FR3090329A1 - Composition comprising a UV filter, an anionic crosslinked hydrophilic polymer, a surfactant having an HLB less than or equal to 5 and a non-volatile alkane - Google Patents

Abstract

Composition comprising a UV filter, an anionic crosslinked hydrophilic polymer, a surfactant having an HLB less than or equal to 5 and a non-volatile alkane The present invention relates to a composition in the form of an oil-in-water emulsion comprising one or more UV filters , one or more hydrophilic anionic crosslinked polymers, one or more surfactants having an HLB less than or equal to 5, and one or more non-volatile alkanes with a viscosity of less than 20 mPa.s (at 20 ° C). The present invention also relates to a method of cosmetic treatment of the skin against UV radiation using said composition.

Description

Description

Title of the invention: Composition comprising a UV filter, an anionic crosslinked hydrophilic polymer, a surfactant having an HLB less than or equal to 5 and a non-volatile alkane

The present invention relates to a composition in the form of an oil-water emulsion comprising one or more UV filters, one or more hydrophilic anionic crosslinked polymers, one or more surfactants having an HLB less than or equal to 5, and one or more non-volatile alkanes preferably having a viscosity of less than 20 mPa.s (at 20 ° C)

The present invention also relates to a method of cosmetic treatment of the skin against UV radiation using said composition.

Light radiation with a wavelength between 280 and 400 nm allows browning of the human epidermis. Wavelength rays between 280 and 320 nm, called UVB rays, cause erythema and skin burns that can affect the development of tanning. Wavelength rays between 320 and 400 nm, called UVA rays, are capable of causing skin alteration, with in particular a loss of elasticity and the appearance of wrinkles, leading to premature aging.

UV rays must therefore be filtered. Currently, there are cosmetic compositions protecting the human epidermis containing UV filters, active with respect to the filtration of UVA and UVB radiation.

The conditions for using a solar composition are extremely varied and depend on the activities practiced by the consumer. The use near water for example on the beach, in the swimming pool is very frequent, which leads to applications as well on dry skin as on wet skin, in particular after the bathing.

However, on wet skin, certain products tend to dilute leading to a transformation of the texture and to a deterioration in the quality of the film formed on the skin, thus altering their protective properties for the skin.

Among the different textures of existing sunscreen compositions, the majority of them are difficult to apply on wet skin. Indeed, spreading the composition on wet skin induces a significant whitening effect, which is not very pleasant for the consumer. Obtaining a homogeneous appearance then requires a very long massage of the composition. This is particularly the case for milk textures widely appreciated elsewhere for their qualities of application on dry skin.

Currently, transparent alcoholic compositions, generally presented in a pump spray packaging, correspond to the most compatible compositions with application on wet skin. The whitening effect on the skin and the application are acceptable but do not however correspond to good qualities of use on wet skin. Their sun protection properties are not entirely satisfactory.

Furthermore, these compositions include substantial alcohol contents and therefore have many drawbacks. For example, they cannot be used on the face and can cause a drying effect on the skin.

Thus, there is a real need to make available a solar composition that does not have the drawbacks mentioned above, that is to say a milk-type solar composition, which is stable, compatible with application on wet skin, which has a high level of sun protection efficiency (SPF) in vivo and which has good cosmetic properties when applied to dry skin and also on wet skin.

The Applicant has surprisingly discovered that a composition in the form of an oil-in-water emulsion comprising one or more UV filters, one or more hydrophilic anionic crosslinked polymers, one or more surfactants having a lower or equal HLB to 5, and one or more non-volatile alkanes of low viscosity, made it possible to achieve the objectives set out above; in particular to obtain a high SPF filtering composition, having excellent compatibility with an application to wet skin which has good cosmetic properties when applied to wet skin, in particular a non-shiny, non-greasy and non-sticky finish.

The present invention which relates in particular to a composition in the form of an oil-in-water emulsion comprising:

An oily phase, dispersed in a continuous aqueous phase,

One or more UV filters,

One or more anionic crosslinked hydrophilic polymers,

One or more surfactants having an HLB less than or equal to 5, and

One or more non-volatile alkanes with a viscosity of less than 20 mPa.s (at 20 ° C).

Unlike conventional sunscreen compositions, the composition of the invention makes it possible to combine a satisfactory application on wet skin with high sun protection.

Indeed, the composition of the invention has good wear properties. It spreads easily and allows a homogeneous application without the appearance of a whitish film on the skin.

The composition also makes it possible to filter UV rays at a high SPF, consequently resulting in better protection of the skin.

The composition of the invention is also stable over time.

Furthermore, the composition of the invention has good cosmetic properties, in particular in terms of non-shiny, non-greasy and non-sticky finish on wet skin as on dry skin.

The present invention also relates to a method of cosmetic treatment of the skin, in particular human skin, against UV radiation consisting in applying to said skin the composition according to the invention.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.

In what follows, and unless otherwise indicated, the limits of a range of values are included in this area, in particular in the expressions "between" and "ranging from ... to .. . "

Furthermore, the expressions “at least one” and “at least” used in the present description are respectively equivalent to the expressions “one or more” and “greater than or equal”.

By "(meth) acrylic" and "(meth) acrylate" within the meaning of the present application, is meant respectively acrylic or methacrylic and acrylate or methacrylate.

By “high SPL” within the meaning of the present application, is meant a sun protection factor (SPL) in vitro which can reach a value of at least 30, and preferably at least 50. The level of protection solar energy is defined by the sun protection factor (SPE) which is determined according to the "in vitro" method described by BL Diffey in J. Soc. Cosmet. Chem. 40, 127-133, (1989).

By “stable over time” according to the present invention, is meant a composition which after 1 month, preferably after 2 months, of storage at a temperature ranging from 4 to 45 ° C. exhibits no macroscopic change in color, odor, viscosity, or variation in pH, as well as no variation in microscopic appearance.

By "good compatibility on wet skin" within the meaning of the present invention is meant that the application of the composition at a rate of ² mg.cm ² , on a substitute substrate of previously wet skin, a film is obtained homogeneous transparent to the naked eye.

By non-volatile alkane is meant a hydrocarbon cosmetic oil, liquid at room temperature, in particular having a vapor pressure at 20 ° C of less than 0.01 kPa, according to the definition of a Volatile Organic Compound (VOC) of Article 2 of Directive 1999/13 / EC of the European Council of March 11, 1992: "Any organic compound having a vapor pressure of 0.01 kPa or more at a temperature of 293.15 K".

UV filters

The composition according to the present invention comprises one or more UV filters.

According to a preferred embodiment, the UV filter or filters are included in the oily phase of the composition.

According to the present invention, the expression "UV filters" is equivalent to the expression "photoprotective agent".

More particularly, the UV filter or filters suitable for the present invention are chosen from water-soluble organic UV filters, liposoluble organic UV filters, insoluble organic UV filters, inorganic UV filters, and mixtures thereof.

Preferably, the UV filter (s) are chosen from water-soluble organic UV filters, liposoluble organic UV filters, insoluble organic UV filters, and mixtures thereof.

More preferably, the UV filter or filters are chosen from water-soluble organic UV filters, liposoluble organic UV filters, and their mixtures, and even more preferably from liposoluble organic UV filters, and their mixtures.

By water-soluble organic UV filter is meant any organic compound filtering UV radiation capable of being completely dissolved in the molecular state or miscible in a liquid aqueous phase or else of being dissolved in colloidal form (for example in micellar form ) in a liquid aqueous phase.

By liposoluble organic UV filter is meant any cosmetic or dermatological organic compound filtering UV radiation capable of being completely dissolved in the molecular state or miscible in an oily phase or else of being dissolved in colloidal form (for example under micellar form) in an oily phase.

By “insoluble organic UV filter” is meant any cosmetic or dermatological organic compound filtering 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 composition according to the present invention may comprise one or more water-soluble organic UV filters chosen from water-soluble organic UVA filters, water-soluble organic UVB filters and their mixtures.

By water-soluble organic UVA filter is meant any organic compound filtering UVA radiation in the range of wavelengths 320 to 400 nm capable of being completely dissolved in the molecular state or miscible in a liquid aqueous phase or else d be solubilized in colloidal form (for example in micellar form) in a liquid aqueous phase.

[0044]

[0045]

Among the water-soluble organic UVA filters that can be used according to the present invention, mention may be made of benzene 1,4-di (3-methylidene-10-camphosulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) and its various salts, described in particular in patent applications FR-A-2528420 and FR-A-2639347.

These filters correspond to the following general formula (I):

[0046]

[0047]

[0048]

In which, F denotes a hydrogen atom, an alkali metal or else an NH (Ri) ₃ ⁺ radical in which the R _H radicals which may be identical or different, denote a hydrogen atom, an alkyl radical or C ₁ -C ₄ hydroxyalkyl or else a group M ^{n + /} n, Mn + denoting a polyvalent metallic cation in which n is equal to 2 or 3 or 4, Mn + preferably denoting a metallic cation chosen from Ca ²⁺ , Zn ²⁺ , Mg ²⁺ , Ba ²⁺ , Al ³⁺ and Zr ⁴⁺ . It is understood that the compounds of formula (I) above can give rise to the cis-trans isomer around one or more double bond (s) and that all the isomers fall within the scope of the present invention.

Among the hydrophilic organic UVA filters which can be used according to the present invention, mention may also be made of compounds comprising at least two benzoazolyl groups with sulphonic groups such as those described in patent application EP-A-0669323.

They are described and prepared according to the syntheses indicated in US Pat. No. 2,463,264 as well as in patent application EP-A-0669323.

The compounds comprising at least two benzoazolyl groups in accordance with the invention correspond to the following general formula (II):

in which,

- Z represents an organic valence residue (1 + n) comprising one or more double bonds placed in such a way that it completes the system of double bonds of at least two benzoazolyl groups as defined inside the

Hooks to form a fully conjugated assembly;

- X 'denotes S, O or NR ⁶

- R ¹ denotes a hydrogen atom, a C 1 to C ₈ alkyl, a C ₄ to C ₄ alkoxy, a C ₅ to C ₁₅ aryl, a C ₂ to C ₈ acyloxy, an SO ₃ Y group or COOY;

- the radicals R ² , R ³ , R ⁴ and R ⁵ , identical or different, denote a nitro group or a radical R ¹ ;

- R ⁶ denotes a hydrogen atom, an alkyl C l -C ₄ hydroxyalkyl or C l -C _4;

- Y denotes hydrogen, Li, Na, K, NH ₄ , 1 / 2Ca, 1 / 2Mg, 1 / 3Al or a cation resulting from the neutralization of a free acid group with an organic nitrogen base;

- m is 0 or 1;

- n is a number from 2 to 6;

- 1 is a number from 1 to 4;

- provided that 1 + n does not exceed the value 6.

Among these compounds, very particularly preferred is the acid 1,4-bis-benzimidazolyl-phenylen-3,3 ', 5,5'-tetrasulfonic (INCI name: Disodium Phenyl Dibenzimidazole Tetra-sulfonate) (compound (d) ) or one of its salts with the following structure, sold in particular under the name NEOHELIOPAN AP® by the company Symrise:

Among the water-soluble organic UVA filters which can be used according to the present invention, mention may also be made of benzophenone compounds comprising at least one sulfonic acid function, such as for example the following compounds:

Benzophenone-4, sold in particular by the company BASF under the name Uvinul MS40®

II O

Benzophenone-5 structure

Benzophenone-9, sold in particular by the company BASF under the name Uvinul DS49®

Among the water-soluble organic UVA filters, use will be made more particularly of benzene l, 4-di (3-methylidene-10-camphosulfonic acid) and its various salts (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) manufactured by the company CHIMEX under the trade name MEXORYL SX®.

The water-soluble organic UVB filters which can be used according to the present invention are in particular chosen from water-soluble cinnamic derivatives such as ferulic acid or 3-methoxy-4-hydroxycmnamic acid; water-soluble benzylidene camphor compounds; water-soluble phenylbenzimidazole compounds; water-soluble p-aminobenzoic compounds (PABA); water-soluble salicylic compounds, and mixtures thereof.

As examples of water-soluble organic UVB filters, mention may be made of the following compounds, designated by their name INCI:

Para-aminobenzoic compounds, such as PABA, PEG-25 PABA sold in particular under the name "UVINUL P 25®" by BASF;

salicylic compounds, such as dipropylene glycol salicylate sold in particular under the name "DIPSAL®" by SCHER, and TEA Salicylate, sold in particular under the name "NEO HELIOPAN TS®" by Symrise;

benzylidene camphor compounds, such as the benzylidene camphor sulfonic acid sold in particular under the name "MEXORYL SL®" by CHIMEX, and the camphor benzalkonium methosulfate sold in particular under the name "MEXORYL SO®" by CHIMEX;

phenyl benzimidazole compounds, such as phenylbenzimidazole sulfonic acid sold in particular under the trade name "EUSOLEX 232®" by MERCK.

Use will be made more particularly of the phenylbenzimidazole sulfonic acid filter sold in particular under the trade name "EUSOLEX 232®" by MERCK.

The composition according to the present invention may comprise one or more liposoluble organic UV filters, chosen from liposoluble organic UVA filters, liposoluble organic UVB filters and their mixtures.

The fat-soluble organic UV filters are in particular chosen from cinnamic derivatives; anthranilates; salicylic derivatives, dibenzoylmethane derivatives, camphor derivatives; benzophenone derivatives; derivatives of, -diphenylacrylate; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives such as those cited in US Pat. No. 5,624,663; imidazolines; p-aminobenzoic acid derivatives (PABA); benzoxazole derivatives such as those described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844; filter polymers and filter silicones such as those described in particular in application WO-93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE19855649; 4,4-diarylbutadienes such as those described in applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EPI 133980 and EP133981; merocyanine derivatives and merocyanines such as those described in patent US4195999, application W02004 / 006878, applications W02008 / 090066, WO2011113718, W02009027258, and documents IP COM JOURNAL N ° 000179675D published on February 23, 2009, IP COM JOURNAL N ° 000182396D published on April 29, 2009, IP COM JOURNAL N ° 000189542D published on November 12, 2009, IP COM Journal N ° IPCOM000011179D published on 04/03/2004; and their mixtures.

As examples of complementary organic UV filters, mention may be made of those designated below under their INCI name:

Dibenzoylmethane derivatives, such as butyl methoxy dibenzoylmethane or avobenzone, offered for sale in particular under the trade name of PARSOL 1789 ”by the company DSM NUTRITIONAL PRODUCTS;

Derivatives of para-aminobenzoic acid, such as ethyl PABA, ethyl Dihydroxypropyl PABA, ethylhexyl Dimethyl PABA sold in particular under the name "ESCALOL 507" by ISP;

Salicylic derivatives, such as 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;

Cinnamic derivatives, such as ethylhexyl methoxycinnamate sold in particular under the trade name "PARSOL MCX" by DSM NUTRITIONAL PRODUCTS,

Opropisopropyl methoxy cinnamate, Γisoamyl methoxy cinnamate sold in particular under the trade name “NEO HELIOPAN E 1000” by SYMRISE, cinoxate, diisopropyl methylcinnamate;

Derivatives of, -diphenylacrylate, such as octocrylene sold in particular under the trade name "UVINUL N539" by BASF, etocrylene, sold in particular under the trade name "UVINUL N35" by BASF;

Benzophenone derivatives, such as benzophenone-1 sold in particular under the trade name "UVINUL 400" by BASF, benzophenone-2 sold in particular under the trade name "UVINUL D50" by BASF, benzophenone-3 or oxybenzone, sold in particular under the trade name "UVINUL M40" by BASF, benzophenone-6 sold in particular under the trade name "Helisorb 11" by Norquay, benzophenone-8 sold in particular under the trade name "Spectra-Sorb UV-24" by American Cyanamid, benzophenone-12, 2- (4-diethylamino-2-hydroxybenzoyl) -n-hexyl benzoate sold in particular under the trade name "UVINUL A +" such as "UVINUL A + GRANULAR" or in the form of a mixture with octylmethoxycinnamate in particular under the trade name * UVINUL A + B "by BASF;

Benzylidene camphor derivatives, such as 3-benzylidene camphor sold in particular under the name "MEXORYL SD" by CHIMEX, 4-methylbenzylidene camphor sold in particular under the name "EUSOLEX 6300" by MERCK, the polyacrylamidomethyl benzylidene camphor sold in particular under the name "MEXORYL SW" by CHIMEX;

Phenyl benzotriazole derivatives, such as Drometrizole Trisiloxane sold in particular under the name "Silatrizole" by RHODIA CHIMIE;

Triazine derivatives, such as bis-ethylhexyloxyphenol methoxyphenyl triazine sold in particular under the trade name "TINOSORB S" by BASF, ethylhexyl triazone sold in particular under the trade name "UVINUL T150" by BASF, diethylhexyl butamido triazone sold in particular under the trade name "UVASORB HEB" by SIGMA 3V, triazine silicones substituted by two aminobenzoate groups as described as patent EP0841341 in particular 2,4-bis- (n-butyl 4'-aminobenzahnalonate) -6- [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyloxy] disiloxanyl} propyl) amino] -s-triazine;

- anthranilic derivatives, such as menthyl anthranilate sold in particular under the commercial name “NEO HELIOPAN MA” by SYMRISE;

- imidazoline derivatives, such as ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate;

- Benzalmalonate derivatives, such as di-neopentyl 4’-methoxybenzalmalonate, polyorganosiloxane with benzalmalonate functions such as Polysilicone-15 sold in particular under the trade name "PARSOL SLX" by DSM;

- 4,4-diarylbutadiene derivatives, such as 1,1-dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene;

- Benzoxazole derivatives, such as

2,4-bis- [5-l (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -immo] -6- (2-ethylhexyl) -imin ol, 3,5-triazine sold especially under the name d 'Uvasorb K2A by Sigma 3V;

- lipophilic merocyanine derivatives, such as roctyl-5-N, N-diethylamino-2-phenysulfonyl-2,4-pentadienoate.

Preferably, the liposoluble organic filter or filters are chosen from butyl methoxy dibenzoylmethane, ethylhexyl methoxycinnamate, ethylhexyl salicylate, homosalate, butyl methoxydibenzoylmethane, octocrylene, benzophenone-3, 2- (4-diethylamino-2-hydroxybenzoyl) -n-hexyl benzoate, 4-methylbenzylidene camphor, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, diethylhexyl butamido triazone, 2,4,6-tris (4 ' dineopentyl amino benzalmalonate) -s-triazine, 2,4,6-tris- (4'-ammo diisobutyl benzalmalonate) -striazine, 2,4-bis (4'-dineopentyl aminobenzalmalonate) -6- ( N-butyl 4'-ammobenzoate) -s-triazine, drometrizole trisiloxane, polysilicone-15, 1,1-dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene, 2,4 -bis- [5-l (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -immo] -6- (2-ethylhexyl) -imin ol, 3,5-triazine, and mixtures thereof.

More preferably, the liposoluble organic filter (s) are chosen from homosalate, ethylhexyl salicylate, drometrizole trisiloxane, bisethylhexyloxyphenol methoxyphenyl triazine, octocrylene, butyl methoxydibenzoylmethane, ethylene mixtures and ethylene.

Among these liposoluble organic UV filters, some of them are liquid at room temperature (20-25 ° C) under 1 atmosphere, while others are in a solid form (powder or granules) which is soluble. in an oil.

The composition according to the present invention may comprise one or more insoluble organic UV filters, chosen from insoluble organic UVA filters, insoluble organic UVB filters and their mixtures.

The insoluble organic UV filters according to the invention preferably have an average particle size which varies from 0.01 to 5 μιη and more preferably from 0.01 to 2 μιη and more particularly from 0.020 to 2 μιη.

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 grinding process of an insoluble organic UV filter in the form of coarse particles in the presence of an appropriate surfactant making it possible to improve the dispersion of the particles thus obtained in cosmetic formulations.

An example of the micronization process of 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 _2n + i 0 (C ₆ Hio0 ₅ ) _x H in which n is an integer from 8 to ₅ , are used as surfactants for the grinding of said filters. 16 and x is the average degree of polymerization of the unit (C ₆ Hio0 ₅ ) and varies from 1.4 to 1.6. They can be chosen from C1-C12 esters of a compound of structure C _n H _2n + i O (C ₆ H _m O0 _x H and more precisely an ester obtained by reaction of a C1-C12 carboxylic acid such as formic, acetic, propionic, butyric, sulfosuccinic, citric or tartaric acid with one or more free OH functions on the glucoside unit (C ₆ Hio0 ₅ ). One can cite as alkylpolyglucoside in particular decylglucoside.

Said surfactants are used in general 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 bisbenzoxazinone derivative type, of the amide, sulfonamide or acrylonitrile carbamate derivative type or mixtures thereof.

In the sense that it is used in the present invention, the term benzazole includes both benzothiazoles, benzoxazoles and benzimidazoles.

Among the UV filters of the oxalanilide type in accordance with the invention, mention may be made of those corresponding to the following formula (III):

[0093]

[0094]

(HI) wherein T _b T _'b T ₂ and T' ₂ are, same or different, an alkyl radical -C ₈ alkoxy or C l -C _8. These compounds are described in patent application WO95 / 22959.

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

C (CH ₃ ) ₃

[0095]

[0096]

[0097]

[0098]

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 (IV):

P t N \

T ₄ 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, C _r Ci ₈ alkyl or C _r Ci ₈ alkoxy, C _r Ci ₈ carboxyalkyl, C ₅ -C ₈ cycloalkyl, a methylbenzylidenecamphor group, a group (CH = CH) _n (CO) -OT ₆ , with T ₆ either C _r Ci ₈ alkyl or cinnamyl.

These compounds are described in WO 97/03642, GB 2286774, EP-743309, WO 98/22447, and 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 EPA-0790243 (forming an integral part of the content of the description).

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

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

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

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

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

Among the UV filters of the triazine type in accordance with the invention, mention may also be made of insoluble s-triazine derivatives 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'-benzotriazol-2-yl-2'-hydroxy-5'-methyl) phenylamino] -s-triazine, - 2,4,6-tris [(3'- benzotriazol-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 Derivatives" IP.COM Journal, IP.COM 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, and W02006 / 034985.

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 (V) 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 to C alkyl radical _[8 ; T ₈ and T ₉ , identical or different, denote a C 1 to C ₈ alkyl radical optionally substituted by a phenyl.

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

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 US Pat. Nos. 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'-be nzoyl] diphenylmethane sold in particular under the name MIXXIM PB 30® by the company FAIRMOUNT CHEMICAL of 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:

In which the radicals T _w and Tu, which are identical or different, denote a C 1 to C alkyl radical _{[8 which} can be substituted by one or more radicals chosen from C 1 to C ₄ alkyl, C ₅ to C cycloalkyl ₂ or an aryl residue. These compounds are known per se and described in applications 5 US 5 237 071, 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 (VI) defined above: the C1 to C alkyl groups _[8 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; cycloalkyl groups, C ₅ to Ci ₂ are for example cyclopentyl, cyclohexyl, cyclooctyl; aryl groups are, for example phenyl, benzyl.

Among the compounds of formula (VI), mention may be made of those of the following structure: [YES]

[0112]

[0113]

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 especially sold under the trade name MIXXIM BB / 200® by the company EAIRMOUNT CHEMICAL.

The nomenclature compound (c)

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 the company EAIRMOUNT CHEMICAL.

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

T ₁₂ - (Y) _r -C (= O) -C (T ₁₃ ) = C (T ₁₄ ) -N (T ₁₅ ) (T ₁₆ ) (VII)

[0118] wherein T ₁₂ is alkyl to C _[8, preferably C, to C ₅ or a phenyl group optionally substituted with one, two or three radicals chosen from OH, C to C _[8 alkoxy, Ci to C _8, or -C (= O) -OTi ₇ where T _[7 is alkyl to C _[8; T _[3 , T _[4 , Ti ₅ and T _[6, identical or different, denote a C 1 to C _[8 , preferably C 1 to C ₅ alkyl radical or a hydrogen atom; Y is N or O and r is 0 or 1.

Among these compounds, there may be mentioned more particularly 4-octylamino-3-penten-2-one; ethyl-3-octylamino-2-butenoate; 3-octylamino-1-phenyl-2-buten-1-one and 3-dodecylamino-1-phenyl-2-buten-1-one.

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 (VIII) z = \ Il /

T _{: $} O— (y // - CH ^{= :: =} CH ”~~ C” ~~ N \

V_U T '23

[0121] wherein OT _[8 is hydroxy or alkoxy radical C l -C _4, preferably methoxy or ethoxy; Τ _[9 is hydrogen, alkyl to C _4, preferably methyl or ethyl; T ₂₀ 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 to C alkyl _[8 , C1 to C ₈ alkoxy , or a group -C (= O) -OT ₂ i where T _{2 [} is a C1 to C alkyl _[8 and more preferably T _{2 [} 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,

[0125] each of R independently represents an OH group, a halogen atom, an alkyl group -C ₈ linear or branched, optionally containing a silicon atom, or an alkoxy group -C ₈ linear or branched,

Each of the numbers m is independently 0, 1 or 2,

N represents an integer ranging from 1 to 4,

P is equal to 0 or 1,

Each of the numbers q is independently equal to 0 or 1,

[0130] each R ₂ is independently hydrogen, benzyl or alkyl group -C ₈ linear or branched, optionally containing a silicon atom,

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

wherein, each of R ₃ independently represents a halogen atom or an alkyl or alkoxy group CIA -C ₄ linear or branched, or hydroxy, R ₄ represents a hydrogen atom or an alkyl group -C ₄ , linear or branched, c = 0-4, d = 0-3, e = 0oul, etf = 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 (IX) of the family of 2-arylbenzazoles, mention may be made of 2-benzoxazol-2-yl-4-methylphenol, 2- (1H-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 (IX) 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- (1H-benzimidazol-2-yl) - benzothiazole, 2- (1H-benzimidazol-2-yl) -benzoxazole and N, N'-dimethyl-2,2'-bis-benzimidazole, these compounds being able to be prepared according to the procedures described in US Patents 5,961 960 and US 2,463,264.

As examples of preferred compounds of formula (IX) of the family of phenylenebenzazoles, mention will be made of 1,4-phenylene-bis- (2-benzoxazolyl), 1,4-phenylene-bis- (2 -benzimidazolyle), 1,3-phenylene-bis- (2-benzoxazolyl), 1,2-phenylene-bis- (2-benzoxazolyl), 1,2-phenylene-bis- (benzimidazolyl), 4-phenylene-bis- (N-2-ethylhexyl-2-benzimidazolyl) and 1,4-phenylene-bis- (Ntrimethylsilylmethyl-2-benzimidazolyl), these compounds being able to be prepared according to the procedures described in US patent 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 (IX) of the family of benzofuranyl-benzoxazoles, mention may 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 (X), mention may be made, for example, of 2,6-diphenyl-1,7-dihydro-benzo [1,2-d; 4,5-d '] - corresponding di-imidazole 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 (XI), mention may be made of

5,5'-bis - [(2-phenyl) -benzimidazole] of formula:

The preparation of which is described in J. Chim. Phys., 64, 1602 (1967).

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

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

(Xiî)

In which,

[0146] n ’= 1 or 2,

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

\ © 1 °),

-V 5 -4 ywfcO- 4 [V {Y ~ y_j ⁼ \ \ = Α (Λ) - 'KA ^ = —Ç \ y (e') d'i (g ·) (h ')

[0148] wherein, each R ₈ independently represents an OH group, a halogen atom, an alkyl group -C ₆ linear or branched and optionally containing a silicon atom, an alkoxy group -C ₆ , linear or branched and optionally containing a silicon atom, a C1 to C alkoxycarbonyl group ₅ , linear or branched, or a C1 to C ₆ alkylsulfonamide group, linear or branched and optionally containing a silicon atom or an amino acid function ,

P ’represents an integer ranging from 0 to 4,

That represents 0 or 1,

R ₅ represents hydrogen or an OH group,

[0152] R ₆ is hydrogen, alkyl to C _6, linear or branched and optionally containing a silicon atom, a cyano group, an alkylsulfonyl group to C _6, a phenylsulfonyl group,

R ₇ represents a C 1 to C ₆ alkyl group, linear or branched and optionally containing a silicon atom or a phenyl group which can form a bicycle and optionally substituted by one or two radicals R ₄ ,

Or R ₆ and R ₇ together form a monocyclic, bicyclic or tricylic C ₂ to Ci ₀ hydrocarbon residue, optionally interrupted by one or more atoms of nitrogen, sulfur and oxygen and which may contain another carbonyl, and optionally substituted with a alkylsulfonamide group to C ₈ linear or branched, and optionally containing a silicon atom or an amino acid function; provided that when n '= l, R ₆ and R ₇ do not form a camphor nucleus.

By way of examples of compounds of formula (XII) in which n ′ = l, insoluble, filtering UV radiation, having an average particle size of between 10 nm and 5 nm, the following families can be mentioned:

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

[0157]

[0158]

[0159]

[0160]

OMe

- Benzylidene cineole type compounds such as those described in the article by E.

Mariani et al, 16th IFSCC Congress, New York (1990)) such as l, 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-chromèn-4-one:

OMe

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

[0162] O

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

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

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:

MeO

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:

- Benzylidene tetralone type compounds such as those described in application JP 04 134 043 such as

2- (4-methoxy-benzylidene) -3,4-dihydro-2H-naphthalen- 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:

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

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

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

- 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-dimethyl-pyrimidine-2,4,6-trione:

o

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

- Benzylidene imidazolone type compounds such as

5- (4-methoxybenzylidene) -2-phenyl-3,5-dihydro-imidazol-4-one:

[0186]

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

[0188]

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:

OH O OH

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- {3-methylidenebicyclo [2.2.1] heptan-2-one] :

X

The 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-trimethyl-bicyclo [2.2.1] heptan-2-one}:

[0194] - compounds of the phenylene bis methylidene camphor sulfonamide type such as those described in document FR2 529 887 such as 1,4-phenylene-bis-3,3'-methylidene camphor-10,10'-ethyl sulfonamide or 2-ethylhexyl:

or

- 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}:

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

The compounds of the phenylene bis alkylene ketone type such as those described in application JP 04 134 041 such as 1,4-phenylene-bis- (4,4-dimethyl-pent-1-en-3-one) :

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

- Phenylene bis methylidene quinuclidinone type compounds 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 (XIII), the following families can be mentioned:

- Compounds of the bis benzylidene cycloalkanone type such as

2,5-dibenzylidene-cyclopentanone:

[0202] - 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:

O 'Αγ' ·· ’'O' 'Af

Ôfefe OMe

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

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

with R representing a divalent aromatic residue chosen from the following formulas (e) to (h):

in which,

[0205] each R ₉ independently represents an OH group, a halogen atom, an alkyl group -C ₆ linear or branched and optionally containing a silicon atom, an alkoxy group -C ₆ linear or branched and optionally containing a silicon atom, an alkoxycarbonyl group to C ₅ linear or branched alkylsulfonamide group or a C, to C ₆ linear or branched and optionally containing a silicon atom or an amino acid function,

P ”represents an integer ranging from 0 to 4,

Q ”represents 0 or 1.

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

[0209] - 2,2’-p-phenylene bis (3, l-benzoxazin-4-one), sold in particular under the trade name of CYASORB UV-3638® by the company CYTEC,

[0210] - 2,2 ’- (4,4’-biphenylene) bis (3, l-benzoxazin-4-one),

[0211] - 2,2 ′ - (2,6-naphthylene) bis (3, l-benzoxazin-4-one).

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 (XV):

(XV)

NC _? γ y / 7--4 4— NH — NH — 4 4 y - //% 44

In which,

[0214] Rio is alkyl to C ₈ linear or branched,

[0215] n "’ is 0, 1 or 2,

- X ₂ represents a divalent radical of formula - (C = O) -Rn- (C = O) -, -SO ₂ -Rn-SO ₂ - or

- (C = O) -O-Rn-O- (C = O) -,

[0217] - Y represents a radical - (C = O) -R _[2 or -SO ₂ R _[3 ,

- Ru represents a single bond or a divalent C 1 to C ₃₀ alkylene or C ₃ to C ₃₀ alkenylene radical, linear or branched, which may carry one or more hydroxyl substituents and which may contain, in the carbon chain, one or several heteroatoms chosen from oxygen, nitrogen and silicon atoms,

[0219] - R _[2 represents a radical -OR _[4 or -NHR _[4 ,

[0220] - R ₃ represents an alkyl radical -C ₃₀ linear or branched or a phenyl ring unsubstituted or substituted by alkyl or alkoxy radicals to C _4,

[0221] - R | ₄ represents a linear or branched C ₁ -C ₃₀ alkyl or C ₃ -C ₃₀ alkenyl radical which may carry one or more hydroxyl substituents and which may contain, in the carbon chain, one or more heteroatoms chosen from oxygen atoms , nitrogen and silicon.

Although in formula (XV) above, only the isomers are represented in which the cyano substituent is in the cis position relative to the paraamino-phenyl substituent, 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-ammo-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:

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 organic sulfonic or carboxylic filters 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 UV-A and / or UV-B organic filters as described in patent applications WO93 / 10753, WO93 / 11095 and WO95 / 05150.

Among the insoluble organic UV filters, mention may also be made of compound 1, Γ- (1,4-piperazinediyl) bis [1 - [2- [4- (diethylamino) -2-hydroxybenzoyl] phenyl] -methan one (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 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 W02004 / 085412 (see compounds 6 and 9) or the document "Symetrical Triazine Derivatives" 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 listed 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) obtainable 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 as well as Phenylene bisdipheny Itriazine);

(Ii) the methylene bis- (hydroxyphenyl benzotriazole) compounds of formula (XVI) below:

te 11

In which the radicals Τ _[0 and Tu, identical or different, denote a C 1 to C alkyl radical _{[8 which} may be substituted by one or more radicals chosen from C 1 to C ₄ alkyl, C ₅ to C cycloalkyl ₂ 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 (XVI) are in the form of an aqueous dispersion of particles having an average particle size which varies from 0.01 to 5 μιη and more preferably from 0.01 to 2 μιη and more particularly from 0.020 to 2 μιη with at least one surfactant of structure C _n H _{2n +} i O (C ₆ Hi ₀ O ₅ ) _x H in which n is an integer from 8 to 16 and x is the average degree of polymerization of the unit (C ₆ Hi ₀ O ₅ ) and varies from 1.4 to 1.6. 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 dispersion aqueous preferably ranges 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 (XVI) may be in the form of an aqueous dispersion of particles having an average particle size which varies from 0.02 to 2 μιη and more preferably from 0.01 to 1.5 μιη and more particularly from 0.02 to 1 μιη in the presence of at least one mono- (C ₈ -C ₂₀ ) 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 monoesters (C ₈ -C ₂₀ ) alkylesters, there may be mentioned decaglyceryl caprate, decaglyceryl laurate, decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate, l decaglyceryl isostearate, hexaglyceryl caprate, hexaglyceryl laurate, hexaglyceryl myristate, hexaglyceryl oleate, hexaglyceryl stearate, hexaglyceryl isostearate, pentaglyceryl caprate pentaglyceryl, pentaglyceryl myristate, pentaglyceryl oleate, pentaglyceryl stearate, pentaglyceryl isostearate.

We will use more particularly:

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 the company Nikko Chemicals Co. Ltd, RYOTO-Polyglycerylester L-10D® and L-7D® by the company 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. Etd., NIKKOE 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 the company Nikko Chemicals Co. Ltd, RYOTO-Polyglycerylester S-15D® by the company 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 OU Industrial Co. Ltd., UNIGLY GL-106 ® by Nippon Oil & Fats Co. Ltd.,

[0242] 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 OU Industrial Co . Ltd., UNIGLY GL-106 by Nippon Oil & Fats Co. Ltd.,

[0243] 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, [0245] pentaglyceryl caprate such as the products sold under the trade names following SUNSOFT A10E®, by 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.,

[0247] pentaglyceryl myristate such as the products sold under the following commercial names SUNSOFT A14E®, SUNSOFT A141E®, by the company Taiyo Kagaku Co. Ltd.,

Pentaglyceryl oleate such as the products sold under the following trade names SUNSOFT A17E®, SUNSOFT A171E®, by the company Taiyo Kagaku Co. Ltd., [0249] pentaglyceryl stearate such as the products sold under the following trade names SUNSOFT A18E®, SUNSOFT A181E®, by 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 mono- (C ₈ -C ₂ o) alkyl esters of polyglycerol having a degree of glycerol polymerization of at least 5 and 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, and pentaglyceryl stearate. As examples of polyglycerol mono- (C ₈ -C ₂ o) alkylesters having a degree of glycerol polymerization of at least 5 and having an HLB greater than or equal to 15, mention may be made of decaglyceryl caprate, and laurate decaglyceryl.

The amount of methylene bis- (hydroxyphenyl benzotriazole) compound of formula (XVI) 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 dispersion.

Preferably, the weight ratio between the amount of the methylene bis- (hydroxyphenyl benzotriazole) compound and the amount of the mono- (C ₈ -C ₂₀ ) polyglycerol alkyl ester varies from 0.05 to 0.5, and more preferably from 0.1 to 0.3.

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

[0254]

compound (a)

[0255] 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).

Preferably, the insoluble organic UV filter is methylene bis-benzotriazolyl tetramethylbutylphenol.

The composition according to the present invention may comprise one or more inorganic UV filters, chosen from inorganic UVA filters, inorganic UVB filters and their mixtures.

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 μιη 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.

By "elementary average size" according to the present invention means the size of non-aggregated particles.

They can be chosen in particular from oxides of titanium, zinc, iron, zirconium, cerium and 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 in particular of the products sold by the companies SACHTLEBEN PIGMENTS, TAYCA, MERCK AND DEGUSSA.

The metallic oxide pigments can be coated or uncoated.

The coated pigments are pigments which have undergone one or more surface treatments of chemical, electronic, mechanochemical and / or mechanical nature with compounds such as amino acids, beeswax, fatty acids, alcohols fatty, 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: [0265] - silica, such as the product SUNVEIL from the company IKEDA;

- of silica and iron oxide, such as the product SUNVEIL F from the company IKEDA;

[0267] - silica and alumina, such as the MICROTITANIUM DIOXIDE MT products

500 SA and MICROTITANIUM DIOXIDE MT 100 SA from the company TAYCA, and TIOVEIL from the company TIOXIDE;

- of 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 ^

[0269] - alumina and aluminum stearate, such as the MICROTITANIUM products

DIOXIDE MT 100 T, MT 100 TX, MT 100 Z, MT-01 from TAYCA, the products Solaveil CT-10 W and Solaveil CT 100 from the company UNIQEMA, and the product Eusolex T-AVO from the company MERCK;

[0270] - silica, alumina and alginic acid, such as the product MT-100 AQ from the company TAYCA;

[0271] - alumina and aluminum laurate, such as the product MICROTITANIUM

DIOXIDE MT 100 S from the company TAYCA;

[0272] - iron oxide and iron stearate, such as the product MICROTITANIUM

DIOXIDE MT 100 F from TAYCA;

- Zinc oxide and zinc stearate, such as the product BR 351 from the company

TAYCA;

- of 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;

- of silica, of alumina, of aluminum stearate and treated with a silicone, such as the product STT-30-DS from the company TITAN KOGYO;

- of silica and treated with a silicone, such as the product UV-TITAN X 195 from the company SACHTLEBEN PIGMENTS;

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

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

[0279] - 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;

- TiO ₂ treated with octyl trimethyl silane sold in particular under the trade name T 805 by the company DEGUSSA SILICES;

- TiO ₂ treated with a polydimethylsiloxane sold in particular under the trade name 70250 Cardre UE TÎO2SI3 by the company CARDRE;

- TiO ₂ anatase / rutile treated with a polydimethylliydrogénosiloxane sold in particular under the trade name MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBIC by the company COLOR TECHNIQUES.

One can also cite the pigments of TiO ₂ 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 T sorbitan isostearate, a fatty acid ester of polyoxyalkylenated glycerol 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 TiO ₂ doped with manganese in the triglyceride of capric / caprylic acid in the presence of tri-PPG-3 myristylether citrate and polyglyceryl37

3-polyricinoleate and or sorbitan isostearate (INCI name: titanium dioxide (and) tri-PPG-3 myristylether citrate (and) polyglyceryl-3 ricinoleate (and) sorbitan isostearate) as the product sold in particular under the trade name OPTISOL TD50 by CRODA.

The 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 Transparent titanium oxide PW, by the company MIYOSHI KASEI under the name UFTR, by the company TOMEN under the name ITS and by the company TIOXIDE under the name TIOVEIL AQ.

The uncoated zinc oxide pigments are, for example:

- those marketed in particular under the name Z-cote by the company

Sunsmart;

[0289] - those sold in particular under the name Nanox by the company

Elementis;

[0290] - those sold in particular under the name Nanogard WCD 2025 by the company Nanophase Technologies;

The coated zinc oxide pigments are for example:

[0292] - those sold in particular under the name Zinc Oxide CS-5 by the company Toshibi (ZnO coated with polymethylhydrogenesiloxane);

- Those sold in particular under the name Nanogard Zinc Oxide FN by the company Nanophase Technologies (in 40% dispersion in Finsolv TN, benzoate of Ci ₂ to Ci ₅ alcohols);

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

[0296] - those sold in particular under the name SPD-Z1 by the company

Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane);

[0297] - those sold in particular 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);

[0298] - those sold in particular under the name Fuji ZnO-SMS-10 by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane);

- Those sold in particular under the name Nanox Gel TN by the company Elementis (ZnO dispersed at 55% in benzoate of Ci ₂ to Ci ₅ alcohols with polycondensate of hydroxy stearic acid).

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

The 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 the company MITSUBISHI under the name TY220.

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 OXYDE DE FER TRANSPARENT.

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 glycerin such than the product M 211 sold by the company SACHTLEBEN PIGMENTS.

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

[0305] Preferably, the composition according to the present invention comprises one or more liposoluble organic UV filters; more preferably chosen from dibenzoylmethane compounds, salicylic compounds, β, β-diphenylacrylate compounds, benzophenone compounds, phenyl benzotriazole compounds, triazine compounds and their mixtures; and even better among homosalate, ethylhexyl salicylate, drometrizole trisiloxane, bis-ethylhexyloxyphenol methoxyphenyl triazine, octocrylene, butyl methoxydibenzoylmethane, ethylhexyl triazone, 2- (4-diethylamino-2-hydroxy) n-hexyl benzoate, diethylhexyl butamido triazone and mixtures thereof.

The amount of the UV filter (s) present in the composition according to the invention can range from 0.1 to 50% by weight, relative to the total weight of the composition. It preferably ranges from 10 to 50% by weight, more preferably from 20 to 50% by weight, and better still ranges from 20 to 40% by weight, relative to the total weight of the composition.

[0307] Anionic crosslinked hydrophilic polymers

The composition according to the present invention further comprises one or more anionic crosslinked hydrophilic polymers.

By “hydrophilic polymer” within the meaning of the present invention, is meant a polymer which, introduced into water at a concentration equal to 1% by weight, at 25 ° C., leads to a macroscopically homogeneous solution, the light transmittance, at a wavelength equal to 500 nm, through a 1 cm thick sample, is at least 10%, which corresponds to an absorbance [abs = -log (transmittance)] less than 1.5.

The anionic crosslinked hydrophilic polymer or polymers according to the invention generally do not contain fatty chain monomers, that is to say that they do not comprise a repeating unit having an alkyl group C _n H _{2n +} i where the integer n is greater than or equal to 6, preferably greater than or equal to 7.

By “crosslinked” within the meaning of the present invention is meant a polymer whose monomer has been polymerized with an olefinically polyunsaturated monomer commonly used for the crosslinking of polymers obtained by radical polymerization.

As crosslinking agents, mention may in particular be made of divinylbenzene, diallyl ether, dipropylene glycol-diallylether, polyglycol-diallyl ethers, triethylene glycol-divinyl ether, hydroquinone-diallyl ether, di (meth) acrylate ethylene glycol or tetraethylene glycol, trimethylol propane triacrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallylamine, triallylcyanurate, diallylmaleate, tetraallylethylenediamine, tetra-allylethyl-ethanolpropylene trimethyl ally le (meth) acrylate, allyl ethers of alcohols from the sugar series, or other allyl- or vinyl-ethers of polyfunctional alcohols, as well as allyl esters of derivatives of phosphoric acid and / or vinylphosphonic, or mixtures of these compounds.

According to a preferred embodiment of the invention, the crosslinking agent is chosen from methylene-bis-acrylamide, allyl methacrylate, trimethylol propane triacrylate (TMPTA) and their mixtures. The crosslinking rate generally ranges from 0.01% to 10% by mole and more particularly from 0.2% to 2% by mole relative to the polymer.

The anionic crosslinked hydrophilic polymer (s) used in the composition of the present invention can advantageously be chosen from crosslinked 2-acrylamido 2-methylpropane sulfonic acid homo- and copolymers, homo- and co-polymers of at least one α, β-ethylenically unsaturated carboxylic acid monomer, and mixtures thereof. These polymers can optionally be neutralized in whole or in part.

The anionic crosslinked hydrophilic polymers used in the composition of the present invention may thus be crosslinked homopolymers or copolymers comprising at least one acrylamido 2-methyl propane sulfonic acid monomer (AMPS ^), in partially or completely neutralized form with a base mineral such as soda or potash.

They are preferably neutralized completely or almost completely neutralized, that is to say neutralized at least 90%.

The AMPS polymers suitable for the invention are water-soluble or water-dispersible. They are in this case:

- or “homopolymers” comprising only AMPS® monomers and, one or more crosslinking agents such as those defined above;

[0319] - or copolymers obtained from one or more AMPS ^ monomers, from one or more hydrophilic or hydrophobic ethylenically unsaturated monomers and, from one or more crosslinking agents such as those defined above. The hydrophobic ethylenically unsaturated monomers do not contain a fatty chain and are preferably present in small amounts.

By "fatty chain" within the meaning of the present invention means a hydrocarbon chain containing at least 6 carbon atoms.

The hydrophilic crosslinked copolymers of AMPS ^ according to the present invention contain one or more co-monomers which can be chosen in particular from water-soluble ethylenically unsaturated monomers, hydrophobic monomers and their mixtures.

[0322] The water-soluble co-monomers can be ionic or non-ionic.

Among the ionic water-soluble co-monomers, mention may be made, for example, of the following compounds and their salts:

- (meth) acrylic acid,

- styrene sulfonic acid,

- vinylsulfonic acid and (meth) allylsulfonic acid,

- vinyl phophonic acid,

- maleic acid,

- itaconic acid,

- crotonic acid,

- the water-soluble vinyl monomers of formula (A) below:

H, C — CR i

CO: i.

(AT)

In which,

- Ri is chosen from H, -CH ₃ , -C ₂ H ₅ or -C ₃ H ₇ ;

- Xi is chosen from alkyl oxides of type -OR ₂ where R ₂ is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbon atoms, substituted by at least one sulfonic group (-SO ₃ -) and / or sulfate (-SO ₄ -) and / or phosphate (-PO ₄ H ₂ -).

Among the nonionic water-soluble co-monomers, there may be mentioned, for example:

- (meth) acrylamide,

- N-vinylacetamide and N-methyl N-vinylacetamide,

- N-vinylformamide and N-methyl N-vinylformamide,

- maleic anhydride,

- vinylamine,

- N-vinyllactams comprising a cyclic alkyl group having from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam,

- vinyl alcohol of formula CH ₂ = CHOH,

- the water-soluble vinyl monomers of formula (B) below:

H, C = CR, | ύ

CO

I x ₂

In which,

- R ₃ is chosen from H, -CH ₃ , -C ₂ H ₅ or -C ₃ H ₇ ;

- X ₂ is chosen from alkyl oxides of the -OR ^ type where R ₄ is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbons, optionally substituted by a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxy group (-OH); ether.

[0327] Examples include glycidyl (meth) acrylate, hydroxyethyl methacrylate, and (meth) acrylates of ethylene glycol, of diethylene glycol or of polyalkylene glycol.

Among the hydrophobic comonomers without a fatty chain, there may be mentioned for example: - styrene and its derivatives such as 4-butylstyrene, alpha methylstyrene and vinyltoluene;

- vinyl acetate of formula CH ₂ = CH-OCOCH ₃ ;

- vinyl ethers of formula CH ₂ = CHOR in which R is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbons;

- 1 acrylonitrile;

- caprolactone;

- vinyl chloride and vinylidene chloride;

- silicone derivatives, leading after polymerization to silicone polymers such as methacryloxypropyltris (trimethylsiloxy) silane and silicone methacrylamides; - the hydrophobic vinyl monomers of formula (C) below:

H „C = CR ^A I * (C)

CO ⁷ • I

X, 3

In which,

R4 is chosen from H, -CH ₃ , -C ₂ H ₅ or -C ₃ H ₇ ;

X ₃ is chosen from alkyl oxides of type -OR ₅ where R ₅ is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbon atoms.

Let us quote for example, methyl methacrylate, ethyl methacrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl acrylate and (meth) acrylate. 'isobutyle.

The water-soluble or water-dispersible AMPS ^ polymers of the invention preferably have a molar mass ranging from 50,000 g / mole to 10,000,000 g / mole, preferably from 80,000 g / mole to 8,000,000 g / mole, and even more preferably from 100,000 g / mole to 7,000,000 g / mole.

As crosslinked hydrophilic homopolymers in accordance with the present invention, there may be mentioned, for example:

[0333] - crosslinked polymers of acrylamide-2-methyl propane sulfonate such as that used in the commercial product Simulgel 800 (CTFA name: Sodium Polyacryloyldimethyl Taurate), crosslinked polymers of acrylamide 2-methyl propane sulfonate d ammonium (INCI name: Ammonium Polydimethyltauramide) as those described in patent EP 0 815 928 B1 and such as the product sold under the trade name Hostacerin AMPS ^ by the company Clariant;

Crosslinked acrylamide / acrylamido-2-methyl propane sulfonate copolymers such as that used in the commercial product SEPIGEL 305 (INCI name: Polyacrylamide / Ci ₃ -Ci4 Isoparaffin / Laureth-7) or that used in the product commercial sold under the name Simulgel 600 (INCI name: Acrylamide / Sodium acryloyldimethyltaurate / Isohexadecane / Polysorbate-80) by the company Seppic;

- the copolymers of AMPS ^ and of vinylpyrrolidone or of vinylformamide such as that used in the commercial product sold under the name Aristoflex AVC ^ by the company Clariant (name CTFA: Ammonium Acryloyldimethyltaurate / VP Copolymer) but neutralized by soda or potash;

- the copolymers of AMPS ^ and sodium acrylate, such as for example the copolymer AMPS / sodium acrylate such as that used in the commercial product sold under the name Simulgel EG ^ by the company Seppic or under the name commercial Sepinov EM (CTFA name: Hydroxyethyl Acrylate / Sodium Acryloyl43 dimethyl taurate copolymer);

- the copolymers of AMPS ^ and hydroxyethyl acrylate, such as for example the copolymer AMPS ^ / hydroxyethyl acrylate such as that used in the commercial product sold under the name Simulgel NS ^ by the company Seppic (CTFA name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyltaurate copolymer (And) Squalane (And) Polysorbate 60) or as the product marketed under the name Copolymer Acrylamido-2-Methyl propane Sodium Sulfonate / Hydroxyethylacrylate as the commercial product Sepinov EMT 10 (INCI name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyl taurate copolymer).

As hydrophilic crosslinked copolymers of AMPS® preferred in accordance with the present invention, mention may be made of the copolymers of AMPS ^ and of hydroxyethyl acrylate.

The anionic crosslinked hydrophilic polymers can also be homopolymers or copolymers of at least one α, β-ethylenically unsaturated carboxylic acid monomer. They can in particular be chosen from copolymers resulting from the polymerization of at least one monomer (a) chosen from α, β-ethylenically unsaturated carboxylic acids or their esters, with at least one ethylenically unsaturated monomer (b).

By “copolymers” within the meaning of the present invention is meant both the copolymers obtained from two kinds of monomers as those obtained from more than two kinds of monomers such as the terpolymers obtained from three kinds of monomers.

Preferably, these copolymers are chosen from the copolymers resulting from the polymerization:

[0342] - at least one monomer of formula (1) below:

CH ~ C— C — OH ( ¹ ) I II Ri O

In which, Ri denotes H or CH ₃ or C ₂ H ₅ , that is to say monomers of acrylic acid, methacrylic acid or ethacrylic acid.

Among the polymers containing at least one carboxylic acid monomer, mention may also be made of sodium polyacrylates such as those sold under the name Cosmedia SP ^, or Cosmedia SPL ^ in reverse emulsion containing about 60% dry matter, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by the company Cognis.

Mention may also be made of partially neutralized sodium polyacrylates which are in the form of a reverse emulsion comprising at least one polar oil, for example that sold under the name Luvigel ^ EM by the company BASF.

These polymers can also be chosen from homopolymers of crosslinked (meth) acrylic acid.

By way of example, mention may be made of those sold by Lubrizol under the names Carbopol, 910, 934, 940, 941, 934 P, 980, 981, 2984, 5984, Carbopol Ultrez 10 Polymer, or by 3V-Sigma under the name Synthalen ^ K, Synthalen ^ L, or Synthalen ^ M.

Preferably, the anionic crosslinked hydrophilic polymer or polymers present in the composition according to the invention are chosen from polymers comprising at least one carboxylic acid monomer with α, β-ethylenic unsaturation, more preferably from acid homopolymers (meth) acrylic crosslinked, and better still among Carbopol 980 (CTFA name: carbomer), Carbopol Ultrez 10 Polymer, and mixtures thereof.

The amount of anionic crosslinked hydrophilic polymer (s) present in the composition of the invention preferably ranges from 0.05 to 5% by weight, more preferably from 0.08 to 2.5% by weight, and more preferably from 0.1 to 1.5% by weight, relative to the total weight of the composition.

The surfactants

The composition according to the present invention further comprises one or more surfactants having an HLB less than or equal to 5.

The term HLB (from the English "Hydrophilic Lipophilie Balance") is well known to those skilled in the art, and designates the hydrophilic-lipophilic balance of a surfactant at 25 ° C in the sense of Griffin.

By hydrophilic-lipophilic balance (HLB) is meant the balance between the size and the strength of the hydrophilic group and the size and the strength of the lipophilic group of the surfactant. The HLB value according to Griffin is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256.

The surfactant (s) having an HLB less than or equal to 5 can be ionic or nonionic. One can in particular use the surfactants having an HLB less than or equal to 5 which are cited in the reference work McCutcheons Emulsifiers & Dertergents, International Edition of 1998 and following.

One can also refer to the document "Encyclopedia of Chemical Technology, KIRK-OTHMER", volume 22, p. 333-432, 3rd edition, 1979, WILEY, for the definition of the properties and emulsifying functions of surfactants, in particular p.347-377 of this reference, for nonionic surfactants.

[0356] Preferably, the surfactants of the invention have an HLB less than or equal to 4.

More particularly, the surfactants suitable for the present invention are nonionic.

[0358] The nonionic surfactants having an HLB of less than or equal to 5 can in particular be chosen from alkyl- and polyalkylesters of poly (ethylene oxide); oxyalkylenated fatty alcohols; poly (ethylene oxide) alkyl and polyalkyl ethers; alkyl- and polyalkylesters of sorbitan, polyoxyethylenated or non-polyoxyethylenated; non-polyoxyethylenated alkyl and polyalkyl ethers of sorbitan; alkyl- and polyalkyl-glycosides or polyglycosides, in particular alkyl- and polyalkylglucosides or polyglucosides; sucrose alkyl and polyalkyl esters; alkyl and polyalkyl esters of glycerol, polyoxyethylenated or not; alkyl- and polyalkyl ethers of glycerol, polyoxyethylenated or not; and their mixtures, these compounds comprising at least one fatty chain comprising from 6 to 30 carbon atoms, preferably from 12 to 30 carbon atoms, and more preferably from 14 to 24 carbon atoms.

They can be chosen from fatty alcohols, fatty alpha-diols and alkyl (Ci. ₂ o) phenols, these compounds being polyethoxylated and / or polypropoxylated and / or polyglycerolated, the number of ethylene oxide groups and / or propylene oxide which can range from 1 to 15, preferably from 1 to 10 and the number of glycerol groups which can range from 1 to 10, preferably from 2 to 6; these compounds comprising at least one fatty chain comprising from 6 to 30 carbon atoms, preferably from 12 to 30 carbon atoms, and more preferably from 14 to 24 carbon atoms.

Mention may also be made of condensates of ethylene oxide and propylene oxide on fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 ethylene oxide units, polyglycerolated fatty amides comprising on average from 1 to 5 glycerol groups and in particular from 1.5 to 4; fatty acid esters of sorbitan, fatty acid esters of sucrose, polyoxyalkylenated, preferably polyoxyethylenated fatty acid esters having from 2 to 10 moles of ethylene oxide, including oxyethylenated vegetable oils.

As alkyl- and polyalkyl-esters of poly (ethylene oxide), use is preferably made of those having a number of ethylene oxide (EO) units ranging from 2 to 10, and more preferably from 2 to 6. Mention may for example be made of 2 EO stearate, diethylene glycol monostearate, polyoxyethylene monostearate with 5 EO.

As oxyalkylenated fatty alcohols, in particular oxyethylenated and / or oxypropylenated, those having preferably from 1 to 10 and more preferably from 2 to 5 oxyethylene and / or oxypropylene units are used, in particular C ₈ to C fatty alcohols ₂₄ , and preferably at C _[2 to C _[8 , ethoxylated such as stearyl alcohol ethoxylated with 2 oxyethylene units (name CTFA Steareth-2) such as BRU 72 sold by the company UNIQEMA. Mention may also be made of cetyl ether 2 EO, phytosterol 2 EO, steareth 4, beheneth 2, oleth-2.

As non-polyoxyethylenated sorbitan alkyl and polyalkyl esters, sorbitan monostearate, sorbitan tristearate is preferably used

As alkyl- and polyalkyl-ethers of sorbitan, polyoxyethylenated or non-polyoxyé thylénés, preferably used those having a number of units of ethylene oxide (EO) ranging from 0 to 10, and more preferably from 0 to 5.

As alkyl- and polyalkyl-glucosides or polyglucosides, use is preferably made of those containing an alkyl group comprising from 12 to 30 carbon atoms and preferably from 16 to 22 carbon atoms, and containing a glucoside group preferably comprising 1 to 5, in particular 1, 2 to 3 units of glucoside. Among the alkylpolyglucosides which can be used, mention may in particular be made of arachidylglucoside.

As alkyl- and polyalkyl-esters of sucrose, mention may, for example, be made of Crodesta F150, sucrose monolaurate sold under the name Crodesta SL 40, the products sold by Ryoto Sugar Ester, such as, for example, sucrose palmitate sold under the reference Ryoto Sugar Ester P1670, Ryoto Sugar Ester LWA 1695, Ryoto Sugar Ester 01570 or sucrose distearate.

As alkyl- and polyalkyl-esters of glycerol, polyoxyethylenated or non-polyoxyethylenated, those having a number of ethylene oxide (EO) units ranging from 0 to 10 and a number of glycerol units ranging from 0 to 10 are preferably used. 1 to 8. More preferably, the alkyl- and polyalkyl-esters of glycerol are non-polyoxyethylenated.

Mention may for example be made of glyceryl mono oleate, hexaglyceryl monolaurate, diglyceryl distearate, glyceryl stearate, glyceryl isostearate, tetraglyceryl tristearate, decaglyceryl decastearate, diglyceryl monostearate hexaglyceryl tristearate, decaglyceryl pentasterearate, glyceryl monobehenate, glyceryl dibehenate and the ester of glycerol and palmitic and stearic acids.

As alkyl- and polyalkyl-ethers of glycerol, polyoxyethylenated or non-polyoxyethylenated, preferably those having a number of ethylene oxide (EO) units ranging from 0 to 10, and more preferably from 0 to 5 and a number of glycerol units ranging from 1 to 10.

[0370] Preferably, the surfactant (s) having an HLB less than or equal to 5, present in the composition according to the invention, are chosen from steareth-2, beheneth-2, oleth-2, distearate sucrose, glyceryl mono oleate, glyceryl stearate, glyceryl isostearate, diglyceryl distearate, tetraglyceryl tristearate, decaglyceryl decastearate, diglyceryl monostearate, hexaglyceryl tristearate, pentaglyceryl tristearate sorbitan monostearate, sorbitan tristearate, diethylene glycol monostearate, glycerol ester of palmitic and stearic acids, glyceryl monobehenate, glyceryl dibehenate, and mixtures thereof; and more preferably the glycerol mono oleate.

The amount of the surfactant (s) having an HLB less than or equal to 5, present in the composition according to the invention, preferably ranges from 0.1 to 3% by weight, more preferably from 0.2 to 2% by weight, and better still from 0.3 to 1% by weight, relative to the total weight of the composition.

[0372] The non-volatile alkanes

The composition according to the present invention further comprises one or more non-volatile alkanes, preferably with a viscosity of less than 20 mPa.s at 20 ° C.

By nonvolatile alkane is meant a cosmetic hydrocarbon oil, liquid at room temperature, in particular having a vapor pressure at 20 ° C of less than 0.01 kPa, according to the definition of a Volatile Organic Compound (VOC) of Article 2 of Directive 1999/13 / EC of the European Council of March 11, 1992: "Any organic compound having a vapor pressure of 0.01 kPa or more at a temperature of 293.15 K".

According to a particular embodiment, the non-volatile alkanes have a viscosity at 20 ° C of less than 20 mPa.s.

The viscosity is measured at 20 ° C. with a Rheomat RM100® viscometer from Lamy Rheology.

According to a particular embodiment, the non-volatile alkanes comprise from 10 to 30 carbon atoms, in particular from 12 to 26 carbon atoms, and more particularly from 15 to 19 carbon atoms.

In a particularly preferred form, a mixture of alkanes of 15 to 19 carbon atoms will be used, such as the products sold under the references of Emogreen L19 and Emosmart L19 from SEPPIC.

The amount of the non-volatile alkane (s) present in the composition of the invention of the invention preferably ranges from 0.5 to 10% by weight, more preferably from 1 to 8% by weight, and again better from 2 to 5% by weight, relative to the total weight of the composition.

Preferably, the weight ratio between the amount of linear alkanes) and the amount of hydrophilic polymer (s) crosslinked anionically, present in the composition according to the invention, is less than or equal to 5, preferably less than or equal to 4.5, and more preferably ranges from 1 to 4.5.

[0381] Efficiency boosters

The composition according to the present invention may optionally further comprise one or more efficiency boosters.

By “efficiency booster” within the meaning of the present application, is meant a raw material which does not itself filter UV radiation but which makes it possible to amplify the filtering performance of the composition of the invention.

As examples of efficiency boosters, mention may be made of particles of copolymer of styrene and acrylates such as those marketed under the name Sunspheres Powder by Dow Chemicals; waxes such as polymethylene wax (Cirebelle 303 sold by Cirebelle); lipophilic gelling polymers such as semi-crystalline polyacrylates sold under the names of Interlimer IPA 13-1, Interlimer IPA 13-6 or Uniclear 100 VG; and their mixtures.

According to a preferred embodiment, the composition according to the invention further comprises one or more particles of copolymer of styrene and acrylates, sold under the name Sunspheres Powder by Dow Chemicals.

Insoluble particles

The composition according to the present invention may optionally further comprise one or more insoluble particles, having no UV filtration property or efficiency booster property.

These particles make it possible to obtain excellent sensory or optical properties after application of the composition to the skin.

These particles can be chosen from nylon such as the ORGASOL 2002 marketed by Arkema; polymethylsilsesquioxane such as, for example, micro-beads of methylsilsesquioxane resin sold under the name Tospearl 145A by the company Momentive Performance Materials; polymethylmethacrylate such as PMMA hollow spheres sold under the name Covabeads LH 85 by the company Sensient; starches such as corn starch; talc; silica; microspheres of crosslinked polyacrylates such as Aquakeep 10 SH-NFC sold by the company Sumitomo Seika; perlite such as ΓΟΡΤΙΜΑΤ 2550 OR sold by the company World Minerais; iron oxide or titanium oxide pigments and mixtures thereof.

[0390] Preferably, the composition according to the invention also comprises nylon particles, such as ORGASOL 2002.

[0391] The additives

The composition according to the present invention may optionally further comprise one or more additives, different from the compounds of the invention and usually used in cosmetics, and particularly in the field of sun products, skincare and make-up.

The aqueous phase may optionally comprise surfactants different from the surfactants having an HLB less than or equal to 5, such as those mentioned above; alcohols, such as ethanol; glycols, such as dipropylene glycol, and butylene glycol; glycerol; actives ; salts; organic particles; amphiphilic polymers, such as Pemulens TRI or TR2 or Carbopol ETD2020 sold by the company Lubrizol; hydrophilic polymers, such as poly Nvinylpyrrolidone; polysaccharides, such as guar gum, xanthan gum and cellulose derivatives; water-soluble or water-dispersible silicone derivatives, such as acrylic silicones, polyether silicones and cationic silicones; and their mixtures.

As active agents, mention may in particular be made of vitamins (A, C, E, K, PP, etc.) alone or as a mixture, as well as their derivatives; keratolytic and / or scaling agents (salicylic acid and its derivatives, alpha-hydroxy acids, ascorbic acid and its derivatives); anti-inflammatory agents; soothing agents; depigmenting agents; tightening agents, such as synthetic polymers; vegetable proteins; polysaccharides of plant origin in the form or not of microgels; wax dispersions; mixed silicates and colloidal particles of inorganic fillers; matting agents; anti-hair loss and / or hair regrowth agents; anti-wrinkle agents; and their mixtures.

The oily phase may optionally further comprise lipophilic gelling agents; surfactants other than surfactants having an HLB less than or equal to 5, such as those mentioned above; waxes; organic or mineral particles; alkane, silicone, fluorinated oils; and their mixtures.

Of course, a person skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition according to the invention are not, or not substantially, affected by the or the additions envisaged.

The above additives can generally be present in an amount for each of them between 0 and 20% by weight relative to the total weight of the composition.

[0398] The emulsion

The composition according to the invention is in the form of an oil-in-water emulsion (also called direct emulsion, or O / W for short), containing oil droplets dispersed in a continuous aqueous phase.

As indicated above, the compositions according to the invention comprise at least one continuous aqueous phase.

The aqueous phase contains water, and optionally other organic solvents soluble or miscible in water.

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

Solvents or water-miscible solvents suitable for the invention include short chain monoalcohols, for example C ₂ to C ₄ such as ethanol, isopropanol; diols or polyols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, propane 1,3-diol, pentylene glycol, hexylene glycol, caprylyl glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycerol, and sorbitol, and mixtures thereof.

According to a preferred embodiment, it is possible to use more particularly ethanol, propylene glycol, glycerol, propane 1,3-diol, and their mixtures.

The aqueous phase of the composition according to the invention comprises at least water in a total amount greater than or equal to 30% by weight, preferably greater than or equal to 50% by weight, and preferably greater than or equal to 60% by weight, relative to the total weight of the aqueous phase.

In particular, the water may be present in an amount ranging from 30 to 99% by weight, preferably from 50 to 99% by weight, and preferably from 60 to 98% by weight, relative to the total weight of the aqueous phase.

The water may be present in a total amount greater than or equal to 30% by weight, preferably greater than or equal to 45% by weight, and preferably ranges from 45 to 65% by weight, relative to the total weight of composition.

[0408] As indicated above, the composition according to the invention comprises at least one oily phase dispersed in the aqueous phase.

Within the meaning of the invention, the term "oily phase" means a phase comprising at least the alkanes according to the invention and optionally other oils and all of the liposoluble and lipophilic ingredients and fatty substances used for the formulation of the compositions of the invention.

The term “oil” means any fatty substance in liquid form at room temperature (25 ° C) and at atmospheric pressure (1.013.10 ⁵ Pa).

By “fatty substance” is meant an organic compound insoluble in water at room temperature (25 ° C) and at atmospheric pressure (1.013.10 ⁵ Pa) (solubility less than 5% by weight, and preferably less at 1% by weight, even more preferably less than 0.1% by weight). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms and / or a chain of at least two siloxane groups. In addition, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as, for example, chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran ( THE), petrolatum oil or decamethylcyclopentasiloxane.

[0412] The oils other than the alkanes according to the invention can be volatile or nonvolatile.

These oils can be chosen from hydrocarbon oils, silicone oils, fluorinated oils and their mixtures.

[0414] An additional hydrocarbon oil can be an animal hydrocarbon oil, a vegetable hydrocarbon oil, a mineral hydrocarbon oil, or a synthetic hydrocarbon oil.

An additional oil suitable for the invention can advantageously be chosen from mineral hydrocarbon oils, vegetable hydrocarbon oils, synthetic hydrocarbon oils, silicone oils, and mixtures thereof.

For the purposes of the present invention, the term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group.

[0417] The term "hydrocarbon-based oil" means an oil mainly containing hydrogen and carbon atoms.

[0418] An additional hydrocarbon oil can also optionally comprise oxygen, nitrogen, sulfur and / or phosphorus atoms, for example, in the form of hydroxyl, amine, amide, ester, ether or acid groups, and in particular in the form of hydroxyl, ester, ether or acid groups.

The oily phase may comprise one or more volatile or non-volatile hydrocarbon oils and / or one or more volatile and or non-volatile silicone oils.

Among the additional non-volatile hydrocarbon oils, there may be mentioned glyceride triesters and in particular the triglycerides of caprylic / capric acids such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel, fatty amides such as Isopropyl N-lauroyl sarcosinate such as the product sold under the trade name Eldew SL 205® from Ajinomoto, synthetic esters and in particular isononyl isononanoate, diisopropyl sebacate , the benzoate of C12-C15 alcohols such as the product sold under the trade name “Finsolv TN®” or “Witconol TN®” by the company WITCO or “TEGOSOFT TN®” by the company EVONIK GOLDSCHMIDT, the Benzoate of 2- ethylphenyl such as the commercial product sold under the name "X-TEND 226®" by the company ISP, and fatty alcohols, in particular octyldodecanol.

[0421] As additional volatile hydrocarbon oils, mention may be made of hydrocarbon oils having from 8 to 16 carbon atoms, and especially branched alkanes, C ₈ to C ₆ isoalkanes C ₈ to Ci ₆ of petroleum origin ( also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, oils sold under the trade names of Isopars or Permyls, branched esters in C ₈ to Ci ₆ , isohexyl neopentanoate, and mixtures thereof.

Among the non-volatile silicone oils, non-volatile polydimethylsiloxanes (PDMS) may be mentioned, polydimethylsiloxanes comprising alkyl or alkoxy groups, pendant and / or at the end of the silicone chain, groups each having 2 to 24 carbon atoms , phenylated silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dhnethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates.

Among the volatile silicone oils, mention may be made, for example, of volatile linear or cyclic silicone oils, in particular those having a viscosity at 25 ° C. of less than or equal to 8 centistokes (8 × 10 ⁶ m ² / s), and having in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil which can be used in the invention, mention may in particular be made of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisil tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.

An oily phase according to the invention can also comprise, mixed with or dissolved in oil, other fatty substances.

Another fatty substance which may be present in the oily phase can be, for example:

[0426] - a fatty acid, for example chosen from fatty acids containing from 8 to 30 carbon atoms, such as lauric acid, palmitic acid, oleic acid and stearic acid;

[0427] - a wax chosen from waxes such as lanolin, beeswax,

Carnauba or Candellila, paraffin, lignite or microcrystalline waxes, ceresin or ozokerite, synthetic waxes such as polyethylene waxes, Fischer-Tropsch waxes;

[0428] - a gum chosen from silicone gums (dimethiconol),

[0429] - a pasty compound, such as polymeric or non-polymeric silicone compounds, esters of an oligomeric glycerol, arachidyl propionate, triglycerides of fatty acids and their derivatives,

[0430] - and their mixtures.

The amount of oily phase preferably ranges from 5 to 50% by weight, and more preferably from 10 to 45% by weight, relative to the total weight of the composition.

The number average size of the oil droplets present in the composition of the invention preferably ranges from 0.1 to 20 microns, and more preferably from 1 to 15 microns.

This number average size can be measured using a granulometer.

The emulsification processes that can be used to prepare the compositions according to the invention can, for example, be of the pale type or propeller and rotor-stator.

The subject of the present invention is also a method of cosmetic treatment of the skin, in particular human skin, against UV radiation consisting in applying the composition according to the invention to the skin.

Preferably, the UV radiation corresponds to solar radiation.

[0437] More particularly, the present invention relates to a cosmetic method for limiting the darkening of the skin and / or improving the color and / or the uniformity of the complexion comprising the application to the surface of the skin of minus a composition as defined above.

The subject of the invention is also a non-therapeutic cosmetic method for preventing and / or treating the signs of aging of a skin comprising the application to the surface of the skin of at least one composition as defined below. -before.

The present invention also relates to a composition as defined above for its use against UV radiation, in particular against solar radiation.

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

Example

In the examples which follow, all the amounts are indicated in percentage by mass of active material (MA) relative to the total weight of the composition.

EXAMPLE 1

[0443] Preparation of the compositions

The following compositions 1 to 4 were prepared from the ingredients, the contents of which are indicated in the table below.

[0445]

[Tables 1]

INCI NAME Phase 1 2 3 Invention 4 Invention AQUA Al 54.95 54.95 54.95 54.95 CAPRYLYL GLYCOL Al 0.3 0.3 0.3 0.3 PHENOXYETHANOL Al 0.5 0.5 0.5 0.5 DISODIUM EDTA Al 0.1 0.1 0.1 0.1 GLYCERIN Al 6 6 6 6 CARBOMER (1/1 mixture of CARBOPOL 980 POLYMER (LUBRIZOL) and CARBOPOL ULTREZ 10 POLYMER (LUBRIZOL)) A2 0.5 0.5 0.5 0.5 TRIETHANOLAMINE A2 0.25 0.25 0.25 0.25 HOMOSALATE B 8 8 8 8 ETHYLHEXYL SALICYLATE B 5 5 5 5 BUTYL METHOXYDIBENZOYL METHANE B 4 4 4 4 BIS-ETHYLHEXYLOXYPHENO L METHOXYPHENYL TRIAZINE B 2.5 2.5 2.5 2.5 OCTOCRYLENE B 3.5 3.5 3.5 3.5 GLYCERYL OLEATE B 0.4 0.4 0.4 0.4 DICAPRYLYL ETHER B 3 3 3 3 DICAPRYLYL CARBONATE B 3 3 3 3 DIMETHICONE and ACRYLATES / DIMETHICONE copolymer (KP-545L from SHIN ETSU) B 5 ISODODECANE B 5 C15-19 ALKANE (EMOGREEN SEPPIC L19) B 5 C15-19 ALKANE (EMOSMART L19 (SEPPIC) B 5

ETHANOL DENATURE VS 3 3 3 3

[0446] Procedure

[0447] Preparation of phases Al and Λ2

The raw materials of Al are weighed beforehand using a balance (precision = 0.01 g), are heated to a temperature of 65 ° C in a tank of a cos 1000 with double wall. Phase A2 is introduced with stirring (scraping blades) until a homogeneous and translucent preparation is obtained.

[0449] Phase B

[0450] Phase B is heated to 90 ° C, cooled to 65 ° C, and introduced into phase A1 + A2 with turbine stirring, turax type and scraper blades.

The stirring is continued for 10 minutes.

The preparation is brought to room temperature.

[0453] Addition of phase C

[0454] Phase C is introduced into phase (A1 + A2 + B) with stirring scraper blades for 10 minutes.

The level of sun protection, as well as the cosmetic properties on wet skin of each of the compositions 1 to 4 were evaluated according to the following methods.

Sun protection level

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

Each composition was applied to a rough plate of PMMA, in the form of a homogeneous and regular deposit at the rate of 1 mg.cm ² .

The sun protection factors (SPF) were measured using a UV-2000S spectrophotometer from the company Labsphère.

[0460] Cosmetic properties on wet skin

[0461] Release evaluation protocol (appearance of white marks) when spraying water on the skin treated with the product:

[0462] Each composition is applied to the forearm at a dose of 2 mg / cm2. The product is spread in circular movements until the product has penetrated (for about 30 seconds).

After 10 minutes of drying, distilled water is sprayed onto the treated area. The amount of water sprayed is 190 pL.

The evaluation of the release, that is to say white traces and streaks created during the spraying, is carried out by eye according to a scale ranging from 1 to 5 where 1 constitutes a reference which has no white traces and 5 constitutes a reference which presents very marked white traces.

[0465] Protocol for evaluating white traces when applied to wet skin: [0466] A quantity of 50 μL of distilled water is applied to the forearm using an Eppendorf pipette. The water is distributed by spreading it out evenly over a rectangular area measuring 8cm by 4cm.

Each composition is applied to the wet area of the forearm according to the dose of 2 mg / cm2. The product is spread in circular movements for 30 seconds.

The evaluation of the white traces is carried out by visual control, on a scale ranging from 1 to 5 where 1 constitutes a non-white (transparent) reference and 5 constitutes a very white reference.

[0469] Evaluation protocol for tights after application to wet skin:

[0470] The tights are evaluated by a panel of 10 sensory experts. 50 µL of distilled water is applied to the forearm using an Eppendorf pipette. Each composition is applied to the wet area of the forearm at a dose of 2 mg / cm2. The product is spread in circular movements until the product penetrates (about 30 seconds). The evaluation of the tights is carried out after 2 minutes of drying by applying the back of the hand to the treated area, on a scale from 1 to 15 where 1 is a very sticky reference and 15 is a non-sticky reference.

[0471] Protocol for evaluating the fatty aspect after application to wet skin [0472] The fatty aspect is evaluated by a panel of sensory experts of 10 people. 50 µL of distilled water is applied to the forearm using an Eppendorf pipette. Each composition is applied to the wet area of the forearm at a dose of 2 mg / cm2. The product is spread in circular movements until the product penetrates (about 30 seconds). The fatty aspect is evaluated with the finger after 2 minutes of drying according to a scale going from 1 to 15 where 1 represents a very oily reference and 15 constitutes a low oily reference.

[0473] Protocol for evaluating the shiny appearance after application to wet skin

[0474] The fatty aspect is evaluated by a panel of sensory experts of 10 people. 50 µL of distilled water is applied to the forearm using an Eppendorf pipette. Each composition is applied to the wet area of the forearm at a dose of 2 mg / cm2. The product is spread in circular movements until the product penetrates (about 30 seconds). The gloss appearance is evaluated by eye after 2 minutes of drying on a scale from 1 to 15 where 1 represents a very shiny reference and 15 constitutes a non-shiny reference.

[0475] Results

The results are given in the table below.

[0477]

[Paintings!]

1 2 3 Inv 4 Inv SPF VITRO 56.3 +/- 5.1 54.8 +/- 3.2 58.6 +/- 3.9 55.2 +/- 3.1 FLASH POINT 66 ° C 54 ° C 62 ° C 62 ° C Appearance of white marks when spraying water (Release). Note / 5 (1 = no trace) 4 2 2 2 Evaluation of white traces when applying the product to wet skin 2 2 2 2 Non-sticky finish on wet skin (Panel score out of 15; 1 = Very sticky; 15 = Non-sticky) 11.0 +/- 1.5 11.8 +/- 1.4 12.0 +/- 1.1 11.6 +/- 1.0 Non-oily finish on wet skin (Panel score out of 15; 1 = Oily finish; 15 = Non-oily finish) 4.3 +/- 0.3 12.0 +/- 1.2 10.6 +/- 2.4 10.3 +/- 1.3 Non-shiny finish on wet skin (Panel score of 15; 1 = Shiny finish; 15 = Non-shiny finish) 5.1 +/- 0.7 6.9 +/- 1.1 10.0 +/- 0.7 9.1 +/- 1.5

The results obtained above have shown that only compositions 3 and 4 according to the invention, ie comprising an anionic crosslinked hydrophilic polymer, a surfactant having an HLB less than or equal to 5, and a non-volatile alkane as claimed , exhibited good UV filtration properties, a satisfactory flash point, excellent compatibility with wet skin and excellent cosmetic properties on wet skin, in particular the non-shiny finish.

EXAMPLE 2

The following compositions 5 to 8 were prepared from the ingredients, the contents of which are indicated in the table below.

[0481]

[Tables3]

INCI NAME Phase 5 6 7 8 AQUA Al QS 100 QS 100 QS 100 QS 100 CAPRYLYL GLYCOL Al 0.3 0.3 0.3 0.3 PHENOXYETHANOL Al 0.5 0.5 0.5 0.5 DISODIUM EDTA Al 0.1 0.1 0.1 0.1 GLYCERIN Al 6 6 6 6 CARBOMER (1/1 mixture of CARBOPOL 980 POLYMER (LUBRIZOL) and CARBOPOL ULTREZ 10 POLYMER (LUBRIZOL)) A2 0.5 0.5 0.5 1 TRIETHANOLAMINE A2 0.25 0.25 0.25 0.25 HOMOSALATE B 8 8 8 8 ETHYLHEXYL SALICYLATE B 5 5 5 5 BUTYL METHOXY- DIBENZOYL METHANE B 4 4 4 4 BIS-ETHYLHEXYLOXYPHENO L METHOXYPHENYL TRIAZINE B 2.5 2.5 2.5 2.5 OCTOCRYLENE B 3.5 3.5 3.5 3.5 GLYCERYL OLEATE B 0.4 0.4 SORBITAN TRISTEARATE 0.4 0.4 DICAPRYLYL ETHER B 3 3 3 3 DICAPRYLYL CARBONATE B 3 3 3 3 C15-19 ALKANE (EMOGREEN SEPPIC L19) B 3 2 3 C15-19 ALKANE (EMOSMART L19 (SEPPIC) B 4 2 8 ETHANOL DENATURE VS 3 3 3 3

Compositions 5 to 8 according to the invention, ie comprising an anionic crosslinked hydrophilic polymer, a surfactant having an HLB less than or equal to 5, and a non-volatile alkane as claimed, exhibit good UV filtration properties, a satisfactory flash point, excellent compatibility with wet skin and excellent cosmetic properties on wet skin.

Claims (1)

Claims [Claim 1] Composition in the form of an oil-in-water emulsion comprising: at. an oily phase, dispersed in an aqueous phase keep on going, b. one or more UV filters, vs. one or more anionic crosslinked hydrophilic polymers, d. one or more surfactants with an HLB less than or equal to 5, and e. one or more non-volatile alkanes preferably of viscosity less than 20 mPa.s. [Claim 2] Composition according to the preceding claim, characterized in that the UV filter or filters are chosen from water-soluble organic UV filters, liposoluble organic UV filters, insoluble organic UV filters, inorganic UV filters, and their mixtures. [Claim 3] Composition according to any one of the preceding claims, characterized in that the UV filter or filters are chosen from fat-soluble organic UV filters; preferably chosen from dibenzoylmethane compounds, salicylic compounds, β, β-diphenylacrylate compounds, benzophenone compounds, phenyl benzotriazole compounds, triazine compounds and their mixtures; and more preferably from homosalate, ethylhexyl salicylate, drometrizole trisiloxane, bis-ethylhexyloxyphenol methoxyphenyl triazine, octocrylene, butyl methoxydibenzoylmethane, ethylhexyl triazone, 2- (4-diethylamino) n-hexyl benzoate, diethylhexyl butamido triazone and mixtures thereof. [Claim 4] Composition according to any one of the preceding claims, characterized in that the amount of the UV filter (s) ranges from 0.1 to 50% by weight, preferably from 10 to 50% by weight, more preferably from 20 to 50% by weight weight, and better still from 20 to 40% by weight, relative to the total weight of the composition. [Claim 5] Composition according to any one of the preceding claims, characterized in that the anionic crosslinked hydrophilic polymer (s) are chosen from cross-linked homo- and co-polymers of 2-acrylamido 2-methylpropane sulfonic acid, homo- and co-polymers at least one α, β-ethylenically unsaturated carboxylic acid monomer, and their mixtures, preferably from polymers comprising at least one α, β-ethylenically unsaturated carboxylic acid monomer, and more preferably from crosslinked (meth) acrylic acid homopolymers. [Claim 6] Composition according to any one of the preceding claims, characterized in that the quantity of anionic crosslinked hydrophilic polymer or polymers ranges from 0.05 to 5% by weight, preferably from 0.08 to 2.5% by weight, and more preferably from 0.1 to 1.5% by weight, relative to the total weight of the composition. [Claim 7] Composition according to any one of the preceding claims, characterized in that the surfactant (s) having an HLB less than or equal to 5 are nonionic, and are preferably chosen from alkyl and polyalkyl esters of poly (ethylene oxide ); oxyalkylenated fatty alcohols; poly (ethylene oxide) alkyl and polyalkyl ethers; alkyl- and polyalkyl-esters of sorbitan, polyoxyethylenated or non-polyoxyethylenated; non-polyoxyethylenated alkyl and polyalkyl ethers of sorbitan; alkyl- and polyalkyl-glycosides or polyglycosides, in particular alkyl- and polyalkyl-glucosides or polyglucosides; sucrose alkyl and polyalkyl esters; alkyl and polyalkyl esters of glycerol, polyoxyethylenated or not; alkyl- and polyalkyl ethers of glycerol, polyoxyethylenated or not; and their mixtures, these compounds comprising at least one fatty chain comprising from 6 to 30 carbon atoms, preferably from 12 to 30 carbon atoms, and more preferably from 14 to 24 carbon atoms. [Claim 8] Composition according to any one of the preceding claims, characterized in that the surfactant (s) having an HLB less than or equal to 5 are chosen from steareth-2, beheneth-2, oleth-2, sucrose distearate, glyceryl mono oleate, glyceryl stearate, glyceryl isostearate, diglyceryl distearate, tetraglyceryl tristearate, decaglyceryl decasterearate, diglyceryl monostearate, hexaglyceryl tristearate, monastereaglycerylate, pentastylate sorbitan, sorbitan tristearate, diethylene glycol monostearate, glycerol ester of palmitic and stearic acids, glyceryl monobehenate, glyceryl dibehenate, and mixtures thereof, and preferably glycerol mono oleate. [Claim 9] Composition according to any one of the preceding claims, characterized in that the amount of the surfactant (s) having an HLB in- less than or equal to 5 ranges from 0.1 to 3% by weight, preferably from 0.2 to 2% by weight, and more preferably from 0.3 to 1% by weight, relative to the total weight of the composition. [Claim 10] Composition according to any one of the preceding claims, characterized in that the non-volatile alkane (s) are chosen from alkanes comprising from 10 to 30 carbon atoms, in particular from 12 to 26 carbon atoms and their mixtures. [Claim 11] Composition according to any one of the preceding claims, characterized in that the amount of the non-volatile alkane (s) ranges from 0.5 to 10% by weight, preferably from 1 to 8% by weight, and more preferably from 2 to 5 % by weight, relative to the total weight of the composition. [Claim 12] Composition according to any one of the preceding claims, characterized in that the weight ratio between the quantity of non-volatile alkane (s) and the quantity of anionic crosslinked hydrophilic polymer (s) is lower or equal to 5, preferably less than or equal to 4.5, and more preferably ranges from 1 to 4.5. [Claim 13] Composition according to any one of the preceding claims, characterized in that it further comprises one or more efficiency boosters, preferably chosen from particles of styrene and acrylate copolymer; waxes; lipophilic gelling polymers; and their mixtures. FRENCH REPUBLIC