WO2013117550A2 - Cosmetic composition comprising silica aerogel particles and a semicrystalline polymer - Google Patents

Abstract

A subject matter of the present invention is a composition for topical application comprising hydrophobic silica aerogel particles; at least one semicrystalline polymer which is solid at ambient temperature and which has a melting point of less than 70°C, comprising a) a polymeric backbone and b) at least one crystallizable organic side chain and/or one crystallizable organic block forming part of the backbone of said polymer, said polymer having a number-average molecular weight of greater than or equal to 2000; and at least one fatty phase. Another subject matter of the invention is a method for the cosmetic treatment of keratinous substances which consists in applying, to the keratinous substances, a composition as defined above, and also the use of this composition in the cosmetic or dermatological field, in particular for caring for, protecting and/or making up the skin of the body or face or for caring for the hair. The present invention exhibits the advantage of improving the sensory properties of cosmetic compositions, while making possible faster and fuller absorption in the skin.

Description

Cosmetic composition comprising silica aerogel particles and a semicrystalline polymer

The present patent application relates to a composition for topical application comprising hydrophobic silica aerogel particles, at least one specific semicrystalline polymer and at least one fatty phase, and to the use of said composition in the cosmetic and dermatological fields, in particular for caring for or treating keratinous substances.

In the cosmetic field and more particularly in the field of the care of the skin and photoprotection, it is commonplace to use formulation architectures comprising a fatty phase structured/thickened by a lipophilic thickener. This makes it possible to improve the efficacy and the stability of the products.

In particular, in the field of photoprotection, the thickening of the fatty phase comprising the lipophilic screening agents makes it possible to improve the homogeneity of the protective film and the SPF, while improving the resistance to water and sand.

Thus, patent FR 0 200 882 describes the improvement in the SPF factor obtained by virtue of the use of a semicrystalline polymer in the fatty phase of a sun protection composition.

Furthermore, the structuring of the fatty phase by lipophilic thickeners is particularly advantageous in order to give consistency to anhydrous or emulsified compositions intended for caring for or making up the skin. Very often, waxy or pasty fatty substances are used to obtain a thickening effect.

Nevertheless, these types of preparation exhibit the disadvantage of resulting in compositions which are greasy on application and which penetrate slowly and incompletely on the skin, leaving an unpleasant residual greasy film.

The need thus remains to produce compositions comprising a structured fatty phase which would not exhibit these disadvantages but which would be quickly absorbed without leaving a greasy film on the skin.

The Applicant Company has found, surprisingly, that the combination of a silica aerogel with a semicrystalline polymer makes it possible to improve the sensory properties of the cosmetic compositions in which they are present, by making possible faster and more complete absorption into the skin.

Thus, a subject matter of the present invention is a composition for topical application comprising hydrophobic silica aerogel particles; at least one semicrystalline polymer which is solid at ambient temperature and which has a melting point of less than 70°C, comprising a) a polymeric backbone and b) at least one crystallizable organic side chain and/or one crystallizable organic block forming part of the backbone of said polymer, said polymer having a number-average molecular weight of greater than or equal to 2000; and at least one fatty phase.

As the composition of the invention is intended for topical application to the skin or superficial body growths, it comprises a physiologically acceptable medium, that is to say a medium compatible with all keratinous substances, such as the skin, nails, mucous membranes and keratinous fibers (such as the hair or eyelashes).

The semicrystalline acrylic polymer acts as thickener of the oily phase but, depending on the properties and the viscosity desired, the composition can comprise other lipophilic thickeners, such as waxes. This can be advantageous for obtaining formulations in the form of butter or paste, or also sticks.

Even when the content of lipophilic thickeners and/or the content of fatty phase is high, the compositions according to the invention rapidly penetrate without leaving a greasy film.

Another subject matter of the invention is a method for the cosmetic treatment of keratinous substances which consists in applying, to the keratinous substances, a composition as defined above.

Another subject matter of the invention is the use of said composition in the cosmetic or dermatological field, in particular for caring for, protecting and/or making up the skin of the body or face or for caring for the hair.

In that which follows, the expression "at least one" is equivalent to "one or more" and, unless otherwise indicated, the limits of a range of values are included within this range.

Hydrophobic silica aerogels

Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air.

They are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, the one most commonly used being supercritical C0₂. This type of drying makes it possible to avoid shrinkage of the pores and of the material. The sol-gel process and the various drying operations are described in detail in Brinker C.J. and Scherer G.W., Sol-Gel Science, New York, Academic Press, 1990.

The hydrophobic silica aerogel particles used in the present invention exhibit a specific surface per unit of weight (S_w) ranging from 500 to 1500 m²/g, preferably from 600 to 1200 m²/g and better still from 600 to 800 m²/g, and a size, expressed as the volume- average diameter (D[0.5]), ranging from 1 to 1500 μηη, better still from 1 to 1000 μηη, preferably from 1 to 100 μηη, in particular from 1 to 30 μηη, more preferably from 5 to 25 μηη, better still from 5 to 20 μηη and even better still from 5 to 15 μηη. According to one embodiment, the hydrophobic silica aerogel particles used in the present invention exhibit a size, expressed as volume-average diameter (D[0.5]), ranging from 1 to 30 μηη, preferably from 5 to 25 μηη, better still from 5 to 20 μηη and even better still from 5 to 15 μηη.

The specific surface per unit of weight can be determined by the nitrogen absorption method, known as the BET (Brunauer-Emmett-Teller) method, described in The Journal of the American Chemical Society, Vol. 60, page 309, February 1938, which corresponds to international standard ISO 5794/1 (appendix D). The BET specific surface corresponds to the total specific surface of the particles under consideration.

The sizes of the silica aerogel particles can be measured by static light scattering using a commercial particle size analyzer of MasterSizer 2000 type from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter. This theory is described in particular in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957.

According to an advantageous embodiment, the hydrophobic silica aerogel particles used in the present invention exhibit a specific surface per unit of weight (S_w) ranging from 600 to 800 m²/g and a size, expressed as the volume-average diameter (D[0.5]), ranging from 5 to 20 μηη and even better still from 5 to 15 μηη.

The silica aerogel particles used in the present invention can advantageously exhibit a packed density (p) ranging from 0.04 g/cm³ to 0.10 g/cm³ and preferably from 0.05 g/cm³ to 0.08 g/cm³.

In the context of the present invention, this density, known as the packed density, can be assessed according to the following protocol:

40 g of powder are poured into a graduated measuring cylinder; the measuring cylinder is then placed on the Stav 2003 device from Stampf Volumeter; the measuring cylinder is subsequently subjected to a series of 2500 packing actions (this operation is repeated until the difference in volume between 2 consecutive tests is less than 2%); the final volume Vf of packed powder is then measured directly on the measuring cylinder. The packed density is determined by the ratio w/Vf, in this instance 40/Vf (Vf being expressed in cm³ and w in g).

According to one embodiment, the hydrophobic silica aerogel particles used in the present invention exhibit a specific surface per unit of volume S_v ranging from 5 to 60 m²/cm³, preferably from 10 to 50 m²/cm³ and better still from 15 to 40 m²/cm³. The specific surface per unit of volume is given by the relationship: S_v = S_w x p ; where p is the packed density expressed in g/cm³ and S_w is the specific surface per unit of weight expressed in m²/g, as defined above.

Preferably, the hydrophobic silica aerogel particles according to the invention have an oil absorption capacity, measured at the wet point, ranging from 5 to 18 ml/g, preferably from 6 to 15 ml/g and better still from 8 to 12 ml/g.

The absorption capacity measured at the wet point, denoted Wp, corresponds to the amount of oil which it is necessary to add to 100 g of particles in order to obtain a homogeneous paste.

It is measured according to the "wet point" method or method of determination of oil uptake of a powder described in standard NF T 30-022. It corresponds to the amount of oil adsorbed onto the available surface of the powder and/or absorbed by the powder by measurement of the wet point, described below:

An amount w = 2 g of powder is placed on a glass plate, and the oil (isononyl isononanoate) is then added dropwise. After addition of 4 to 5 drops of oil to the powder, mixing is carried out using a spatula, and addition of oil is continued until conglomerates of oil and powder have formed. From this point, the oil is added at the rate of one drop at a time and the mixture is subsequently triturated with the spatula. The addition of oil is stopped when a firm and smooth paste is obtained. This paste must be able to be spread over the glass plate without cracks or the formation of lumps. The volume Vs (expressed in ml) of oil used is then noted.

The oil uptake corresponds to the ratio Vs/w.

The aerogels used according to the present invention are hydrophobic silica aerogels, preferably silylated silica (INCI name: silica silylate) aerogels.

The term "hydrophobic silica" is understood to mean any silica, the surface of which is treated with silylating agents, for example with halogenated silanes, such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes, such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups

Si-Rn, for example trimethylsilyl groups.

As regards the preparation of hydrophobic silica aerogel particles modified at the surface by silylation, reference may be made to the document US 7 470 725.

Use will in particular be made of hydrophobic silica aerogel particles modified at the surface with trimethylsilyl groups (trimethylsiloxylated silica).

Mention may be made, as hydrophobic silica aerogels which can be used in the invention, for example, of the aerogel sold under the name VM-2260 (INCI name: Silica silylate) by Dow Corning, the particles of which exhibit an average size of approximately 1000 microns and a specific surface per unit of weight ranging from 600 to 800 m²/g. Mention may also be made of the aerogels sold by Cabot under the references Aerogel TLD 201 , Aerogel OGD 201 , Aerogel TLD 203, Enova® Aerogel MT 1 100 and Enova Aerogel MT 1200.

Use will more particularly be made of the aerogel sold under the name VM-2270 (INCI name: Silica silylate) by Dow Corning, the particles of which exhibit an average size ranging from 5 to15 microns and a specific surface per unit of weight ranging from 600 to 800 m²/g.

The hydrophobic silica aerogel particles can be present in the composition according to the invention in a content as active material ranging from 0.1 % to 15% by weight, preferably from 1 % to 10% by weight, better still from 1 % to 5% by weight and more preferably from 1 % to 3% by weight, with respect to the total weight of the composition. Semicrystalline polymer

The semicrystalline polymer used in the composition of the invention is generally introduced into the fatty phase of the composition.

Within the meaning of the invention, the term "polymers" is understood to mean compounds comprising at least 2 repeat units, preferably at least 3 repeat units and more especially at least 10 repeat units.

The term "semicrystalline polymer" is understood to mean polymers comprising a crystallizable portion, a crystallizable pendent and/or end chain or a crystallizable block in the backbone and/or at the ends, and an amorphous portion in the backbone, and exhibiting a first-order reversible phase change temperature, in particular a melting point (solid-liquid transition). When the crystallizable portion is in the form of a crystallizable block of the polymer backbone, the amorphous portion of the polymer is in the form of an amorphous block; the semicrystalline polymer is, in this case, a block copolymer, for example of the diblock, triblock or multiblock type, comprising at least one crystallizable block and at least one amorphous block. The term "block" is understood to mean generally at least 5 identical repeat units. The crystallizable block or blocks are then different in chemical nature from the amorphous block or blocks.

According to a specific embodiment, the semicrystalline polymer or polymers used in the composition of the invention exhibit a melting point M.p. of less than 70°C, preferably of less than 50°C, this temperature being at least equal to the temperature of the keratinous substrate which has to receive the composition according to the invention. The semicrystalline polymer or polymers can thus have a melting point M.p. such that 25°C < M.p. < 70°C and preferably 30°C < M.p. < 50°C. This melting point is a first-order change in state temperature.

The melting point can be measured by any known method and in particular using a differential scanning calorimeter (DSC).

Advantageously, the semicrystalline polymer or polymers of the composition of the invention have a number-average molecular weight Mn ranging from 2000 to 800 000, preferably from 3000 to 500 000, better still from 4000 to 150 000, in particular of less than 100 000 and better still from 4000 to 99 000. Preferably, they exhibit a number- average molecular weight of greater than 5600, for example ranging from 5700 to 99 000. In the composition according to the invention, the semicrystalline polymers are advantageously soluble in the fatty phase at at least 1 % by weight, at a temperature greater than their melting point.

Apart from the crystallizable chains or blocks, the blocks of the polymers are amorphous.

Within the meaning of the invention, the expression "crystallizable chain or block" is understood to mean a chain or block which, if it were alone, would change from the amorphous state to the crystalline state reversibly, according to whether the temperature is above or below the melting point. Within the meaning of the invention, a "chain" is a group of atoms, which is pendent or lateral with respect to the backbone of the polymer.

A block is a group of atoms belonging to the backbone, this group constituting one of the repeat units of the polymer. Advantageously, the "pendent crystallizable chain" can be a chain comprising at least 6 carbon atoms.

Preferably, the crystallizable block or blocks or chain or chains of the semicrystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%. The semicrystalline polymers of the invention having crystallizable blocks are block or multiblock polymers. They can be obtained by polymerization of a monomer having reactive double bonds (or ethylenic bonds) or by polycondensation. When the polymers of the invention are polymers having crystallizable side chains, these side chains are advantageously in random or statistical form.

Preferably, the semicrystalline polymers of the invention are of synthetic origin. In addition, they do not comprise a polysaccharide backbone. In general, the crystallizable units (chains or blocks) of the semicrystalline polymers according to the invention originate from monomer(s) having crystallizable block(s) or chain(s) used for the manufacture of the semicrystalline polymers.

According to the invention, the semicrystalline polymer can be chosen from block copolymers comprising at least one crystallizable block and at least one amorphous block, homopolymers and copolymers carrying at least one crystallizable side chain per repeat unit, and their mixtures.

The semicrystalline polymers which can be used in the invention are in particular:

- block copolymers of polyolefins having controlled crystallization, in particular those whose monomers are described in EP-A-0 951 897,

- polycondensates, in particular of aliphatic or aromatic polyester or aliphatic/aromatic copolyester type,

- homo- or copolymers carrying at least one crystallizable side chain and homo- or copolymers carrying at least one crystallizable block in the backbone, such as those described in the document US-A-5 156 91 1 ,

- homo- or copolymers carrying at least one crystallizable side chain, in particular having fluorinated group(s), as described in the document WO-A-01/19333,

- and their mixtures.

In the last two cases, the crystallizable side chain or chains or block or blocks are hydrophobic. a) Semicrystalline polymers having crystallizable side chains

Mention may in particular be made of those defined in the documents US-A-5 156 91 1 and WO-A-01/19333. They are homopolymers or copolymers comprising from 50% to 100% by weight of units resulting from the polymerization of one or more monomers carrying a crystallizable hydrophobic side chain.

These homo- or copolymers are of any nature, provided that they exhibit the conditions indicated above.

They can result:

- from the polymerization, in particular radical polymerization, of one or more monomers having reactive or ethylenic double bond(s) with respect to a polymerization, namely having a vinyl, (meth)acrylic or allylic group,

- from the polycondensation of one or more monomers carrying co-reactive groups (carboxylic acid, sulfonic acid, alcohol, amine or isocyanate), such as, for example, polyesters, polyurethanes, polyethers, polyureas or polyamides.

Generally, these polymers are chosen in particular from homopolymers and copolymers resulting from the polymerization of at least one monomer having crystallizable chain(s) which can be represented by formula (I): c

with M representing an atom of the polymer backbone, S representing a spacer and C representing a crystallizable group.

The crystallizable "-S-C" chains can be aliphatic or aromatic, and optionally fluorinated or perfluorinated. "S" represents in particular a (CH₂)_n or (CH₂CH₂0)n or (CH₂0) group, which can be linear or branched or cyclic, with n being an integer ranging from 0 to 22.

Preferably, "S" is a linear group. Preferably, "S" and "C" are different.

When the crystallizable "-S-C" chains are aliphatic hydrocarbon chains, they comprise alkyl hydrocarbon chains having at least 1 1 carbon atoms and at most 40 carbon atoms and better still at most 24 carbon atoms. They are in particular aliphatic chains or alkyl chains having at least 12 carbon atoms and they are preferably Ci₄-C₂₄ alkyl chains.

When they are fluoroalkyl or perfluoroalkyl chains, they comprise at least 6 fluorinated carbon atoms and in particular at least 1 1 carbon atoms, at least 6 of which carbon atoms are fluorinated.

Mention may be made, as examples of semicrystalline polymers or copolymers having crystallizable chain(s), of those resulting from the polymerization of one or more following monomers: saturated alkyl (meth)acrylates with the alkyl group a Ci -C₂ alkyl group, perfluoroalkyl (meth)acrylates with a Cn-Ci₅ perfluoroalkyl group, N- alkyl(meth)acrylamides with the alkyl group a Ci₄ to C₂ alkyl group, with or without a fluorine atom, vinyl esters having alkyl or perfluoro(alkyl) chains with the alkyl group a Ci₄ to C₂ alkyl group (with at least 6 fluorine atoms per one perfluoroalkyl chain), vinyl ethers having alkyl or perfluoro(alkyl) chains with the alkyl group a Ci₄ to C₂ alkyl group and at least 6 fluorine atoms per one perfluoroalkyl chain, Ci₄ to C₂ oolefins, such as, for example, octadecene, para-alkylstyrenes with an alkyl group comprising from 12 to 24 carbon atoms, and their mixtures.

When the polymers result from a polycondensation, the crystallizable hydrocarbon and/or fluorinated chains as defined above are carried by a monomer which can be a diacid, a diol, a diamine or a diisocyanate.

When the polymers which are subject matters of the invention are copolymers, they additionally comprise from 0% to 50% of Y or Z groups resulting from the copolymerization:

a) of Y, which is a polar or nonpolar monomer or a mixture of the two:

. When Y is a polar monomer, it is either a monomer carrying polyoxyalkylenated groups (especially oxyethylenated and/or oxypropylenated groups), a hydroxyalkyl (meth)acrylate, such as hydroxyethyl acrylate, (meth)acrylamide, an N- alkyl(meth)acrylamide, an N,N-dialkyl(meth)acrylamide, such as, for example, N,N- diisopropylacrylamide, N-vinylpyrrolidone (NVP) or N-vinylcaprolactam, a monomer carrying at least one carboxylic acid group, such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, or carrying a carboxylic acid anhydride group, such as maleic anhydride, and their mixtures.

When Y is a nonpolar monomer, it can be an ester of the linear, branched or cyclic alkyl (meth)acrylate type, a vinyl ester, an alkyl vinyl ether, an oc-olefin, styrene or styrene substituted by a Ci to Cio alkyl group, such as oc-methylstyrene.

The term "alkyl" is understood to mean, within the meaning of the invention, a saturated group, in particular a C₈ to C₂₄ group, except when expressly mentioned otherwise, and better still a Ci₄ to C₂₄ group.

β) of Z, which is a polar monomer or a mixture of polar monomers. In this case, Z has the same definition as the "polar Y" defined above.

Preferably, the semicrystalline polymers having a crystallizable side chain are alkyl (meth)acrylate or alkyl(meth)acrylamide homopolymers with an alkyl group as defined above, in particular a Ci₄-C₂₄ alkyl group, copolymers of these monomers with a hydrophilic monomer preferably different in nature from (meth)acrylic acid, such as N- vinylpyrrolidone or hydroxyethyl (meth)acrylate, and their mixtures. b) Polymers carrying in the backbone at least one crystallizable block

These polymers are in particular block copolymers composed of at least 2 blocks of different chemical nature, one of which is crystallizable.

- Use may be made of the block polymers defined in the patent US-A-5 156 91 1 ;

- The block copolymers of olefin or of cycloolefin having a crystallizable chain, such as those resulting from the block polymerization of:

. cyclobutene, cyclohexene, cyclooctene, norbornene (that is to say, bicyclo[2.2.1 ]hept-2- ene), 5-methylnorbornene, 5-ethylnorbornene, 5,6-dimethylnorbornene, 5,5,6- trimethylnorbornene, 5-ethylidenenorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-vinylnorbornene, 1 ,4,5,8-dimethano-1 ,2,3,4,4a,5,8,8a-octahydronaphthalene, dicyclopentadiene or their mixtures,

. with ethylene, propylene, 1 -butene, 3-methyl-1 -butene, 1 -hexene, 4-methyl-1 -pentene, 1 -octene, 1 -decene, 1 -eicosene or their mixtures,

and in particular block copoly(ethylene/norbornene)s and (ethylene/propylene/ethylidenenorbornene) block terpolymers. Use may also be made of those resulting from the block copolymerization of at least two C₂-Ci₆, better still C₂-Ci₂ and even better still C4-C12 oc-olefins, such as those mentioned above, in particular block bipolymers of ethylene and of 1 -octene.

- The copolymers can be copolymers exhibiting at least one crystallizable block, the remainder of the copolymer being amorphous (at ambient temperature). These copolymers can additionally exhibit two crystallizable blocks which are different in chemical nature. The preferred copolymers are those which simultaneously have, at ambient temperature, a crystallizable block and an amorphous block which are simultaneously hydrophobic and lipophilic, and sequentially distributed; mention may be made, for example, of polymers having one of the crystallizable blocks and one of the amorphous blocks below:

. Block which is crystallizable by nature: a) polyester, such as poly(alkylene terephthalate), b) polyolefin, such as polyethylenes or polypropylenes.

. Amorphous and lipophilic block, such as amorphous polyolefins or copoly(olefin)s, such as poly(isobutylene), hydrogenated polybutadiene or hydrogenated poly(isoprene).

Mention may be made, as examples of such copolymers having a separate crystallizable block and a separate amorphous block, of:

a) poly(e-caprolactone)-b-poly(butadiene) block copolymers, preferably used hydrogenated, such as those described in the paper "Melting behavior of poly(e- caprolactone)-block-polybutadiene copolymers" by S. Nojima, Macromolecules, 32, 3727- 3734 (1999),

β) the hydrogenated block or multiblock poly(butylene terephthalate)-b-poly(isoprene) block copolymers cited in the paper "Study of morphological and mechanical properties of PP/PBT" by B. Boutevin et al., Polymer Bulletin, 34, 1 17-123 (1995),

γ) the poly(ethylene)-b-copoly(ethylene/propylene) block copolymers cited in the papers "Morphology of semi-crystalline block copolymers of ethylene-(ethylene-alt-propylene)" by P. Rangarajan et al., Macromolecules, 26, 4640-4645 (1993), and "Polymer aggregates with crystalline cores: the system poly(ethylene)-poly(ethylene-propylene)" by P. Richter et al., Macromolecules, 30, 1053-1068 (1997),

δ) the poly(ethylene)-b-poly(ethylethylene) block copolymers cited in the general article "Crystallization in block copolymers" by I.W. Hamley, Advances in Polymer Science, vol. 148, 1 13-137 (1999).

The semicrystalline polymers of the composition of the invention may or may not be partially crosslinked, provided that the degree of crosslinking does not interfere with their dissolution or dispersion in the liquid fatty phase by heating above their melting point. It may then be a case of chemical crosslinking, by reaction with a polyfunctional monomer during the polymerization. It may also be a case of physical crosslinking, which can then be due either to the establishment of bonds of hydrogen or dipolar type between groups carried by the polymer, such as, for example, dipolar interactions between carboxylate ionomers, these interactions being in low amount and carried by the backbone of the polymer; or to a phase separation between the crystallizable blocks and the amorphous blocks carried by the polymer.

Preferably, the semicrystalline polymers of the composition according to the invention are noncrosslinked.

According to a specific embodiment of the invention, the polymer is chosen from copolymers resulting from the polymerization of at least one monomer having a crystallizable chain chosen from saturated Cu to C₂₄ alkyl (meth)acrylates, Cn to Ci₅ perfluoroalkyl (meth)acrylates, N-(Ci₄ to C₂₄ alkyl)(meth)acrylamides, with or without a fluorine atom, vinyl esters having Cu to C₂₄ alkyl or perfluoroalkyl chains, vinyl ethers having Cu to C₂₄ alkyl or perfluoroalkyl chains, Cu to C₂₄ oolefins, para-alkylstyrenes with an alkyl group comprising from 12 to 24 carbon atoms, with at least one optionally fluorinated Ci to Cio monocarboxylic acid ester or amide, which can be represented by the following formula (ω):

H₂C^C C X R

R-i O in which R-i is H or CH₃, R represents an optionally fluorinated C-I-C-IO alkyl group and X represents O, N H or NR₂, where R₂ represents an optionally fluorinated C-I-C-IO alkyl group.

According to a more specific embodiment of the invention, the polymer results from a monomer having a crystallizable chain chosen from saturated Cu to C₂₂ alkyl (meth)acrylates and more particularly still poly(stearyl acrylate)s and poly(behenyl acrylate)s.

Mention may be made, as specific example of structuring semicrystalline polymer which can be used in the composition according to the invention, of polymers having the INCI name "Poly C1 0-30 Alkyl Acrylate", such as the Intelimer® products from Air Products, such as the product Intelimer® IPA 1 3-1 , which is a polystearyl acrylate, or the product Intelimer® IPA 13-6, which is a behenyl polymer.

The semicrystalline polymers can in particular be: those described in examples 3, 4, 5, 7, 9 and 13 of the patent US-A-5 156 91 1 having a -COOH group, resulting from the copolymerization of acrylic acid and of C₅ to Ci₆ alkyl (meth)acrylate and more particularly from the copolymerization:

^■ of acrylic acid, of hexadecyl acrylate and of isodecyl acrylate in a 1/16/3 ratio by weight, ^■ of acrylic acid and of pentadecyl acrylate in a 1/19 ratio by weight,

^■ of acrylic acid, of hexadecyl acrylate and of ethyl acrylate in a 2.5/76.5/20 ratio by weight,

^■ of acrylic acid, of hexadecyl acrylate and of methyl acrylate in a 5/85/10 ratio by weight,

^■ of acrylic acid and of octadecyl methacrylate in a 2.5/97.5 ratio by weight,

- of hexadecyl acrylate, of polyethylene glycol methacrylate monomethyl ether having 8 ethylene glycol units, and of acrylic acid in an 8.5/1/0.5 ratio by weight.

Use may also be made of the polymer of structure "O" from National Starch, such as that described in the document US-A-5 736 125, with a melting point of 44°C, and also of semicrystalline polymers having crystallizable pendent chains comprising fluorinated groups, such as described in examples 1 , 4, 6, 7 and 8 of the document WO-A-01/19333. Use may also be made of the semicrystalline polymers obtained by copolymerization of stearyl acrylate and of acrylic acid or of NVP, such as described in the document US-A-5 519 063 or EP-A-550 745, with melting points of 40°C and 38°C respectively.

Use may also be made of the semicrystalline polymers obtained by copolymerization of behenyl acrylate and of acrylic acid or of NVP, such as described in the documents US-A- 5 519 063 and EP-A-550 745, with melting points of 60°C and 58°C respectively.

Preferably, the semicrystalline polymers do not comprise a carboxylic group.

The semicrystalline polymer or polymers can be present in the composition in an amount of active material ranging from 0.1 % to 12% by weight, preferably from 1 % to 6% by weight and better still from 1 % to 3% by weight, with respect to the total weight of the composition.

The composition according to the invention can be provided in various formulation forms conventionally used for topical applications and in particular in the form of dispersions of the serum type, of emulsions with a liquid or semiliquid consistency of the milk type, obtained by dispersion of a fatty phase in an aqueous phase (O/W) or vice versa (W/O), or of suspensions or emulsions with a soft, semisolid or solid consistency of the cream or gel type, or alternatively of multiple emulsions (W/O/W or 0/W/O), of microemulsions, or of vesicular dispersions of ionic and/or nonionic type. These compositions are prepared according to the usual methods. In addition, the compositions used according to the invention can be more or less fluid and can have the appearance of a gel, a white or colored cream, an ointment, a milk, a serum, a paste or a foam. According to a specific embodiment, the composition according to the invention is provided in the form of an anhydrous composition.

According to another specific embodiment, the composition according to the invention is provided in the form of a water-in-oil emulsion comprising a continuous oily phase and an aqueous phase dispersed in said oily phase or in the form of an oil-in-water emulsion comprising a continuous aqueous phase and an oily phase dispersed in said aqueous phase.

Within the meaning of the present invention, the term "anhydrous" is understood to mean a composition comprising a content of less than or equal to 1 % by weight of water, preferably of less than or equal to 0.5% by weight, with respect to the total weight of said composition, indeed even devoid of water. If appropriate, such small amounts of water may in particular be introduced by ingredients of the composition, which may comprise residual amounts thereof. Fatty phase

The composition according to the invention comprises at least one fatty phase.

When the composition is provided in the form of an anhydrous composition, the proportion of the fatty phase can range, for example, from 30% to 99% by weight and preferably from 50% to 90% by weight, with respect to the total weight of the composition. When the composition is provided in the form of an emulsion, the proportion of the fatty phase can range, for example, from 1 % to 80% by weight and preferably from 5% to 40% by weight, with respect to the total weight of the composition.

This indicated amount does not comprise the content of lipophilic surfactants.

Within the meaning of the invention, the fatty phase includes any fatty substance which is liquid at ambient temperature and atmospheric pressure, generally oils, or which is solid at ambient temperature and atmospheric pressure, such as waxes, or any pasty compound, which are present in said composition.

The fatty phase of the composition in accordance with the invention generally comprises at least one volatile or nonvolatile oil.

The term "oil" is understood to mean any fatty substance which is in liquid form at ambient temperature (25°C) and at atmospheric pressure. The volatile or nonvolatile oils can be hydrocarbon oils, in particular of animal or vegetable origin, synthetic oils, silicone oils, fluorinated oils or their mixtures.

Within the meaning of the present invention, the term "silicone oil" is understood to mean an oil comprising at least one silicon atom, and in particular at least one Si-0 group.

The term "hydrocarbon oil" is understood to mean an oil mainly comprising hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur and/or phosphorus atoms.

Nonvolatile oils

Within the meaning of the present invention, the term "nonvolatile oil" is understood to mean an oil having a vapor pressure of less than 0.13 Pa (0.01 mmHg).

The nonvolatile oils can be chosen in particular from nonvolatile hydrocarbon oils, if appropriate fluorinated, and/or nonvolatile silicone oils.

Mention may in particular be made, as nonvolatile hydrocarbon oil suitable for use in the invention, of:

- hydrocarbon oils of animal origin,

- hydrocarbon oils of vegetable origin, such as phytosteryl esters, such as phytosteryl oleate, phytosteryl isostearate and lauroyl/octyldodecyl/phytosteryl glutamate, for example sold under the name Eldew PS203 by Ajinomoto, triglycerides composed of fatty acid esters of glycerol, the fatty acids of which can have varied chain lengths from C₄ to C₂₄, it being possible for the latter to be linear or branched and saturated or unsaturated; these oils are in particular heptanoic or octanoic triglycerides, wheat germ oil, sunflower oil, grape seed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkinseed oil, cucumber oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil or musk rose oil; shea butter; or alternatively caprylic/capric acid triglycerides, such as those sold by Stearineries Dubois or those sold under the names Miglyol 810^®, 812^® and 818^® by Dynamit Nobel; or the refined vegetable perhydrosqualene sold under the name Fitoderm by Cognis,

- hydrocarbon oils of mineral or synthetic origin, such as, for example:

• synthetic ethers having from 10 to 40 carbon atoms,

• linear or branched hydrocarbons of mineral or synthetic origin, such as liquid petroleum, polydecenes, hydrogenated polyisobutene, such as Parleam, squalane and their mixtures, in particular hydrogenated polyisobutene,

· synthetic esters, such as oils of formula RiCOOR₂ in which R-i represents the residue of a linear or branched fatty acid comprising from 1 to 40 carbon atoms and R₂ represents a hydrocarbon chain, in particular a branched hydrocarbon chain, comprising from 1 to 40 carbon atoms, provided that R-i + R₂ is > 10.

The esters can in particular be chosen from esters, in particular fatty acid esters, such as, for example:

❖ dicaprylyl carbonate (Cetiol CC from Cognis), cetearyl octanoate, esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2- ethylhexyl palmitate, isopropyl stearate, isopropyl isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, in particular isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate, 2-ethylhexyl palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol di(2- ethylhexanoate) and their mixtures, benzoates of Ci₂ to Ci₅ alcohols, hexyl laurate, neopentanoic acid esters, such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate or octyldodecyl neopentanoate, isononanoic acid esters, such as isononyl isononanoate, isotridecyl isononanoate or octyl isononanoate, or hydroxylated esters, such as isostearyl lactate or diisostearyl malate,

• polyol esters and pentaerythritol esters, such as d i pentaeryth rity I tetrahydroxystearate/tetraisostearate,

❖ esters of dimer diols and of dimer diacids, such as Lusplan DD-DA5^® and

Lusplan DD-DA7^®, sold by Nippon Fine Chemical and described in patent application FR 03 02809,

• fatty alcohols which are liquid at ambient temperature, comprising a branched and/or unsaturated carbon chain having from 12 to 26 carbon atoms, such as 2-octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2- undecylpentadecanol,

• higher fatty acids, such as oleic acid, linoleic acid, linolenic acid and their mixtures, and

• dialkyl carbonates, it being possible for the two alkyl chains to be identical or different, such as dicaprylyl carbonate, sold under the name Cetiol CC® by Cognis,

• nonvolatile silicone oils, such as, for example, nonvolatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups which are pendent and/or at the ends of the silicone chain, which groups each have from 2 to 24 carbon atoms, phenyl silicones, such as phenyl trimethicones, phenyl dimethicones, phenyl(trimethylsiloxy)diphenylsiloxanes, diphenyl dimethicones, diphenyl(methyldiphenyl)trisiloxanes and (2-phenylethyl)trimethylsiloxysilicates, dimethicones or phenyl trimethicones with a viscosity of less than or equal to 100 cSt, and their mixtures;

- and their mixtures. Volatile oils

Within the meaning of the present invention, the term "volatile oil" is understood to mean an oil (or nonaqueous medium) which is capable of evaporating on contact with the skin in less than one hour, at ambient temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil which is liquid at ambient temperature, having in particular a nonzero vapor pressure at ambient temperature and atmospheric pressure, especially having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10^"3 to 300 mmHg), in particular ranging from 1 .3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

The volatile hydrocarbon oils can be chosen from hydrocarbon oils having from 8 to 16 carbon atoms, in particular branched C₈-Ci₆ alkanes (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane or isohexadecane, for example the oils sold under the Isopar^® or Permethyl^® trade names. Use may also be made, as volatile oils, of volatile silicones, such as, for example, volatile linear or cyclic silicone oils, in particular those having a viscosity < 8 centistokes (8 x 10^"6 m²/s) and having in particular from 2 to 10 silicon atoms and especially from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. Mention may in particular be made, as volatile silicone oil which can be used in the invention, of dimethicones with viscosities of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane and their mixtures.

Use may also be made of volatile fluorinated oils, such as nonafluoromethoxybutane or perfluoromethylcyclopentane, and their mixtures.

It is also possible to use a mixture of the oils mentioned above.

Within the meaning of the present invention, the term "pasty fatty substance" is understood to mean a lipophilic fatty compound which exhibits a reversible solid/liquid change in state, which exhibits, in the solid state, an anisotropic crystalline arrangement and which comprises, at a temperature of 23°C, a liquid fraction and a solid fraction. In other words, the starting melting point of the pasty fatty substance can be less than 23°C. The liquid fraction of the pasty fatty substance, measured at 23°C, can represent from 9% to 97% by weight of the pasty fatty substance. This liquid fraction at 23°C preferably represents between 15% and 85% and more preferably between 40% and 85% by weight.

Within the meaning of the invention, the melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in the standard ISO 1 1357-3; 1999. The melting point of a pasty fatty substance can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2920 by TA Instruments.

The measurement protocol is as follows:

A sample of 5 mg of pasty fatty substance placed in a crucible is subjected to a first temperature rise ranging from -20°C to 100°C, at a heating rate of 10°C/minute, is then cooled from 100°C to -20°C at a cooling rate of 10°C/minute and is finally subjected to a second temperature rise ranging from -20°C to 100°C, at a heating rate of 5°C/minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the sample of pasty fatty substance is measured as a function of the temperature. The melting point of the pasty fatty substance is the value of the temperature corresponding to the tip of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.

The liquid fraction by weight of the pasty fatty substance at 23°C is equal to the ratio of the enthalpy of fusion consumed at 23°C to the enthalpy of fusion of the pasty fatty substance.

The enthalpy of fusion of the pasty fatty substance is the enthalpy consumed by the latter in order to pass from the solid state to the liquid state. The pasty fatty substance is said to be in the solid state when all of its mass is in crystalline solid form. The pasty fatty substance is said to be in the liquid state when all of its mass is in liquid form.

The enthalpy of fusion of the pasty fatty substance is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name MDSC 2920 by TA Instruments, with a temperature rise of 5°C or 10°C per minute, according to the standard ISO 1 1357-3:1999.

The enthalpy of fusion of the pasty fatty substance is the amount of energy required to make the pasty fatty substance change from the solid state to the liquid state. It is expressed in J/g. The enthalpy of fusion consumed at 23°C is the amount of energy absorbed by the sample to change from the solid state to the state which it exhibits at 23°C, consisting of a liquid fraction and a solid fraction.

The liquid fraction of the pasty fatty substance measured at 32°C preferably represents from 30% to 100% by weight of the pasty fatty substance, preferably from 50% to 100%, more preferably from 60% to 100% by weight of the pasty fatty substance. When the liquid fraction of the pasty fatty substance measured at 32°C is equal to 100%, the temperature of the end of the melting range of the pasty fatty substance is less than or equal to 32°C.

The liquid fraction of the pasty fatty substance measured at 32°C is equal to the ratio of the enthalpy of fusion consumed at 32°C to the enthalpy of fusion of the pasty fatty substance. The enthalpy of fusion consumed at 32°C is calculated in the same way as the enthalpy of fusion consumed at 23°C.

The pasty fatty substance is preferably chosen from synthetic fatty substances and fatty substances of vegetable origin. A pasty fatty substance can be obtained by synthesis from starting materials of vegetable origin.

The pasty fatty substance is advantageously chosen from:

lanolin and its derivatives,

polyol ethers chosen from ethers of pentaerythritol and of polyalkylene glycol, ethers of fatty alcohol and of sugar, and their mixtures, the ether of pentaerythritol and of polyethylene glycol comprising 5 oxyethylene (5 OE) units (CTFA name: PEG-5 Pentaerythrityl Ether), the ether of pentaerythritol and of polypropylene glycol comprising 5 oxypropylene (5 OP) units (CTFA name: PPG-5 Pentaerythrityl Ether), and their mixtures, and more especially the PEG-5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether and soybean oil mixture, sold under the name Lanolide by Vevy, in which mixture the constituents are in a 46/46/8 ratio by weight: 46% PEG-5 Pentaerythrityl Ether, 46% PPG-5 Pentaerythrityl Ether and 8% soybean oil,

polymeric or nonpolymeric silicone compounds,

polymeric or nonpolymeric fluorinated compounds,

- vinyl polymers, in particular:

^■ olefin homopolymers and copolymers,

^■ hydrogenated diene homopolymers and copolymers,

fat-soluble polyethers resulting from the polyetherification between one or more C₂- Cioo and preferably C₂-C₅o diols,

- esters,

and/or their mixtures.

The pasty fatty substance is preferably a polymer, in particular a hydrocarbon polymer. Preference is given in particular, among the fat-soluble polyethers, to copolymers of ethylene oxide and/or of propylene oxide with long-chain C₆-C₃₀ alkylene oxides, more preferably such that the ratio by weight of the ethylene oxide and/or of the propylene oxide to the alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, mention will in particular be made of copolymers such that the long-chain alkylene oxides are arranged in blocks having an average molecular weight of from 1000 to 10 000, for example a polyoxyethylene/polydodecyl glycol block copolymer, such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 OE) sold under the brand name Elfacos ST9 by Akzo Nobel.

Preference is given in particular, among the esters, to:

esters of a glycerol oligomer, in particular diglycerol esters, especially condensates of adipic acid and of glycerol, for which a portion of the hydroxyl groups of the glycerols has reacted with a mixture of fatty acids, such as stearic acid, capric acid, isostearic acid and 12-hydroxystearic acid, such as in particular those sold under the brand name Softisan 649 by Sasol,

the arachidyl propionate sold under the brand name Waxenol 801 by Alzo, phytosterol esters,

fatty acid triglycerides and their derivatives,

pentaerythritol esters,

- esters of dimer diol and dimer diacid, if appropriate esterified on their free alcohol or acid functional group(s) by acid or alcohol radicals, in particular dimer dilinoleate esters; such esters can be chosen in particular from esters with the following INCI nomenclature: bis-behenyl/isostearyl/phytosteryl dimer dilinoleyl dimer dilinoleate (Plandool G), phytosteryl isostearyl dimer dilinoleate (Lusplan PI-DA or Lusplan PHY/IS-DA), phytosteryl/isostearyl/cetyl/stearyl/behenyl dimer dilinoleate (Plandool H or Plandool S), and their mixtures,

mango butter, such as that sold under the reference Lipex 203 by AarhusKarlshamn, hydrogenated soybean oil, hydrogenated coconut oil, hydrogenated rapeseed oil or mixtures of hydrogenated vegetable oils, such as the soybean, coconut, palm and rapeseed hydrogenated vegetable oil mixture, for example the mixture sold under the reference Akogel^® by AarhusKarlshamn (INCI name: Hydrogenated Vegetable Oil),

shea butter, in particular that having the INCI name Butyrospermum Parkii Butter, such as that sold under the reference Sheasoft^® by AarhusKarlshamn,

cocoa butter, in particular that which is sold under the name CT Cocoa Butter Deodorized by Dutch Cocoa BV or that which is sold under the name Beurre De Cacao NCB HD703 758 by Barry Callebaut, shorea butter, in particular that which is sold under the name Dub Shorea T by Stearinerie Dubois,

and their mixtures.

According to a preferred embodiment, the pasty fatty substance is chosen from shea butter, cocoa butter, shorea butter, a soybean, coconut, palm and rapeseed hydrogenated vegetable oil mixture, and their mixtures, and more particularly those referenced above.

The waxes under consideration in the context of the present invention are generally deformable or nondeformable solid lipophilic compounds at ambient temperature (25°C) which exhibit a reversible solid/liquid change in state and which have a melting point of greater than or equal to 30°C which can range up to 200°C and in particular up to 120°C.

On bringing one or more waxes in accordance with the invention to the liquid state

(melting), it is possible to render it or them miscible with one or more oils and to form a macroscopically homogeneous mixture of wax(es) and oil(s) but, on bringing the temperature of said mixture back to ambient temperature, recrystallization of the wax(es) in the oil(s) of the mixture is obtained.

Within the meaning of the invention, the melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in the standard ISO 1 1357-3; 1999. The melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2920 by TA Instruments.

The measurement protocol is as follows:

A sample of 5 mg of wax placed in a crucible is subjected to a first temperature rise ranging from -20°C to 100°C, at a heating rate of 10°C/minute, it is then cooled from 100°C to -20°C at a cooling rate of 10°C/minute and finally it is subjected to a second temperature rise ranging from -20°C to 100°C, at a heating rate of 5°C/minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the sample of wax is measured as a function of the temperature. The melting point of the compound is the value of the temperature corresponding to the tip of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.

The waxes capable of being used in a composition according to the invention are chosen from waxes of animal, vegetable, mineral or synthetic origin and their mixtures which are solid at ambient temperature. They can be hydrocarbon, fluorinated and/or silicone waxes. Mention may in particular be made, by way of examples, of hydrocarbon waxes, such as natural beeswax (or bleached beeswax), synthetic beeswax, carnauba wax, rice bran wax, such as that sold under the reference NC 1720 by Cera Rica Noda, candelilla wax, such as that sold under the reference SP 75 G by Strahl & Pitsch, microcrystalline waxes, such as, for example, the microcrystalline waxes having a melting point of greater than 85°C, such as the products HI-MIC® 1070, 1080, 1090 and 3080 sold by Nippon Seiro, ceresins or ozokerites, such as, for example, isoparaffins having a melting point of less than 40°C, such as the product EMW-0003 sold by Nippon Seiro, oolefin oligomers, such as the Performa V® 825, 103 and 260 polymers sold by New Phase Technologies, ethylene/propylene copolymers, such as Performalene® EP 700, polyethylene waxes (preferably with a molecular weight of between 400 and 600), Fischer-Tropsch waxes or the sunflower seed wax sold by Koster Keunen under the reference Sunflower Wax.

Mention may also be made of silicone waxes, such as alkyl or alkoxy dimethicones having from 16 to 45 carbon atoms, or fluorinated waxes.

According to a specific embodiment, the wax used in a composition in accordance with the invention exhibits a melting point of greater than 35°C, better still of greater than 40°C, indeed even of greater than 45°C or also of greater than 55°C.

According to a preferred embodiment, the wax or waxes are chosen from polymethylene waxes; the silicone wax sold under the name Dow Corning 2501 Cosmetic Wax by Dow Corning (INCI name: bis-PEG-18 methyl ether dimethyl silane); beeswax; vegetable waxes, such as carnauba wax; the mixture of polyglycerolated (3 mol) vegetable (mimosa/jojoba/sunflower) waxes sold under the name Hydracire S by Gattefosse; or the hydrogenated castor oil sold under the name Antisettle CVP by Cray Valley. The other fatty substances which can be present in the fatty phase are, for example, fatty acids comprising from 8 to 30 carbon atoms, such as stearic acid, lauric acid or palmitic acid, or fatty alcohols comprising from 8 to 30 carbon atoms, such as stearyl alcohol, cetyl alcohol and their mixtures (cetearyl alcohol).

The fatty phase can also comprise other compounds dissolved in the oils, such as gelling agents and/or structuring agents.

These compounds can in particular be chosen from gums, such as silicone gums (dimethiconol); silicone resins, such as trifluoromethyl C1 -4 alkyl dimethicone and trifluoropropyl dimethicone; and silicone elastomers, such as the products sold under the KSG names by Shin-Etsu, under the Trefil name by Dow Corning or under the Gransil names by Grant Industries; and their mixtures. These fatty substances can be chosen in a manner varied by a person skilled in the art in order to prepare a composition having the desired properties, for example of consistency or texture. According to a specific embodiment of the invention, the composition comprises at least one solid fatty substance, in particular a wax.

Aqueous phase

When the composition in accordance with the invention is provided in the form of an emulsion, the aqueous phase comprises at least water. According to the formulation form of the composition, the amount of aqueous phase can range from 0.1 % to 99% by weight, preferably from 0.5% to 98% by weight, better still from 30% to 95% by weight and even better still from 40% to 95% by weight, with respect to the total weight of the composition.

This amount depends on the formulation form of the composition desired. The amount of water can represent all or a portion of the aqueous phase and it is generally at least 30% by weight, preferably at least 50% by weight and better still at least 60% by weight, with respect to the total weight of the composition.

The aqueous phase can comprise at least one hydrophilic solvent, such as, for example, substantially linear or branched lower monoalcohols having from 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol or isobutanol; polyols, such as propylene glycol, isoprene glycol, butylene glycol, glycerol, sorbitol or polyethylene glycols and their derivatives, and their mixtures.

The emulsions generally comprise at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The emulsifiers are appropriately chosen according to the emulsion to be obtained (W/O or O/W).

The emulsifiers are generally present in the composition in a proportion as active material ranging from 0.1 % to 30% by weight and preferably from 0.2% to 20% by weight, with respect to the total weight of the composition.

Mention may be made, for the W/O emulsions, for example, as emulsifiers, of dimethicone copolyols, such as the mixture of cyclomethicone and of dimethicone copolyol sold under the name DC 5225 C by Dow Corning or the oxyethylenated polydimethylsiloxane PEG-10 Dimethicone sold under the name KF-6017 by Shin-Etsu, and alkyl dimethicone copolyols, such as the lauryl methicone copolyol sold under the name Dow Corning 5200 Formulation Aid by Dow Corning and the cetyl dimethicone copolyol sold under the name Abil EM 90^R by Goldschmidt, or the polyglyceryl-4 isostearate/cetyl dimethicone copolyol/hexyl laurate mixture sold under the name Abil WE 09 by Goldschmidt. One or more coemulsifiers can also be added thereto. The coemulsifier can advantageously be chosen from the group consisting of polyol alkyl esters. Mention may in particular be made, as polyol alkyl esters, of glycerol and/or sorbitan esters, for example polyglyceryl isostearate, such as the product sold under the name Isolan Gl 34 by Goldschmidt, sorbitan isostearate, such as the product sold under the name Arlacel 987 by ICI, sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986 by ICI, and their mixtures.

Mention may be made, for the O/W emulsions, for example, as emulsifiers, of nonionic surfactants and in particular esters of polyols and of fatty acid having a saturated or unsaturated chain comprising, for example, from 8 to 24 carbon atoms and better still from 12 to 22 carbon atoms, and their oxyalkylenated derivatives, that is to say derivatives comprising oxyethylene and/or oxypropylene units, such as glyceryl esters of C₈-C₂4 fatty acid, and their oxyalkylenated derivatives; polyethylene glycol esters of C₈- C₂4 fatty acid, and their oxyalkylenated derivatives; sorbitol esters of C₈-C₂4 fatty acid, and their oxyalkylenated derivatives; fatty alcohol ethers; sugar ethers of C₈-C₂4 fatty alcohols, and their mixtures.

Mention may in particular be made, as glyceryl ester of fatty acid, of glyceryl stearate (glyceryl mono-, di- and/or tristearate) (CTFA name: glyceryl stearate) or glyceryl ricinoleate, and their mixtures.

Mention may in particular be made, as polyethylene glycol ester of fatty acid, of polyethylene glycol stearate (polyethylene glycol mono-, di- and/or tristearate) and more especially polyethylene glycol 50 OE monostearate (CTFA name: PEG-50 stearate), polyethylene glycol 100 OE monostearate (CTFA name: PEG-100 stearate) and their mixtures.

Use may also be made of mixtures of these surfactants, such as, for example, the product comprising glyceryl stearate and PEG-100 stearate, sold under the name Arlacel 165 by Uniqema, and the product comprising glyceryl stearate (glyceryl mono/distearate) and potassium stearate, sold under the name Tegin by Goldschmidt (CTFA name: glyceryl stearate SE).

Mention may be made, as fatty alcohol ethers, for example, of polyethylene glycol ethers of fatty alcohol comprising from 8 to 30 carbon atoms and in particular from 10 to 22 carbon atoms, such as polyethylene glycol ethers of cetyl alcohol, stearyl alcohol or cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol). Mention may be made, for example, of ethers comprising from 1 to 200 and preferably from 2 to 100 oxyethylene groups, such as those with the CTFA name Ceteareth-20 or Ceteareth-30, and their mixtures. Mention may be made, as examples of sugar mono- or polyalkyl esters or ethers, of methyl glucose isostearate, sold under the name Isolan-IS by Degussa Goldschmidt, or else sucrose distearate, sold under the name Crodesta F50 by Croda, and sucrose stearate, sold under the name Ryoto sugar ester S 1570 by Mitsubishi Kagaku Foods. Mention may also be made of lipoamino acids and their salts, such as monosodium and disodium acylglutamates, such as, for example, monosodium stearoyl glutamate, sold under the name Amisoft HS-1 1 PF, and disodium stearoyl glutamate, sold under the name Amisoft HS-21 P, by Ajinomoto. In a known way, all the compositions of the invention can comprise one or more of the adjuvants normal in the cosmetic and dermatological fields: hydrophilic or lipophilic gelling agents and/or thickeners; moisturizers; emollients; hydrophilic or lipophilic active agents; agents for combating free radicals; sequestering agents; antioxidants; preservatives; basifying or acidifying agents; fragrances; film-forming agents; fillers; and their mixtures.

The amounts of these various adjuvants are those conventionally used in the fields under consideration. In particular, the amounts of active agents vary according to the desired objective and are those conventionally used in the fields under consideration, for example from 0.1 % to 20% and preferably from 0.5% to 10% by weight of the total weight of the composition.

Active agents

Mention may be made, by way of example of active agent and without implied limitation, of ascorbic acid and its derivatives, such as 5,6-di-O- dimethylsilylascorbate (sold by Exsymol under the reference PRO-AA), the potassium salt of D,L-a-tocopheryl 2-L-ascorbyl phosphate (sold by Senju Pharmaceutical under the reference Sepivital EPC), magnesium ascorbyl phosphate, sodium ascorbyl phosphate (sold by Roche under the reference Stay-C 50); phloroglucinol; enzymes; and their mixtures. According to a preferred embodiment of the invention, use is made, among oxidation-sensitive hydrophilic active agents, of ascorbic acid. The ascorbic acid can be of any nature. Thus, it can be of natural origin in the powder form or in the form of orange juice, preferably orange juice concentrate. It can also be of synthetic origin, preferably in the powder form.

Mention may be made, as other active agents which can be used in the composition of the invention, for example, of moisturizing agents, such as protein hydrolyzates and polyols, such as glycerol, glycols, such as polyethylene glycols; natural extracts; anti- inflammatories; procyanidol oligomers; vitamins, such as vitamin A (retinol), vitamin E (tocopherol), vitamin B5 (panthenol), vitamin B3 (niacinamide), the derivatives of these vitamins (in particular esters) and their mixtures; urea; caffeine; depigmenting agents, such as kojic acid, hydroquinone and caffeic acid; salicylic acid and its derivatives; - hydroxy acids, such as lactic acid and glycolic acid and their derivatives; retinoids, such as carotenoids and vitamin A derivatives; hydrocortisone; melatonin; extracts of algae, of fungi, of plants, of yeasts or of bacteria; steroids; antibacterial active agents, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether (or triclosan), 3,4,4'-trichlorocarbanilide (or triclocarban) and the acids indicated above, in particular salicylic acid and its derivatives; mattifying agents, such as fibers; tensioning agents; UV screening agents, in particular organic UV screening agents; and their mixtures.

Of course, a person skilled in the art will take care to choose the optional adjuvant or adjuvants added to the composition according to the invention so that the advantageous properties intrinsically attached to the composition in accordance with the invention are not, or not substantially, detrimentally affected by the envisaged addition.

The examples which follow will make possible a better understanding of the invention without, however, exhibiting a limiting nature. The amounts indicated are given as % by weight of starting material, unless otherwise mentioned. The names of the compounds are shown as INCI names.

EXAMPLES The rate of absorption is evaluated by a panel of 8 experts trained in the description of care products. The sensory evaluation is carried out as follows: 0.05 ml of product is applied to the back of the hand and the time necessary for the complete penetration of the product is evaluated.

The rate of absorption is recorded on a scale having 4 levels: very slow, medium, fast and very fast.

Mature skin nutritive balm

The following compositions were prepared.

A

B (invention)

(comparative)

A Water q.s. for 100 q.s. for 100 Preservative(s) 0.25 0.25

Glycerin 7 7

Behenyl alcohol (and) glyceryl stearate (and)

disodium ethylene dicocamide PEG-15 disulfate

B 3 3

(and) glyceryl stearate citrate

(Ceralution H from Sasol)

Isononyl isononanoate 5 5

Poly C10-30 alkyl acrylate

2 2 (Intelimer IPA 13-1 from Air Products)

Pentaerythrityl tetraisostearate 2 2

Hydrogenated polyisobutene 4 4

Cetearyl ethylhexanoate (and) isopropyl

5 5 myristate

Synthetic wax 4 4

Carnauba wax 2 2

Caprylyl methicone 1 .5 1 .5

Dimethicone (and) dimethiconol

2 2 (Mirasil D-DML LV from Bluestar)

Steareth-20 1 1

Ammonium polyacryloyldimethyl taurate 0.5 0.5 (Hostacerin AMPS® from Clariant)

Xanthan gum 0.25 0.25

C

Dimethicone

(Xiameter PMX-200 Silicone Fluid 5CS from 2 2 Dow Corning)

Silica Silylate

D - 1

(Aerogel VM2270 from Dow Corning)

Silica

E 3 3

(SB 700 from Miyoshi Kasei)

Manufacturing process

Phase A is homogenized while heating to 80°C;

Phase B is melted on a water bath and homogenized;

- The emulsion is formed by adding phase B to phase A at 75°C with stirring;

Phase C is added with stirring; Cooling is carried out with gentle stirring and then the fillers D and E are added at 25°C.

Results of the comparative evaluation

In conclusion, the composition B according to the invention is absorbed more rapidly than the comparative composition A.

Anti-aging smoothing butter

The following compositions were prepared.

C D

(comparative) (invention)

Water q.s. for 100 q.s. for 100

A Preservatives 0.25 0.25

Glycerin 7 7

Oxyethylenated (16 OE) dimethylsiloxane

5 5

having a methoxy end

Behenyl alcohol (and) glyceryl stearate (and)

disodium ethylene dicocamide PEG-15 disulfate

B 3 3

(and) glyceryl stearate citrate

(Ceralution H from Sasol)

Isohexadecane 12 12

Poly C10-30 alkyl acrylate

2 2

(Intelimer IPA 13-1 from Air Products)

Hexadecyl laurate and hexyldecanol 3 3

Beeswax 3 3

Synthetic wax 6 6

Carnauba wax 0.75 0.75

Wax 5 5

C Ammonium polyacryloyldimethyl taurate 1 1 (Hostacerin AMPS® from Clariant)

Xanthan gum 0.25 0.25

Dimethicone

(Xiameter PMX-200 Silicone Fluid 5CS from 3.5 1

Dow Corning)

Silica Silylate

D - 0.8

(Aerogel VM2270 from Dow Corning)

Aluminum Starch Octenylsuccinate

E 3 3

(Dry Flow from Akzo Nobel)

Manufacturing process

Phase A is homogenized while heating to 80°C;

Phase B is melted on a water bath and homogenized;

- The emulsion is formed by adding phase B to phase A at 75°C with stirring;

Phase C is added with stirring;

Cooling is carried out with gentle stirring and then the fillers D and E are added at 25°C. Results of the comparative evaluation

In conclusion, the composition D according to the invention is absorbed more rapidly than the comparative composition C.

SPF15 day moisturizing fluid

The following compositions were

E

F (invention)

(comparative)

Water q.s. for 100 q.s. for 100

A

Preservatives 0.25 0.25 Glycerin 7 7

Xanthan gum 0.2 0.2

Behenyl alcohol (and) glyceryl stearate (and)

disodium ethylene dicocamide PEG-15 disulfate

B 3 3

(and) glyceryl stearate citrate

(Ceralution H from Sasol)

Isohexadecane 6 6

Poly C10-30 alkyl acrylate

2 2

(Intelimer IPA 13-1 from Air Products)

UV screening agent(s) 9 9

Ammonium polyacryloyldimethyl taurate

C

(Hostacerin AMPS® from Clariant) 0.5 0.5

Aluminum Starch Octenylsuccinate

D 3 3

(Dry Flow from Akzo Nobel)

Silica Silylate

E - 1

(Aerogel VM2270 from Dow Corning)

Manufacturing process:

Phase A is homogenized while heating to 80°C;

Phase B is melted on a water bath and homogenized;

- The emulsion is formed by adding phase B to phase A at 75°C with stirring;

Phase C is added with stirring;

Cooling is carried out with gentle stirring and then the fillers D and E are added at 25°C. Results of the comparative evaluation

In conclusion, the composition F according to the invention is absorbed more rapidly than the comparative composition E.

Claims

1 . A composition for topical application comprising:

hydrophobic silica aerogel particles exhibiting a specific surface per unit of weight (Sw) ranging from 500 to 1500 m²/g, preferably from 600 to 1200 m²/g and better still from 600 to 800 m²/g, and a size, expressed as volume-average diameter (D[0.5]), ranging from 1 to 1500 μηη, preferably from 1 to 1000 μηη, more preferentially still from 1 to 100 μηη, in particular from 1 to 30 μηη, more preferably from 5 to 25 μηη, better still from 5 to 20 μηη and even better still from 5 to 15 μηη;

- at least one semicrystalline polymer which is solid at ambient temperature and which has a melting point of less than 70°C, comprising a) a polymeric backbone and b) at least one crystallizable organic side chain and/or one crystallizable organic block forming part of the backbone of said polymer, said polymer having a number-average molecular weight of greater than or equal to 2000; and

- at least one fatty phase.

2. The composition as claimed in claim 1 , in which the hydrophobic silica aerogel particles exhibit a specific surface per unit of volume S_v ranging from 5 to 60 m²/cm³, preferably from 10 to 50 m²/cm³ and better still from 15 to 40 m²/cm³ and/or an oil absorption capacity, measured at the wet point, ranging from 5 to 18 ml/g of particles, preferably from 6 to 15 ml/g and better still from 8 to 12 ml/g.

3. The composition as claimed in either of claims 1 and 2, in which the hydrophobic silica aerogel particles are trimethylsiloxylated silica particles.

4. The composition as claimed in any one of claims 1 to 3, in which the hydrophobic silica aerogel particles are present in a content as active material ranging from 0.1 % to 15% by weight, preferably from 1 % to 10% by weight, better still from 1 % to 5% by weight and more preferably from 1 % to 3% by weight, with respect to the total weight of the composition.

5. The composition as claimed in any one of claims 1 to 4, in which the semicrystalline polymer or polymers have a number-average molecular weight ranging from 3000 to 500 000 and better still from 4000 to 99 000.

6. The composition as claimed in any one of claims 1 to 5, in which the semicrystalline polymer or polymers are soluble in the fatty phase at at least 1 % by weight at a temperature greater than its melting point.

7. The composition as claimed in any one of claims 1 to 6, in which the semicrystalline polymer or polymers have a melting point M.p. such that 30°C < M.p. < 50°C.

8. The composition as claimed in any one of claims 1 to 7, in which the semicrystalline polymer or polymers are chosen from:

- block copolymers of polyolefins having controlled crystallization;

- aliphatic or aromatic polyester polycondensates and aliphatic/aromatic copolyesters;

- homo- or copolymers carrying at least one crystallizable side chain and homo- or copolymers carrying at least one crystallizable block in the backbone;

- homo- or copolymers carrying at least one crystallizable side chain having fluorinated group(s);

- and their mixtures.

9. The composition as claimed in any one of claims 1 to 8, in which the semicrystalline polymer or polymers are chosen from homopolymers and copolymers comprising from 50% to 1 00% by weight of units resulting from the polymerization of one or more monomers carrying crystallizable hydrophobic side chain(s).

1 0. The composition as claimed in any one of claims 1 to 9, in which the semicrystalline polymer or polymers are chosen from homopolymers and copolymers resulting from the polymerization of at least one monomer having a crystallizable chain chosen from saturated C14-C24 alkyl (meth)acrylates, Cn-Ci₅ perfluoroalkyl (meth)acrylates, N-(Ci₄ to C₂₄ alkyl)(meth)acrylamides, with or without a fluorine atom, vinyl esters having Ci₄ to C₂₄ alkyl or perfluoroalkyl chains, vinyl ethers having Ci₄ to C₂₄ alkyl or perfluoroalkyl chains, CM to C₂₄ oolefins, para-alkylstyrenes with an alkyl group comprising from 1 2 to 24 carbon atoms, and their mixtures.

1 1 . The composition as claimed in any one of claims 1 to 1 0, in which the semicrystalline polymer or polymers are chosen from Ci₄ to C₂₄ alkyl (meth)acrylate or (Ci₄ to C₂₄ alkyl)(meth)acrylamide homopolymers; copolymers of these monomers with a hydrophilic monomer; and their mixtures.

12. The composition as claimed in any one of claims 1 to 1 1 , in which the semicrystalline polymer or polymers are chosen from copolymers of alkyl (meth)acrylate or alkyl(meth)acrylamide, with a Cu to C₂₄ alkyl group, with N-vinylpyrrolidone or hydroxyethyl (meth)acrylate; or their mixtures.

13. The composition as claimed in any one of claims 1 to 12, in which the semicrystalline polymer or polymers can be present in the composition in an amount of active material ranging from 0.1 % to 12% by weight, preferably from 1 % to 6% by weight and better still from 1 % to 3% by weight, with respect to the total weight of the composition.

14. The composition as claimed in any one of claims 1 to 13, comprising at least one solid fatty substance, in particular a wax.

15. A method for the cosmetic treatment of a keratinous substance, in which a cosmetic composition as defined in any one of claims 1 to 14 is applied to the keratinous substance.

16. The use of a cosmetic composition as defined in any one of claims 1 to 14 in the cosmetic or dermatological field, in particular for caring for, protecting and/or making up the skin of the body or face or for caring for the hair.