 2- (4-methoxy-benzylidene) -3,4-dihydro-2Hnaphthalen-1-one:

- Benzylidene furanone type compounds such as those described in application EP 0 390 683 such as 4- (4-methoxy-benzylidene) -2,2,5,5-tetramethyl-dihydro-furan-3-one:

\ o. /

-Λ • —C> Me

- Benzylidene benzofuranone type compounds such as those described in application JP 04 134 041 such as 2-benzylidene-benzofuran-3-one:

- Benzylidene indanedione type compounds such as 2- (3,5-di-tert-butyl ~ 4hydroxy-benzylidene) -indan-1,3-dione:

\ /

O π-ι

- Benzylidene benzothiofuranone type compounds such as those described in application JP 04,134,043) such as 2-benzylidene-benzo [b] thiophen-3-one:

- compounds of the barbiturate benzylidene type such as 5- (4-methoxybenzylidene) -1,3-dirnethyl-pyrimidine-2,4,6-trione:

- Benzylidene pyrazolone type compounds such as 4- (4-methoxy benzylidene) -5-methyl-2-phenyl-2,4-dihydro-pyrazol-3-one:

p. ... J

MeO

- Benzylidene imidazolone type compounds such as 5- (4-methoxybenzylidene) -2-phenyl-3,5-dihydro-imidazol-4-one:

We

¹ Nh

N -'- v · '·

- chalcone type compounds such as 1- (2-hydroxy-4-methoxy-phenyl) -3-phenyl-propenone:

/ ·>.

..II.

OH

- the benzylidene one compounds as described in document FR 2 506 156 such as 3-hydroxy-1- (2-hydroxy-4-methoxy-phenyl) -3-phenyl-propenone:

MeO

OH O CH

OMe

As examples of compounds of formula (X) in which n ’= 2 insoluble, filtering UV radiation, having an average particle size of between 10 nm and 5 μm, the following families can be mentioned:

the compounds of the phenylene bis methylidene-nor-camphor type as described in document EP 0 693 471 such as 1,4-phenylene-bis- {3methylidenebicyclo [2.2.1] heptan-2-one}:

- compounds of the phenylene bis methylidene camphor type as described in document FR 2 528 420 such as 1,4-phenylene-bis- {3-methylidene-1,7,7-trimethyl-bicyclo [2.2.1] heptan- 2-one}:

or 1,3-phenylene-bis- {3-methylidene-1,7,7-tnmethyl-bicyclo [2.2.1] heptan-2-one}:

- Phenylene bis methylidene camphor sulfonamide type compounds such as those described in document FR2 529 887 such as 1,4-phenylene-bis-3,3'-methylidene camphor-10,10'-sulfonamide of ethyl or 2 -ethylhexyl:

^And \

'.H- ^! or wJ / -i ζ · t *

K / 7

0 * / 7 \ A

7 / W

\. .7

0.

% \\

4And

Λ

X '·

A 'r’7

s.

- Phenylene bis methylidene cineole type compounds as described in the article E. Mariani et al, 16th IFSCC Congress, New York (1990) such as 1,4-phenylene-bis- {5-methylidene-3,3- dimethyl-2-oxa-bicyclo [2.2.2] octan-6-one}:

-I> j

the compounds of the phenylene bis methylidene ketotricyclodecane type as described in application EP 0 694 521 such as 1,4-phenylene-bis- (octahydro-4,7-methano-6-inden-5-one):

- Phenylene bis alkylene ketone type compounds such as those described in application JP 04 134 041 such as 1,4-phenylene-bis- (4,4-dimethyl-pent-1-en-

3-one):

- Phenylene bis methylidene furanone type compounds as described in application FR 2 638 354 such as 1,4-phenylene-bis- (4-methylidene-2,2,5,5-tetramethyl-dihydrofuran-3-one) :

Û îo - compounds of the phenylene bis methylidene quinuclidinone type such as those described in application EP 0 714 880 such as 1,4-phenylene-bis- {2-methylidene-1-aza-bicyclo [2.2.2] octan-3 -one}:

As compounds of formula (XI), the following families can be mentioned:

- compounds of the bis benzylidene cycloalkanone type such as 2,5-dibenzylidene-cyclopentanone:

- compounds of the gamma pyrone type as described in document JP 04

290 882 such as 2,6-bis- (3,4-dimethoxy-phenyl) -pyran-4-one:

MeO 'CMe

C'Me 2Me

Among these insoluble organic compounds filtering UV radiation of the aryl vinylene ketone type, very particularly preferred are the compounds of formula (X) in which n ’= 2.

HZ Phenylene bis-benzoxazinones

Among the insoluble organic filters of the phenylene bis-benzoxazinone type, mention may be made of those corresponding to the following formula (XII):

... N, .., .R, N

-, „o Û (XII) ^v ï Π ~ oo with R representing a divalent aromatic residue chosen from the following formulas (e) to (h):

in which :

each of the symbols R ₉ independently represents an OH group, a halogen atom, a C1-E alkyl group, linear or branched and optionally containing a silicon atom, a C1-E alkoxy group, linear or branched and optionally containing a silicon atom, a linear or branched C1-5 alkoxycarbonyl group, or a linear or branched C1-alkylsulphonamide group and optionally containing a silicon atom or an amino acid function, p ”represents an integer between 0 and 4 inclusive, q represents 0 or 1,

As examples of compounds of formula (XII), insoluble, filtering UV radiation, having an average particle size of between 10 nm and 5 μm, the following derivatives may be mentioned:

- 2,2’-p-phenylene bis (3,1-benzoxazin-4-one), commercial product CYASORB UV-3638® from the company CYTEC,

- 2,2 ’- (4,4’-biphenylene) bis (3,1-benzoxazin-4-one),

- 2,2 ’- (2,6-naphthylene) bis (3,1-benzoxazin-4-one).

IZ Amide, sulfonamide or acrylonitrile carbamate derivatives

Among the insoluble organic filters of the amide, sulfonamide or acrylonitrile carbamate derivative type, mention may be made of those corresponding to the following formula (XIII)

in which :

Rio represents a C1-Cs alkyl group, linear or branched, n ’” is 0, 1 or 2,

X ₂ represents a divalent radical of formula - (C = O) -Rn- (C = O) -, -SO2-R11-SO2-ou - (C = O) -O-Rii-O- (C = O) -,

Y represents a radical - (C = O) -Ri2 or -SO2R13,

R11 represents a single bond or a divalent C1-C30 alkylene or C3-C30 alkenylene radical, linear or branched, which can carry one or more hydroxyl substituents and which can contain, in the carbon chain, one or more heteroatoms chosen from atoms oxygen, nitrogen and silicon,

R12 represents a radical -ORu or -NHRu,

R13 represents a C1-C30 alkyl radical, linear or branched, or a phenyl ring unsubstituted or substituted by C1-C4 alkyl or alkoxy radicals, Ru represents a C1-C30 alkyl or C3-C30 alkenyl radical, linear or branched, which can carry one or more hydroxyl substituents and which can contain, in the carbon chain, one or more heteroatoms chosen from oxygen, nitrogen and silicon atoms.

Although in formula (XIII) above, only the isomers in which the cyano substituent is in the c / s position relative to the para-amino-phenyl substituent are represented, this formula should be understood as also including the corresponding trans isomers ; for each of the two double bonds and independently, the cyano and para-amino-phenyl substituents may be in the cis or trans configuration with respect to each other.

By way of example, mention may be made of the 2-cyano-3- [4- (acetylamino) phenyl] 2-ethylhexylacrylate dimer of formula:

And

J / Multipurpose metals

Another particular family of insoluble organic filters in accordance with the invention are the polyvalent metal salts (for example Ca ²⁺ , Zn ²⁺ , Mg ²⁺ , Ba ²⁺ , Al ³⁺ or Zr ⁴⁺ ) of sulfonic organic filters or carboxylic such as the polyvalent metal salts of sulfonated benzylidene camphor derivatives such as those described in application FR-A 2 639 347; the polyvalent metal salts of sulfonated benzimidazole derivatives such as those described in application EP-A-893119; polyvalent metal salts of cinnamic acid derivatives such as those described in application JP-87 166 517.

Mention may also be made of metal or ammonium or substituted ammonium complexes of organic filters UV-A and / or UV-B as described in patent applications WO93 / 10753, WO93 / 11095 and WO95 / 05150.

Among the insoluble organic UV filters, there may also be mentioned the compound 1,1 '- (1,4-piperazinediyl) bis [1 - [2- [4- (diethylamino) -2-hydroxybenzoyl] phenyl] -methanone (CAS 919803 -06-8) with the following structure:

as described in application WO2007 / 071584; this compound being advantageously used in micronized form (average size of 0.02 to 2 μm) which can be obtained for example according to the micronization process described in applications GB-A-2 303 549 and EP-A-893119 and in particular in the form of aqueous dispersion.

According to a particularly preferred form of the invention, use will be made of the insoluble organic UV filters chosen from (i) symmetrical triazine filters substituted by naphthalenyl groups or polyphenyl groups described in patent US 6,225,467, application WO2004 / 085412 (see compounds 6 and 9) or the document “Symetrical Triazine Dérivatives” IP.COM IPCOM000031257 Journal, INC WEST HENRIETTA, NY, US (September 20, 2004) including 2,4,6-tris (di-phenyl) -triazine and 2 , 4,6-tris (ter-phenyl) -triazine which is included in patent applications W006 / 035000, WO06 / 034982, W006 / 034991, W006 / 035007, W02006 / 034992, W02006 / 034985, these compounds being advantageously used in micronized form (average particle size of 0.02 to 3 μm) which can be obtained for example according to the micronization process described in applications GB-A-2 303 549 and EP-A-893119 and in particular in the form of an aqueous dispersion ;

(ii) the methylene bis- (hydroxyphenyl benzotriazole) compounds of formula (IV) below:

11 in which the radicals T10 and Tu, identical or different, denote a C1-C18 alkyl radical which may be substituted by one or more radicals chosen from C1-C4 alkyl, C5-C12 cycloalkyl or an aryl residue;

(iii) and their mixtures.

According to a particularly preferred embodiment of the invention, the methylene bis- (hydroxyphenyl benzotriazole) compounds of formula (IV) are in the form of an aqueous dispersion of particles having an average particle size which varies from 0.01 to 5 μm and more preferably from 0 , 01 to 2 pm and more particularly 0.020 to 2 pm with at least one surfactant of structure C _n H ₂ n + i O (C6Hi ₀ O5) _x H in which n is an integer from 8 to 16 and x is the degree means of polymerization of the unit (ΟβΗ-ιοΟδ) and varies from 1.4 to 1.6 as defined above. Said surfactant is preferably used at a concentration ranging from 1 to 50% by weight and more preferably from 5 to 40% by weight relative to the benzotriazole filter and the amount of benzotriazole filter of formula (I) in the aqueous dispersion varies from preferably from 10 to 50% by weight and more preferably from 30 to 50% by weight relative to the total weight of the dispersion.

The average particle diameter being measured by a Culter N4 PLUS® type particle size distribution analyzer manufactured by Bechman Coulter INC.

According to a particularly preferred form of the invention, the methylene bis- (hydroxyphenyl benzotriazole) compounds of formula (IV) may be in the form of an aqueous dispersion of particles having an average particle size which varies from 0.02 to 2 μm and more preferably from 0.01 to 1.5 μm and more particularly from 0.02 to 1 μm in the presence of at least one mono- (C8-C2o) alkyl-ester of polyglycerol having a degree of polymerization of glycerol of at least 5 such as the aqueous dispersions described in application WO2009 / 063392.

As an example of polyglycerol mono- (C8-C2o) alkyl esters, there may be mentioned decaglyceryl caprate, decaglyceryl laurate, decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate, decaglyceryl isostearate, hexaglyceryl caprate, hexaglyceryl laurate, hexaglyceryl myristate, hexaglyceryl oleate, hexaglyceryl stearate, hexaglyceryl isostearate, pentaglyceryl caprate, pentaglyceryl laurate, pentaglyceryl laurate pentaglyceryl, pentaglyceryl oleate, pentaglyceryl stearate, pentaglyceryl isostearate.

We will use more in particular

- decaglyceryl caprate such as the products sold under the following trade names SUNSOFT Q10Y®, SUNSOFT Q10S®, SUNSOFT

Q12Y®, SUNSOFT Q12S®, SUNSOFT M12J® by the company Taiyo

Kagaku Co. Ltd., NIKKOL Decaglyn 1-L by Nikko Chemicals Co.

Ltd, RYOTO-Polyglycerylester L-10D® and L-7D® by MitsubishiKagaku Co. Ltd.,

- decaglyceryl laurate such as the products sold under the following commercial names SUNSOFT Q14Y®, SUNSOFT Q14S®, SUNSOFT Q12Y®, SUNSOFT Q12S®, SUNSOFT M12J® by the company Taiyo Kagaku Co. Ltd., NIKKOL Decaglyn 1-M ® by the company Nikko Chemicals Co. Ltd, RYOTO-Polyglycerylester M-10D and M-7D by the company Mitsubishi-Kagaku Co. Ltd.,

- decaglyceryl stearate such as the products sold under the following commercial names SUNSOFT Q18Y®, SUNSOFT Q18S®, SUNSOFT Q12Y®, SUNSOFT Q12S®, SUNSOFT M12J® by the company Taiyo Kagaku Co. Ltd., NIKKOL Decaglyn 1-SV by Nikko Chemicals Co. Ltd, RYOTO-Polyglycerylester S-15D® by Mitsubishi-Kagaku Co. Ltd.,

- Hexagleryl caprate such as the products sold under the following trade names NIKKOL Hexaglyn 1-L® by the company Nikko Chemicals Co. Ltd, GLYSURF 6ML by the company Aoki Oil Industrial Co. Ltd., UNIGLY GL-106® by Nippon Oil & Fats Co. Ltd.,

- Hexaglyceryl myristate such as the products sold under the following trade names NIKKOL Hexaglyn 1-M®, NIKKOL Hexaglyn 1-OV® by the company Nikko Chemicals Co. Ltd, GLYSURF 6ML® by the company Aoki Oil Industrial Co. Ltd ., UNIGLY GL-106 by Nippon Oil & Fats Co. Ltd.,

- Hexaglyceryl stearate such as the products sold under the following trade names NIKKOL Hexaglyn 1-M®, NIKKOL Hexaglyn 1-SV® by the company Nikko Chemicals Co. Ltd, EMALEXMSG-6K® by the company Nihon-Emulsion Co. Ltd., UNIGLY GL-106 by Nippon Oil & Fats Co. Ltd.,

- Hexaglyceryl isostearate such as the products sold under the following trade names MATSUMATE MI-610® by the company Matsumoto Fine Chemical Co. Ltd,

- pentaglyceryl caprate such as the products sold under the following commercial names SUNSOFT A10E®, by the company Taiyo Kagaku Co. Ltd.,

- pentaglyceryl laurate such as the products sold under the following commercial names SUNSOFT A12E®, SUNSOFT A121E®, by the company Taiyo Kagaku Co. Ltd.,

- pentaglyceryl myristate such as the products sold under the following trade names SUNSOFT A14E®, SUNSOFT A141E®, by the company Taiyo Kagaku Co. Ltd.,

- pentaglyceryl oleate such as the products sold under the following commercial names SUNSOFT A17E®, SUNSOFT A171E®, by the company Taiyo Kagaku Co. Ltd.,

- pentaglyceryl stearate such as the products sold under the following commercial names SUNSOFT A18E®, SUNSOFT A181E®, by the company Taiyo Kagaku Co. Ltd.,

Among these surfactants, it is preferred to use those having an HLB greater than or equal to

14.5 and more preferably greater than or equal to 15. As examples of polyglycerol mono- (C8-C2o) alkylesters having a degree of polymerization having a degree of glycerol polymerization of at least 5 having an HLB greater than or equal to 14.5, there may be mentioned decaglyceryl caprate, decaglyceryl laurate, decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate, decaglyceryl isostearate, hexaglyceryl laurate, pentaglyceryl caprate, pentaglyceryl laurate, pentaglyceryl myristate, pentaglyceryl oleate, pentaglyceryl stearate. As examples of polyglycerol mono- (C8-C2o) alkyl esters having a degree of polymerization having a degree of glycerol polymerization of at least 5 having an HLB greater than or equal to 15, there may be mentioned decaglyceryl caprate, laurate decaglyceryl.

The amount of methylene bis- (hydroxyphenyl benzotriazole) compound of formula (IV) in the aqueous dispersion preferably varies from 10 to 50% by weight and more preferably from 30 to 50% by weight relative to the total weight of the dispersion.

Preferably, the weight ratio of methylene bis- (hydroxyphenyl benzotriazole) / mono- (C8-C2o) alkyl ester of polyglycerol varies from 0.05 to 0.5 and more preferably from 0.1 to 0.3.

More preferably in these aqueous dispersions, as the methylene bis- (hydroxyphenyl benzotriazole) compound of formula (IV), the compound 2,2'-methylene-bis- [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3tetramethylbutyl) phenol] of structure:

such as in particular the commercial product sold under the name TINOSORB M® by BASF which is an aqueous dispersion comprising decylglucoside, xanthan gum and propylene glycol (INCI name: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (and) Aqua (and) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum) or the aqueous dispersion of compound (a) in the presence of polyglyceryl-10 laurate.

The insoluble organic UV filter (s) of the invention are present at a concentration of active material preferably ranging from 0.1 to 30% by weight approximately, and more particularly from 0.5 to 20% by weight relative to the total weight of the composition.

IV) INORGANIC UV FILTERS

By "inorganic UV filter" is meant any non-organic chemical molecule capable of absorbing and / or physically blocking (in particular reflection or diffraction) UV radiation in the wavelength range between 280 and 400 nm.

The inorganic UV filters used in accordance with the present invention are metallic oxide pigments. More preferably, the inorganic UV filters of the invention are metal oxide particles having an average elementary particle size less than or equal to 0.5 μm, more preferably between 0.005 and 0.5 μm and even more preferably between 0.01 and 0.2 pm, better still between 0.01 and 0.1 pm, and more particularly preferably between 0.015 and 0.05 pm.

They can in particular be chosen from titanium, zinc, iron, zirconium, cerium oxides or their mixtures.

Such metallic oxide pigments, coated or uncoated are in particular described in patent application EP-A-0 518 773. As commercial pigments, mention may be made of the products sold by the companies SACHTLEBEN PIGMENTS, TAYCA, MERCK AND DEGUSSA .

Metallic oxide 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 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.

The coated pigments are more particularly coated titanium oxides:

- silica such as the SUNVEIL product 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,

- alumina such as the products TIPAQUE TTO-55 (B) and TIPAQUE TTO-55 (A) from the company ISHIHARA, and UVT 14/4 from the company SACHTLEBEN PIGMENTS,

- aluminum alumina and stearate such as MICROTITANIUM DIOXIDE MT 100 T, MT 100 TX, MT 100 Z, MT-01 from TAYCA, Solaveil CT-10 W and Solaveil CT 100 from company UNIQEMA and the Eusolex T-AVO product from 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 the company 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 BR 351 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 SACHTLEBEN PIGMENTS,

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

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

- stearic acid such as the product TIPAQUE TTO-55 (C) from the company ISHIHARA, sodium hexametaphosphate such as the product MICROTITANIUM DIOXIDE MT 150 W 'from the company TAYCA.

- T1O2 treated with octyl trimethyl silane sold under the trade name T 805 by the company DEGUSSA SILICES,

- T1O2 treated with a polydimethylsiloxane sold under the trade name 70250 Cardre UF TÎO2SI3 by the company CARDRE,

- T1O2 anatase / rutile treated with a polydimethylhydrogenosiloxane sold under the trade name MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBIC by the company COLOR TECHNIQUES.

Mention may also be made of T1O2 pigments doped with at least one transition metal such as iron, zinc, manganese and more particularly manganese. Preferably said doped pigments are in the form of an oily dispersion. The oil present in the oily dispersion is preferably chosen from triglycerides including those of capric / caprylic acids. The oily dispersion of titanium oxide particles may additionally comprise one or more dispersing agents such as for example a sorbitan ester such as sorbitan isostearate, a fatty acid and polyoxyalkylenated glycerol ester such as TRI-PPG3 MYRISTYLETHER CITRATE and POLYGLYCERYL-3 POLYRICINOLEATE. Preferably, the oily dispersion of titanium oxide particles comprises at least one dispersing agent chosen from esters of fatty acid and of polyoxyalkylene glycerol. Mention may more particularly be made of the oily dispersion of particles of T1O2 doped with manganese in the triglyceride of capric / caprylic acid in the presence of TRI-PPG-3 MYRISTYLETHER CITRATE and the POLYGLYCERYL-3-POLYRICINOLEATE and SORBITAN ISOSTERATE of INCI name: TITANIUM DIOXIDE (and) TRI-PPG-3 MYRISTYLETHER CITRATE (and) POLYGLYCERYL-3 RICINOLEATE (and) SORBITAN ISOSTEARATE as the product sold under the trade name OPTISOL TD50 by the company CRODA.

Uncoated titanium oxide pigments are for example sold by the company TAYCA under the trade names MICROTITANIUM DIOXIDE MT 500 B or MICROTITANIUM DIOXIDE MT600 B, by the company DEGUSSA under the name P 25, by the company WACKHER under the name Oxide of transparent titanium 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.

Uncoated zinc oxide pigments are, for example:

- those sold under the name Z-cote by the company Sunsmart;

- those marketed under the name Nanox by the company Elementis;

- those marketed under the name Nanogard WCD 2025 by the company Nanophase Technologies;

The coated zinc oxide pigments are for example:

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

- those marketed under the name Nanogard Zinc Oxide FN by the company Nanophase Technologies (in 40% dispersion in Finsolv TN, benzoate of C12-C15 alcohols);

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

- those sold under the name NFD Ultrafine ZnO by the company Daikin (ZnO coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl dispersed in cyclopentasiloxane);

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

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

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

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

The uncoated cerium oxide pigments may for example be those sold under the name COLLOIDAL CERIUM OXIDE by the company RHONE POULENC.

Uncoated iron oxide pigments are for example sold by the company ARNAUD under the names NANOGARD WCD 2002 (FE 45B), NANOGARD IRON FE 45 BL AQ, NANOGARD FE 45R AQ, NANOGARD WCD 2006 (FE 45R), or by MITSUBISHI under the name TY-220.

The coated iron oxide pigments are for example sold by the company ARNAUD under the names NANOGARD WCD 2008 (FE 45B FN),

NANOGARD WCD 2009 (FE 45B 556), NANOGARD FE 45 BL 345,

NANOGARD FE 45 BL, or by BASF under the name

TRANSPARENT IRON OXIDE.

Mention may also be made of mixtures of metal oxides, in particular of titanium dioxide and cerium dioxide, including the equiponderal mixture of titanium dioxide and cerium dioxide coated with silica, 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 SACHTLEBEN PIGMENTS or coated with alumina, silica and glycerine such as the product M 211 sold by SACHTLEBEN PIGMENTS.

According to the invention, the titanium oxide pigments, coated or uncoated, are particularly preferred.

The inorganic insoluble UV filters of the invention are preferably present in the compositions according to the invention at a content ranging from 0.1% to 30% by weight, more particularly from 0.5 to 20% by weight, and in particular from 1 to 10% by weight relative to the total weight of the composition.

The total amount of insoluble organic or inorganic filters is generally included in the compositions according to the invention in proportions ranging from 0.1 to 30% by weight relative to the total weight of the composition, and preferably ranging from 0.5 to 20% by weight relative to the total weight of the composition.

The compositions of the invention can contain all the additives usually used in cosmetics and will find applications in the field of skincare, make-up and sun products.

According to the invention, the compositions according to the invention may contain other UV filters different from the insoluble organic or inorganic UV filters. In particular, water-soluble or liposoluble organic UV filters can be used.

The aqueous compositions in accordance with the present invention may also comprise conventional cosmetic adjuvants in particular chosen from fatty substances, organic solvents, ionic or nonionic thickeners, hydrophilic or lipophilic, softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-foaming agents, perfumes, preservatives, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active agents, fillers, polymers, propellants, basifying or acidifying agents or any other ingredient usually used in the cosmetic and / or dermatological field.

The fatty substances can consist of an oil or a wax or their mixtures. By oil is meant a compound that is liquid at room temperature. The term “wax” is intended to mean a compound which is solid or substantially solid at room temperature, and the melting point of which is generally greater than 35 ° C.

As oils, mention may be made of mineral oils (paraffin); vegetable (sweet almond oil, macadamia oil, blackcurrant seed, jojoba); synthetics such as perhydrosqualene, alcohols, fatty amides (such as isopropyl lauroyl sarcosinate sold under the name of "Eldew SL-205" by the company Ajinomoto), fatty acids or esters (such as the benzoate of alcohols C12-C15 sold under the trade name “Finsolv TN” or “Witconol TN” by the company WITCO, octyl palmitate, isopropyl lanolate, triglycerides including those of capric / caprylic acids, dicaprylyl carbonate sold under the name "Cetiol CC" by the company COGNIS), oxyethylenated or oxypropylenated fatty esters and ethers; silicone oils (cyclomethicone, polydimethysiloxanes or PDMS) or fluorinated oils, polyalkylenes.

As waxy compounds, there may be mentioned paraffin, carnauba wax, beeswax, hydrogenated castor oil.

As hydrophilic thickeners, mention may be made of carboxyvinyl polymers such as Carbopols (Carbomers) and acrylate / C10-C30-alkylacrylate copolymers such as Pemulen TR1 and TR2; methacrylic acid / methyl acrylate / dimethyl meta-isoprpenyl benzyl isocyanate terpolymer of ethoxylated alcohol (INCI name: Polyacrylate-3) as the product sold by Amerchol under the name VISCOPHOBE DB 1000; polyacrylamides such as, for example, crosslinked copolymers sold under the names Sepigel 305 (C.T.F.A. name: polyacrylamide / C13-14 isoparaffin / Laureth 7) or Simulgel 600 (name

C.T.F.A. acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by the company Seppic; polymers and copolymers of 2-acrylamido 2-methylpropane sulfonic acid, optionally crosslinked and / or neutralized, such as the poly (2-acrylamido 2-methylpropane sulfonic acid) sold by the company Clariant under the trade name "Hostacerin AMPS" (name CTFA: ammonium polyacryldimethyltauramide); cellulose derivatives such as hydroxyethylcellulose; polysaccharides and in particular gums such as xanthan gum; and their mixtures.

As lipophilic thickeners, mention may be made of synthetic polymers such as the poly C10-30 alkyl acrylate sold under the name "Doresco IPA 13-1" by the company Landec or alternatively modified clays such as hectorite and its derivatives, such as products marketed under the names of Bentone.

The organic solvents can be chosen from the group consisting of hydrophilic organic solvents, lipophilic organic solvents, amphiphilic solvents or their mixtures.

Among the hydrophilic organic solvents, there may be mentioned, for example, linear or branched monohydric alcohols having from 2 to 8 carbon atoms such as ethanol, propanol, butanol, isopropanol, isobutanol; polyethylene glycols having from 6 to 80 ethylene oxides; polyols such as propylene glycol, propanediol-1,3, isoprene glycol, butylene glycol, pentylene glycol, glycerol, sorbitol; the mono- or di-alkyl of isosorbide in which the alkyl groups have from 1 to 5 carbon atoms such as dimethyl isosorbide; glycol ethers such as diethylene glycol mono-methyl or mono-ethyl ether and propylene glycol ethers such as dipropylene glycol methyl ether.

As amphiphilic organic solvents, mention may be made of polypropylene glycol derivatives (PPG) such as the esters of polypropylene glycol and of fatty acid, of PPG and of fatty alcohol such as PPG-23 oleyl ether and PPG-36 oleate.

As lipophilic organic solvents, mention may be made, for example, of fatty esters such as diisopropyl adipate, dioctyl adipate, alkyl benzoates.

As fillers which can be used in the composition of the invention, mention may be made, for example, of pigments; silica powder; talc; polyamide particles and in particular those sold under the name ORGASOL by the company Atochem; polyethylene powders; powders of natural organic materials such as starch powders, in particular of corn, wheat or rice starches, crosslinked or not, such as starch powders crosslinked with octenylsuccinate anhydride, sold under the name DRY -FLO by the company National Starch; microspheres based on acrylic copolymers, such as those in ethylene glycol dimethacrylate / lauryl methacrylate copolymer sold by the company Dow Corning under the name of POLYTRAP; polymethylmethacrylate powders such as those sold under the name MICROPEARL M 100 by the company Matsumoto; expanded powders such as hollow microspheres and in particular, microspheres marketed under the name EXPANCEL by the company Kemanord Plast or under the name MICROPEARL F 80 ED by the company Matsumoto; silicone resin microbeads such as those sold under the name TOSPEARL by the company Toshiba Silicone; polyurethane powders such as the hexamethylene diisocyanate / trimethylol hexyllactone copolymer powder sold under the name Plastic Powder D-400 by the company Toshiba Pigment (CTFA name: HDI / Trimethylol Hexyllactone Crosspolymer); and their mixtures. When they are present, these fillers can be in amounts ranging from 0.001 to 20% by weight, preferably from 0.1 to 10% by weight and better still from 1 to 5% by weight relative to the total weight of the composition.

Among the active ingredients, we can cite:

- vitamins (A, C, E, K, PP ...) and their derivatives or precursors, alone or in mixtures,

- anti-pollution agents and / or anti-radical agents;

- depigmenting agents and / or pro-pigmenting agents;

- anti-glycation agents;

- soothing agents,

- NO-synthase inhibitors;

- agents stimulating the synthesis of dermal or epidermal macromolecules and / or preventing their degradation;

- agents stimulating fibroblast proliferation;

- agents stimulating the proliferation of keratinocytes;

- muscle relaxants;

- tensing agents,

- matting agents,

- keratolytic agents,

- scaling agents;

- moisturizers;

- anti-inflammatory agents;

- agents acting on the energy metabolism of cells,

- repellents against insects

- substance P or CRGP antagonists.

- anti-hair loss and / or hair regrowth agents

- anti-wrinkle agents.

Of course, those skilled in the art will take care to choose the optional compound (s) mentioned above and / or their quantities in such a way that the advantageous properties intrinsically attached to the compositions according to the invention are not, or substantially not, altered by the planned addition (s).

The compositions according to the invention can be prepared according to techniques well known to those skilled in the art. They can be in particular in the form of aqueous dispersions, of two-phase: solid liquid; three-phase: solid / two immiscible liquids / or emulsions, simple or complex (O / W, W / O, O / W / O or W / O / W) such as a cream, milk or a cream gel; in the form of an aqueous gel; in the form of a lotion. They can optionally be packaged as an aerosol. They can be in the form of foam or aerosol or non-aerosol spray.

The emulsions generally contain at least one surfactant chosen from amphoteric, anionic, cationic or nonionic surfactants, used alone or as a mixture. The surfactants are in particular appropriately chosen for preparing the emulsions.

As emulsifying surfactants which can be used for the preparation of W / O emulsions, mention may, for example, be made 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 the company Dow Corning, and alkyl dimethicone copolyols such as Laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by Dow Corning; Cetyl dimethicone copolyol such as the product sold under the name Abil EM 90R by the company Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the name ABIL WE 09 by Goldschmidt. One or more coemulsifiers can also be added thereto, which advantageously can be chosen from the group comprising alkylated polyol esters.

As alkylated polyol esters, mention may in particular be made of polyethylene glycol esters such as PEG-30 Dipolyhydroxystearate such as the product sold under the name Arlacel P135 by the company ICI;

As glycerol and / or sorbitan esters, mention may, for example, be made of polyglycerol isostearate, such as the product sold under the name Isolan Gl 34 by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company

HERE ; sorbitan isostearate and glycerol, such as the product sold under the name Arlacel 986 by the company ICI, and their mixtures.

For O / W emulsions, non-ionic emulsifiers such as esters of fatty acids and glycerol oxyalkylenated (more particularly polyoxyethylenated) may be mentioned, for example, as emulsifiers; esters of oxyalkylenated fatty acids and sorbitan; esters of oxyalkylenated fatty acids (oxyethylenated and / or oxypropylenated) such as the PEG-100 Stearate / Glyceryl Stearate mixture sold for example by the company ICI under the name Arlacel 165; ethers of oxyalkylenated fatty alcohols (oxyethylenated and / or oxypropylenated); sugar esters such as sucrose stearate; fatty alcohol and sugar ethers, in particular alkylpolyglucosides (APG) such as decylglucoside and laurylglucoside marketed for example by the company Henkel under the respective names Plantaren 2000 and Plantaren 1200, ketostearylglucoside optionally in mixture with cetostearyl alcohol , 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 the company Henkel, as well as arachidyl glucoside, for example in the form 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 can be in the form of a self-emulsifying composition, as described for example in the document WO- A-92/06778.

When it is 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).

According to a particular embodiment of the invention, the oil-in-water or water-in oil emulsions according to the invention may comprise only 1% by weight or less, and even be free of emulsifying surfactants, while being stable to storage. In this case, they can be stabilized by various techniques such as the use of hydrophilic or lipophilic thickening agents such as those of patent EP864320, of amphiphilic polymers such as those cited in patent EP1093796, in patent application WO02 / 44231, solid particles (Pickering type emulsions) such as the emulsions cited in patent applications W098 / 42300, WO98 / 42301, EP987001, EP987002, EP987003, EP987004 EP987005 EP987006 EP-987007 EP-987008,

W02000 / 07548, W02000 / 07549, EP992233.

Another object of the present invention consists of 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, in particular care products, sun protection products and make-up products.

The composition according to the invention can constitute a product for the care of the skin, in particular for the face, the neck, the eye contour, the body; or even a make-up product such as a complexion product (in particular foundation), concealer product, a sun protection product or even a skin cleansing product. Preferably, the composition according to the invention will be a sun protection product.

The cosmetic compositions according to the invention can for example be used as a care and / or sun protection product for the face and / or the body, a protection product for the scalp or the hair. The compositions can be of liquid, semi-liquid or solid consistency, such as lotions, milks, more or less creamy creams, gels, gel-creams. They can optionally be packaged as an aerosol and come in the form of a foam or spray, non-aerosol spray, pump bottle, etc.

The compositions according to the invention in the form of vaporizable fluid lotions in accordance with the invention are applied to the skin or the hair in the form of fine particles by means of vaporizing devices, pressurized or not. The devices according to the invention are well known to those skilled in the art and include aerosol or non-aerosol or atomizer pumps, aerosol containers comprising a propellant as well as aerosol pumps using compressed air as a propellant. These are described in US Patents 4,077,441 and US 4,850,517 (forming an integral part of the content of the description).

The aerosol-conditioned compositions in accordance with the invention generally contain conventional propellants such as, for example, the hydrofluorinated compounds dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane, trichlorofluoromethane, and their mixtures. They are preferably present in amounts ranging from 5 to 95% by weight relative to the total weight of the composition.

The invention will now be described with reference to the following examples given by way of illustration and not limitation. In these examples, unless otherwise indicated, the quantities are expressed in percentages by weight. The following solar formulations were made; the quantities are indicated in percentages by weight:

Examples 1 to 3:

The following three compositions were prepared:

Phas e INCI EU name Example 1 Example 2 Example 3 (Invention) AT AQUA qs 100% 100% 100% PROPYLENE GLYCOL 6 6 6 CAPRYLYL GLYCOL 0.1 0.1 0.1 HEXYLENE GLYCOL 1 1 1 DIPROPYLENE GLYCOL 10 10 10 BUTYLENE GLYCOL 4 4 4 GLYCERIN 3 3 3 BIS-PEG-18 METHYL ETHER 1 1 1

DIMETHYL SILANE B TITANIUM DIOXIDE (and) SILICA (and) ALUMINUM HYDROXIDE (and) ALGINIC ACID (MT 100 AQ de TAYCA) 1 1 1 METHYLENE BIS- BENZOTRIAZOLYL TETRAMETHYLBUTYLPHENO L (TINOSORB M from BASF) 2 2 2 VS Hollow hemispherical particles (5-15 pm) of METHYL METHACRYLATE CROSSPOLYMER (SEPIMAT H10by SEPPIC) 0 3 Hollow spherical particles (5-15 pm) of METHYL METHACRYLATE CROSSPOLYMER (COVABEAD LH 85 from SENSIENT) 3 D PHENOXYETHANOL 0.5 0.5 0.5 ALCOHOL 4 4 4 SPF VITRO 19.1 +/- 3.4 40.9 +/- 1.1 52.8 +/- 4.2 FILM SHINE (Gloss Unit - UB) 75.1 +/- 7 61.8 +/- 5.4 17.5 +/- 3.4 SOFTNESS ON APPLICATION (Score of 15 expert sensory panels; 1 = Not soft; 15 = Very soft) 5.1 +/- 0.2 2.9 +/- 0.2 12.7 +/- 1.3 SOFT FOCUS - BLURRY EFFECT (Score expert sensory panel out of 15; 1 = Bad software focus; 15 = Very good soft focus effect) 3.1 +/- 0.2 4.2 +/- 0.7 11.5 +/- 0.8

The protocol for preparing the compositions is as follows:

Preparation of phase A

The raw materials are carefully weighed beforehand using a balance (precision = 0.01 g), and are mixed using a Rayneri mixer.

Phase B

Phase B is introduced into phase A with stirring using a Rayneri mixer until a homogeneous preparation is obtained.

Addition of phase C îo Phase C is introduced into phase A + B with stirring using a Rayneri mixer.

Phase D

Phase D is introduced into phase A + B + C with Rayneri stirring.

In vitro SPF measurement

The sun protection factor (SPF) is determined according to the "in vitro" method described by B.L. Diffey in J. Soc. Cosmet. Chem. 40, 127-133, (1989).

The measurements were carried out using a UV-1000S spectrophotometer from the company Labsphere. Each composition is applied to a quartz slide, in the form of a homogeneous and regular deposit at the rate of 1.33 mg / cm2.

Gloss measurement

Gloss is measured using a BYK-Gardner gloss meter at an angle of 60 °. Each composition is spread over a contrast card. The thickness of the wet film obtained is 100 μm. The film is dried in an incubator at 37 ° C at 50% humidity for 24 hours. The measurement is made on the black part of the contrast card and reproduced 3 times per composition. The lower the value, the lower the gloss.

Evaluation of softness on application, and of the soft focus effect

The softness on application, and the soft focus effect (blur) are evaluated by a panel of sensory experts of 10 people. Each composition is applied to the forearm at a dose of 2 mg / cm2. The product is spread in circular movements until the product penetrates (about 30 seconds). The softness evaluation is carried out during the application. The soft focus effect is evaluated after 2 minutes of drying:

Softness on application: Softness is evaluated on a scale from 1 to 15 where 1 is a non-soft reference (rough and slowing skin) and 15 is a very soft reference.

Soft focus - Blurring effect: The soft focus effect is evaluated by eye after 2 minutes of drying on a scale from 1 to 15 where 1 is a reference with a low blurring effect and 15 is a very soft focus reference (effect blur).

It is found that the SPF is significantly improved when hollow hemispherical particles are added to the reference composition. In vitro SPF is improved by 176% by adding hemispherical polyacrylate particles while SPF is improved by only 114% with spherical particles.

In addition, these hemispherical particles make it possible to significantly reduce the shine, after application, and to provide softness on application and a soft-focus effect after application.

Examples 4 and 5:

The following two compositions are prepared:

Phase INCI EU name Example 4 (Invention) Example 5 (Invention) AT AQUA qs 100% 100% PROPYLENE GLYCOL 6 6 CAPRYLYL GLYCOL 0.1 0.1 HEXYLENE GLYCOL 1 1 DIPROPYLENE GLYCOL 10 10 BUTYLENE GLYCOL 4 4 GLYCERIN 3 3 BIS-PEG-18 METHYL ETHER DIMETHYL SILANE 1 1 POTASSIUM CETYL PHOSPHATE 1 1 B DICAPRYLYL CARBONATE (Cetiol CC- Cognis) 5 5 ISONONYL ISONONANOATE 3 3 C12-15 ALKYL BENZOATE 5 5 OCTOCRYLENE - 5 GLYCERYL STEARATE (and) PEG-100 STEARATE (Arlacel 165 - Croda) 2 2 CETYL ALCOHOL 1 1 VS TITANIUM DIOXIDE (and) SILICA (and) ALUMINUM HYDROXIDE (and) ALGINIC ACID (MT 100 AQ de TAYCA) 5 1 METHYLENE BIS-BENZOTRIAZOLYL TETRAMETHYLBUTYLPHENOL (TINOSORB M from BASF) 1 8 D Hollow hemispherical particles (5-15 pm) of METHYL METHACRYLATE CROSSPOLYMER (SEPIMAT H10 from SEPPIC) 1.5 4 E PHENOXYETHANOL 0.5 0.5 ALCOHOL 4 4

The protocol for preparing the compositions is as follows:

Preparation of phase A

The raw materials are carefully weighed beforehand using a balance (accuracy = 0.01 g), heated to 70 ° C using a heating plate, and are mixed using a Rayneri mixer.

Addition of phase B and emulsification îo Phase B is heated to 70 ° C. using a heating plate, then introduced into phase A. Emulsification is carried out using a rotor - Moritz type stator. After 10 minutes of emulsification, the preparation is brought to room temperature.

Addition of phase C

Phase C is introduced into phase A + B with stirring using a Rayneri mixer.

Addition of phase D

Phase D is introduced into phase A + B + C with stirring using a Rayneri mixer.

Phase E îo Phase E is introduced into phase A + B + C + D with Rayneri stirring.

Claims (29)

1. Aqueous composition comprising in a physiologically acceptable medium: a) at least one aqueous phase b) concave polyacrylate particles, in particular in the form of portions of hollow spheres; c) at least one insoluble organic or inorganic UV filter. 2 Composition according to claim 1, characterized in that the concave particles are in the form of portions of hollow spheres. 3. Composition according to any one of the preceding claims, characterized in that the concave particles are hollow hemispherical particles. 4. Composition according to any one of the preceding claims, characterized in that the particles of concave shape have an average diameter less than or equal to 30 pm, in particular ranging from 0.5 pm to 25 pm, preferably from 1 to 20 pm, more preferably ranging from 3 to 18 pm. 5. Composition according to any one of the preceding claims, characterized in that the concave particles comprise or consist of homopolymers or copolymers of (meth) acrylic acid or of their C1-C4 esters, preferably crosslinked. 6. Composition according to any one of the preceding claims, characterized in that the concave particles comprise or consist of homopolymers of C1-C4 alkyl acrylate or methacrylate, in particular methyl or ethyl acrylate or methacrylate, preferably crosslinked . 7. Composition according to any one of the preceding claims, characterized in that the concave particles are present in a content ranging from 0.1 to 15% by weight, preferably ranging from 0.25 to 10% by weight, and preferably ranging from 0.5 to 5% by weight relative to the total weight of the composition. 8 Composition according to any one of claims 1 to 7, in which the insoluble organic UV filter is in the form of particles of average size ranging from 0.01 to 5 μm and more preferably from 0.01 to 2 μm and more particularly from 0, 02 to 1.8 pm. 9. Composition according to any one of claims 1 to 8, in which the insoluble organic UV filter is chosen from organic UV filters of the oxalanilide type, of the triazine type, of the benzotriazole type; vinyl amide type; cinnamide type; of the type comprising one or more benzazole and / or benzofuran, benzothiophenene groups or of the indole type; of the aryl vinylene ketone type; of the phenylene bis-benzoxazinone derivative type, of the amide, sulfonamide or acrylonitrile carbamate derivative type or mixtures thereof. 10. Composition according to any one of claims 1 to 9, in which the insoluble organic UV filter is chosen from: (i) symmetrical triazines substituted by naphthalenyl groups or polyphenyl groups, in particular 2,4,6-tris (di-phenyl) -triazine and / or 2,4,6-tris (ter-phenyl) -triazine ; (ii) methylene bis- (hydroxyphenyl benzotriazole) compounds of formula (IV) below: in which the radicals T10 and Tu, identical or different, denote a C-i-C-is alkyl radical which may be substituted by one or more radicals chosen from C1-C4 alkyl, C5-C12 cycloalkyl or an aryl residue; (iii) and their mixtures. 11. Composition according to Claims 10, in which the methylene bis- (hydroxyphenyl benzotriazole) compound of formula (IV) is in the form of an aqueous dispersion of particles of average particle size which varies from 0.01 to 5 μm, and more preferably from 0 , 01 to 2 pm, and more particularly from 0.02 to 1.8 pm, in the presence of at least one surfactant of structure C _n H ₂ n + i O (C6Hi ₀ O5) _x H in which n is an integer from 8 to 16 and x is the average degree of polymerization of the unit (C6H10O5) and varies from 1.4 to 1.6. 12. Composition according to claims 10 or 11, in which the methylene bis- (hydroxyphenyl benzotriazole) compound of formula (IV) is in the form of an aqueous dispersion of particles of average size ranging from 0.02 to 2 μm, and more preferably from 0, 01 to 1.5 μm, and more particularly from 0.02 to 1 μm in the presence of at least one mono- (C8-C2o) alkyl-ester of polyglycerol having a degree of glycerol polymerization of at least 5. 13. Composition according to claims 12, in which the polyglycerol mono- (C8-C2o) alkyl ester is chosen from decaglyceryl caprate, decaglyceryl laurate, decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate , decaglyceryl isostearate, hexaglyceryl caprate, hexaglyceryl laurate, hexaglyceryl myristate, hexaglyceryl oleate, hexaglyceryl stearate, hexaglyceryl isostearate, pentaglyceryl caprate pentaglyceryl laurate, pentaglyceryl myristate, pentaglyceryl oleate, pentaglyceryl stearate, pentaglyceryl isostearate and more particularly among decaglyceryl caprate and decaglyceryl laurate. 14. Composition according to claim 12 or 13, in which the quantity of methylene bis- (hydroxyphenyl benzotriazole) compound of formula (IV) in the aqueous dispersion varies from 10 to 50% by weight, and more preferably from 30 to 50% by weight relative to the total weight of the dispersion. 15. Composition according to any one of claims 12 to 14, wherein the weight ratio of methylene compound bis- (hydroxyphenyl benzotriazole) / mono- (C8-C2o) polyglycerol alkylester varies from 0.05 to 0.5, and more preferably from 0.1 to 0.3. 16. Composition according to any one of claims 13 to 15, in which the methylene bis- (hydroxyphenyl benzotriazole) compound of formula (IV) in the form of an aqueous dispersion is the compound 2,2'-methylene-bis- [6- ( 2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] with the following structure: compound (a) 17. Composition according to any one of claims 1 to 16, in which the insoluble organic UV filter (s) of the invention are present at a concentration of active material ranging from 0.1 and 30% by weight, and more particularly from 0 , 5 to 20% by weight relative to the total weight of the composition. 18 Composition according to any one of claims 1 to 17, in which the insoluble inorganic UV filter is chosen from coated or uncoated metallic oxide pigments chosen in particular from oxides of titanium, zinc, iron, zirconium, cerium or their mixtures 19. Composition according to Claim 18, in which the metal oxide particles have an average elementary particle size of less than or equal to 0.5 μm, more preferably between 0.005 and 0.5 μm, and even more preferably between 0.01 and 0.2 pm, even better between 0.01 and 0.1 pm, and more particularly preferably between 0.015 and 0.05 pm. 20. Composition according to either of claims 18 or 19, in which the insoluble inorganic UV filter is chosen from particles of coated or uncoated titanium dioxide. 21. Composition according to any one of claims 1 to 20, wherein the inorganic insoluble UV filter (s) are present in contents ranging from 0.1% to 30% by weight, more particularly from 0.5 to 20% by weight , and in particular from 1 to 10%, by weight relative to the total weight of the composition. 22. Composition according to any one of the preceding claims, in which the total amount of the insoluble organic or inorganic UV filters varies from 0.1 to 30% by weight relative to the total weight of the composition, and preferably ranging from 0.5 at 20% by weight relative to the total weight of the composition. 23. Composition according to any one of the preceding claims, characterized in that the composition also comprises one or more water-soluble or liposoluble organic UV filters. 24. Composition according to any one of the preceding claims, further comprising at least one cosmetic adjuvant chosen from fatty substances, organic solvents, ionic or nonionic thickeners, hydrophilic or lipophilic, softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-foaming agents, perfumes, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, active agents, fillers, polymers, propellants, alkalizing agents or acidifiers. 25. Composition according to any one of the preceding claims, characterized in that it is in the form of aqueous dispersions, emulsions, simple or complex; in the form of an aqueous gel; in the form of a lotion, preferably in the form of an oil-in-water or water-in-oil emulsion. 26. Use of a composition according to any one of the preceding claims for the manufacture of products for the cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyebrows and / or scalp. 27. Use of a composition according to any one of the preceding claims for the manufacture of a care, makeup and / or sun protection product for the face and / or the body. 28. Use of concave polyacrylate particles, in particular in the form of portions of hollow spheres as defined in the preceding claims in an aqueous composition comprising in a physiologically acceptable medium at least one aqueous phase and at least one insoluble organic or inorganic UV filter, in order to increase the effectiveness of protection against UV radiation and in particular the sun protection factor (SPF). 29. Use of concave polyacrylate particles, in particular in the form of portions of hollow spheres as defined in the preceding claims in an aqueous composition comprising in a physiologically acceptable medium at least one aqueous phase and at least one filter UV insoluble organic or inorganic, in order to reduce the gloss after application.