FR3031673A1 - H / H EMULSION COMPRISING CURVED MICROPARTICLES, COMPOSITIONS COMPRISING SAME, AND USE OF MICROPARTICLES FOR STABILIZING H / H EMULSIONS - Google Patents

Abstract

The present invention relates to an oil / oil emulsion comprising at least: a first oily phase comprising at least a first non-volatile oil chosen from silicone oils, hydrocarbon oils and fluorinated oils, a second oily phase comprising at least a second non-volatile or volatile oil, immiscible with the first oil or oils at 25 ° C, at least one structuring agent chosen from waxes, pasty compounds, polymeric thickeners, mineral thickeners and mixtures thereof, and solid microparticles having at least one curved portion and at least one curvature failure of said curved portion. It also relates to cosmetic compositions comprising an emulsion according to the present invention as well as the use of the microparticles according to the invention for stabilizing oil / oil emulsions.

Description

The present invention relates to the field of cosmetic compositions based on oil / oil (H / H) emulsion. There is still a need for new architectures leading to stable cosmetic compositions and having the comfort properties required by users. The authors of the present invention have oriented their research towards the H / H emulsions. These emulsions are uncommon but nevertheless have the advantage of presenting original properties. One of the problems posed by this type of emulsion is related to their stability: the W / O emulsions are generally stabilized by gelling agents or even emulsifying surfactants and / or (co) polymers. This type of emulsion is in particular used in care products and / or make-up of the lips. For example, the patent application WO 2009/150852 relates to an oil-in-oil cosmetic composition comprising a non-volatile hydrocarbon oil, a non-volatile silicone oil and a fatty acid ester and dextrin, this application does not describe a Pickering type H / H emulsions. Advantageously and surprisingly, the authors of the present invention have used Pickering-type H / H emulsions stabilized by particular solid particles, and having good gloss properties and a good level of tack.

The emulsions according to the invention thus comprise two different immiscible oily phases, one forming the continuous phase and the other forming the dispersed phase, at least one structuring agent chosen from waxes, pasty compounds, semiconducting polymers and crystalline esters, dextrin esters and mixtures thereof, and particular solid particles for stabilizing the emulsion by positioning at the interface of the dispersed and continuous phases. Once positioned at the interface, the solid particles "block" the dispersed phase which leads to a stabilization of the emulsion. The W / O emulsion thus formed is stable for several weeks. Furthermore, the presence of at least one structuring agent chosen from waxes, pasty compounds, polymeric thickeners, mineral thickeners and mixtures thereof makes it possible to improve the gloss and to reduce the tackiness of the emulsion.

The emulsion according to the invention also makes it possible to dispense with the use as stabilizing agents of surfactant-type compounds, especially synthetic compounds, or to limit the amounts thereof. Indeed, some of these agents may present risks of toxicity to the environment depending on the quantities used.

In addition, in the context of the invention it is possible to judiciously choose the oils used to form the two phases, to choose the structuring agents, depending on the destination of the final product and the desired properties. Thus, a first object of the invention is an oil / oil (H / H) emulsion comprising at least: a first oily phase comprising at least a first non-volatile oil chosen from silicone oils, hydrocarbon oils and fluorinated oils a second oily phase comprising at least one second non-volatile or volatile oil immiscible with the first oil or oils at 25 ° C; at least one structuring agent chosen from waxes, pasty compounds and polymeric thickeners; mineral thickeners and mixtures thereof, and solid microparticles having at least one curved portion and at least one curve break of said curved portion. The invention also relates to a cosmetic composition comprising, in a physiologically acceptable medium, at least one W / O emulsion according to the invention. Definitions For the purpose of the present invention, the term "microparticles" is intended to denote a particle whose largest dimension ranges from 0.1 to 100 μm, preferably from 0.1 to 50 μm and more preferably from 0 to 50 μm. , 5 to 20 iam. By "ambient temperature" is meant a temperature of about 25 ° C, for example, from 18 to 25 ° C. It is set at atmospheric pressure (ie a pressure of 1.013, 10 Pa). The compositions and / or emulsions according to the invention comprise a physiologically acceptable medium, that is to say a non-toxic medium which can be applied to the skin of human beings, and of appearance, of odor and to touch nice.

According to a preferred embodiment, the composition according to the invention is a solid composition. According to another preferred embodiment, the composition according to the invention is a liquid composition.

In particular, it is a cosmetic makeup and / or care of the skin, and more particularly of the face, or a composition for treating keratinous fibers. By "skin" is meant the entire skin of the body, including the lips, and preferably the skin of the face, neck and décolleté, as well as the lips.

By "keratinous fibers" is meant more particularly the hair. More specifically, the composition according to the invention is a composition chosen from makeup products and / or lip care, sun products, deodorants, skincare products, perfumes. Preferably, the composition according to the invention is a composition for the makeup and / or care of the lips. In a known manner, the cosmetic composition of the invention may also contain adjuvants customary in the cosmetic field, such as preservatives, perfumes, fillers, UV filters in particular lipophilic, bactericidal, odor absorbers, dyestuffs, plant extracts, antioxidants, nonionic, anionic, cationic, amphoteric surfactants.

The amounts of these various adjuvants are those conventionally used in the field under consideration, and for example from 0.01 to 20% of the total weight of the composition. These adjuvants, depending on their nature, can be introduced into the first oily phase and / or into the second oily phase. According to another object, the invention aims at the use of solid microparticles having at least one curved portion and at least one curvature rupture of said curved portion for stabilizing an H / H emulsion comprising at least a first oily phase comprising at least one first non-volatile oil chosen from silicone oils, hydrocarbon oils and fluorinated oils, at least a second oily phase comprising at least a second non-volatile or volatile oil immiscible with the first oil or oils at 25 ° C, and at least a structuring agent chosen from waxes, pasty compounds, polymeric thickeners, mineral thickeners and mixtures thereof. The solid microparticles that can be used to stabilize the W / O emulsion according to the invention have a particular shape, they thus have at least one curved part and at least one curvature rupture of said curved part, preferably the microparticles have at least one two curved parts. According to a preferred variant, the solid microparticles that can be used in the present invention comprise several curvatures. By "several curvatures" is meant curvatures of different radius.

For the purposes of the present invention, the term "radius of curvature" does not cover the "infinite" value: "00", thus the microparticles used according to the invention are not in the form of platelets or lamellae. In particular, the solid microparticles that can be used in the present invention comprise at least one concave part and at least one convex part.

More particularly, the microparticles according to this variant have a shape chosen from the "bowls", "golf balls" and "polytopes" type shapes. According to a second preferred variant, the solid microparticles that can be used in the present invention comprise a single curvature. By "a single curvature" is meant, in the sense of the invention, when the microparticle comprises several curves, these curves have curvatures of the same radius. They are in particular chosen from fusiform microparticles, for example of the "balloon rugby" type, hemispherical. The solid microparticles that can be used in the present invention can be mineral or organic. In general, the microparticles that can be used in the present invention are such that their largest dimension ranges, on average, from 0.1 to 100 μm, preferably from 0.1 to 50 μm, and more preferably from 0, 5 to 20 1.1.m. The largest dimension of the particles, which corresponds to an average size over 50% by volume of the particles, can be determined by means of a laser diffraction granulometer (eg Mastersizer 2000 from the Malvern Company) 303 1 6 7 3 5 Advantageously, the microparticles that can be used in the present invention have a density ranging from 0.5 to 2.8, preferably from 0.8 to 1.5. The microparticles may be polar or apolar, preferably they are apolar. The microparticles according to the invention are generally obtained by radical polymerization or by polycondensation. By "radical polymerization" is meant a polymerization of at least one ethylenic monomer. In this case, preferably the microparticles according to the invention contain, or even consist of, a polymer chosen from polyacrylates, polymethyl methacrylate (PMMA) and polystyrenes. By "polycondensation" is meant polymerization between two monomers with removal of a small molecule. In this case, preferably the microparticles according to the invention contain, or even consist of, a polymer chosen from polysilicones, polyurethanes and polyesters. Bols According to the first variant of the invention, the microparticles comprise at least one concave part and at least one convex part, more particularly the microparticles have a hollow hemispherical shape, that is to say of the "bols" type. The "bowls" microparticles may comprise or consist of PMMA, and / or a silicone material, and preferably they comprise or consist of a silicone material. This latter preferred mode is described in detail below as "concave particles of silicone material". Microparticles form "bowls polymethyl methacrylate (PMMA) crosslinked" include MICROPEARL ® M310 marketed by the company SEPPIC. Concave particles of silicone material The concave particles present in the H / H emulsion according to the invention may be silicone particles, in particular hollow sphere portions made of a silicone material.

Said particles preferably have an average diameter ranging from 0.1 microns to 20 microns, preferably from 0.5 to 15 microns. By average diameter is meant the largest dimension of the particle. The portions of hollow spheres used in the W / O emulsion according to the invention have the form of truncated hollow spheres, having a single orifice communicating with their central cavity, and having a cross-section in the form of a horseshoe or hoop . The silicone material is a crosslinked polysiloxane of three-dimensional structure; it preferably comprises, or even consists of, units of formula (I) SiO 2 and of formula (II) R 1 SiO 5, in which R 1 denotes an organic group having a carbon atom directly connected to the silicon atom.

Advantageously, the solid microparticles are in the form of bowls and comprise, or even consist of units of formula (I) SiO 2 and of formula (II) R 1 SiO 1/2 in which R 1 denotes an organic group having a carbon atom directly connected to the silicon atom. The organic group R1 may be a reactive organic group; R1 may be more particularly an epoxy group, a (meth) acryloxy group, an alkenyl group, a mercaptoalkyl, aminoalkyl, haloalkyl group, a glyceroxy group, a ureido group, a cyano group, and preferably an epoxy group, a group (meth) acryloxy, alkenyl, mercaptoalkyl, aminoalkyl. These groups generally comprise from 2 to 6 carbon atoms, especially from 2 to 4 carbon atoms.

The organic group R1 may also be a non-reactive organic group; may then be more particularly a C 1 -C 4 alkyl group, especially a methyl, ethyl, propyl, butyl or a phenyl group, and preferably a methyl group. As the epoxy group, there may be mentioned a 2-glycidoxyethyl group, a 3-glycidoxypropyl group, a 2- (3,4-epoxycyclohexyl) propyl group. As the (meth) acryloxy group, there may be mentioned a 3-methacryloxypropyl group, a 3-acryloxypropyl group.

As the alkenyl group, there may be mentioned vinyl, allyl, isopropenyl groups. As the mercaptoalkyl group, mention may be made of mercaptopropyl and mercaptoethyl groups. As the aminoalkyl group, there may be mentioned a 3- (25-aminoethyl) aminopropyl group, a 3-aminopropyl group, a N, N-dimethylaminopropyl group. Haloalkyl is 3-chloropropyl, trifluoropropyl. As the glyceroxy group, there may be mentioned a 3-glyceroxypropyl group, a 2-glyceroxyethyl group. As the ureido group, there may be mentioned a 2-ureidoethyl group. Cyano groups include cyanopropyl and cyanoethyl groups. Preferably, in the unit of formula (II), R1 denotes a methyl group. Advantageously, the silicone material comprises the units (I) and (II) in a molar ratio of the unit (I) / unit (II) ranging from 30/70 to 50/50, preferably ranging from 35/65 to 45/55. . The particles of silicone material may in particular be obtainable by a process comprising: (a) introduction into an aqueous medium, in the presence of at least one hydrolysis catalyst, and optionally at least one surfactant; , a compound (III) of formula SiX4 and a compound (IV) of formula RSiY3, wherein X and Y denote, independently of one another, a C1-C4 alkoxy group, an alkoxyethoxy group-containing group C 1 -C 4 alkoxy, C 2 -C 4 acyloxy group, N, N-dialkylamino group containing C 1 -C 4 alkyl groups, hydroxyl group, halogen atom or hydrogen atom, and R denotes an organic group having a carbon atom directly attached to the silicon atom; and (b) contacting the mixture resulting from step (a) with an aqueous solution containing at least one polymerization catalyst and optionally at least one surfactant, at a temperature of between 30 and 85 ° C, for at least two 30 hours. Step (a) corresponds to a hydrolysis reaction and step (b) corresponds to a condensation reaction.

In step (a), the molar ratio of the compound (III) to the compound (IV) is usually 30/70 to 50/50, preferably 35/65 to 45/45, and is preferably 40/60. The weight ratio of water to total of compounds (III) and (IV) is preferably from 10/90 to 70/30. The order of introduction of the compounds (III) and (IV) generally depends on their rate of hydrolysis. The temperature of the hydrolysis reaction is generally from 0 to 40 ° C and usually does not exceed 30 ° C to avoid premature condensation of the compounds. For the groups X and Y of the compounds (III) and (IV): As alkoxy group C1-C4, there may be mentioned methoxy, ethoxy; As the alkoxyethoxy group containing a C1-C4 alkoxy group, there may be mentioned methoxyethoxy, butoxyethoxy; C 2 -C 4 alkoxy groups include acetoxy and propoxy groups; As N, N-dilakylamino group containing C1-C4 alkyl groups, there may be mentioned dimethylamino groups, diethylamino; As a halogen atom, mention may be made of chlorine and bromine atoms. As compounds of formula (III), there may be mentioned tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, trimethoxyethoxysilane, tributoxyethoxysilane, tetraacetoxysilane, tetrapropioxysilane, tetraacetoxysilane, tetra (dimethylamino) silane, tetra (diethylamino) silane, silane tetraol, chlorosilane triol, dichlorodisilanol, tetrachlorosilane, chlorotrihydrogensilane. Preferably, the compound of formula (III) is chosen from tetramethoxysilane, tetraethoxysilane and tetrabutoxysilane, and mixtures thereof. The compound of formula (III) leads after the polymerization reaction to the formation of units of formula (I).

The compound of formula (IV) leads after the polymerization reaction to the formation of units of formula (II). The group R in the compound of formula (IV) has the meaning as described for the group R1 for the compound of formula (II). Examples of compounds of formula (IV) having a non-reactive organic group R include methyltrimethoxysilane, ethyltriethoxysilane, propyltributoxysilane, butyltributoxysilane, phenyltrimethoxyethoxysilane, methyl tributoxyethoxysilane, methyltriacetoxysilane, methyltripropioxysilane, methyltriacetoxysilane, methyltri (dimethylamino) silane, methyltri (diethylamino) silane, methylsilane triol, methylchlorodisilanol, methyltrichlorosilane, methyltrihydrogensilane. Examples of compounds of formula (IV) having a reactive organic group R include: silanes having an epoxy group such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, 3-glycidoxypropylmethyl dimethoxysilane, 3-glycidoxypropylmethyl dimethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 3-glycidoxypropyl dimethylmethoxysilane, 2-glycidoxyethyl dimethylmethoxysilane; silanes having a (meth) acryloxy group such as 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane; silanes having an alkenyl group such as vinyl trimethoxysilane, allyl trimethoxysilane or isopropenyl trimethoxysilane; silanes having a mercapto group such as mercaptopropyl trimethoxysilane, mercaptoethyl trimethoxysilane; silanes having an aminoalkyl group such as 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, N, N-dimethylaminopropyltrimethoxysilane, N, N-dimethylaminoethyltrimethoxysilane; silanes having a haloalkyl group such as 3-chloropropyltrimethoxysilane, trifluoropropyltrimethoxysilane; silanes having a glyceroxy group such as 3-glyceroxypropyltrimethoxysilane, di (3-glyceroxypropyl) dimethoxysilane; silanes having a ureido group such as 3-ureidopropyltrimethoxysilane, 3-ureidopropylmethyldimethoxysilane, 3-ureidopropyl dimethylmethoxysilane; silanes having a cyano group such as cyanopropyl trimethoxysilane, cyanopropyl methyldimethoxysilane, cyanopropyl dimethylmethoxysilane. Preferably, the compound of formula (IV) having a reactive organic group R is chosen from silanes having an epoxy group, silanes having a (meth) acryloxy group, silanes having an alkenyl group, silanes having a mercapto group, silanes having an aminoalkyl group.

Examples of compounds (III) and (IV) preferred for the practice of this invention are tetraethoxysilane and methyltrimethoxysilane, respectively. As catalysts for hydrolysis and polymerization, it is possible to use independently basic catalysts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia or amines such as trimethylamine, triethylamine, tetramethylammonium hydroxide, or acidic catalysts such as organic acids such as citric acid, acetic acid, methanesulfonic acid, p-toluene sulfonic acid, dodecylbenzene sulfonic acid , dodecylsulphonic acid, or mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid. When present, the surfactant used is preferably a nonionic or anionic surfactant or a mixture of both. Sodium dodecylbenzenesulfonate can be used as anionic surfactant. The end of the hydrolysis is marked by the disappearance of products (III) and (IV), insoluble in water, and obtaining a homogeneous liquid layer. The condensation step (b) may use the same catalyst as the hydrolysis step or another catalyst selected from those mentioned above. At the end of this process, a suspension in water of fine organosilicone particles is obtained which may optionally subsequently be separated from their medium. The process described above may therefore comprise an additional filtration step, for example on a membrane filter, of the product resulting from step (b), optionally followed by a centrifugation step of the filtrate intended to separate the particles from the medium. liquid, then a drying step of the particles. Other separation methods can of course be employed.

The shape of the hollow sphere portions obtained according to the above method, as well as their dimensions, will depend in particular on the method of contacting the products in step (b). A rather basic pH and a cold introduction of the polymerization catalyst into the mixture resulting from step (a) will lead to portions of hollow spheres in the form of "bowls" with a rounded bottom while a rather acid pH, and a dropwise introduction of the mixture from step (a) into the hot polymerization catalyst will result in hollow sphere portions having a horseshoe-shaped cross-section. According to a preferred embodiment of the invention, portions of hollow spheres in the form of "bowls" are used. These can be obtained as described in JP-A-2003-128788 or FR 2 902 654, particularly in the parts of these applications devoted to "bowls" type particles and their methods of preparation. Portions of horseshoe-shaped hollow spheres are described in JP-A-2000-191789. Figure 1 of FR 2 902 654 illustrates a concave particle in the form of 10 bowl-shaped sphere portions in cross-section. The width W2 corresponds to the diameter of the particles. As is apparent from this figure, these concave portions are formed (in section perpendicular to a plane of the opening defined by the hollow sphere portion) of a small internal arc (11), a large external arc (21) and segments (31) which connect the ends of the respective arcs, the width (W1) between the two ends of the small inner arc (11) ranging from 0.01 to 8 μm, preferably from 0.02 to 6 μm by average, the width (W2) between the ends of the large external arc (21) ranging from 0.05 to 10 pra, preferably from 0.06 to 8 pm on average and the height (H) of the large external arc (21 ) ranging from 0.015 to 8 gm, preferably from 0.03 to 6 pm on average. The dimensions mentioned above are obtained by averaging the dimensions of one hundred selected particles on an image obtained with a scanning electron microscope. As concave particles in the form of portions of spheres that can be used according to the invention, mention may be made, for example, of: particles consisting of the crosslinked organosilicone TAK-110 (cross-linked methylsilanol / silicate polymer) of the company TAKEMOTO OIL & FAT, in bowl shape, 2.5 ktm wide, 1.2 m high and 150 min thick (particles sold under the name NLK-506 by Takemoto Oil &Fat); the particles consisting of the cross-linked organosilicone TAK-110 (crosslinked methylsilanolisilicate polymer) from Takemoto OIL & FAT, in the form of a bowl, with a width of 0.8 μm, a height of 0.4 μm and a thickness of 130 nm (Particles sold under the name NLK-515 by the company Takemoto 011 &Fat); particles consisting of the crosslinked organosilicone TAK-110 (methylsilanollsilicate crosslinked polymer) from the company TAKEMOTO OIL & FAT, in the form of a bowl, with a width of 7 μm, a height of 3.5 gin and a thickness of 200 nm (particles sold under the name NLK-510 by Takemoto Oil & Fat).

These particles comprise or consist of methylsilanol / silicate crosspolymer. Advantageously, the silicone concave particles, in particular the bowls, have an average diameter less than or equal to 5 μm, in particular ranging from 0.1 μm to 5 μm, preferably ranging from 0.2 to 5 μm, more preferably ranging from 0.5 to 4 m, and more preferably from 0.5 to 3 gm. Polvtones According to another variant, the microparticles that can be used according to the invention are non-spherical fine particles in the form of polygons having at least six concave faces. These particles are characterized by an average value of the maximum external diameters of said individual non-spherical fine particles ranging from 0.1 to 20 μm; an average value of the ratio between the minimum external diameters and the maximum external diameters of said individual non-spherical fine particles ranging from 0.60 to 0.97; and an average number of concave surfaces, whose ratio of the maximum diameter relative to the maximum outside diameter ranges from 0.50 to 0.90, ranges from 6 to 14 per non-spherical fine particle. These particles are described in more detail in the application EP 2 476 719 A1, in particular the parts of this application devoted to the definition of nonspherical fine particles and their process of preparation. The non-spherical fine particles in the form of polygons having at least six concave faces usable according to the invention are also called "polytopes" or "ossicles", the largest dimension of these particles is preferably from 1 to 10 gm).

In another variant, the microparticles that can be used according to the invention are particles of non-(spherical) shape, in particular fusiform, also called "rugby ball" shape.

In this text, a fusiform or "rugby balloon" shape refers to a shape such as a sphere which is extended in one direction so as to have a major axis along which the fusiform particle has the largest diameter L1 which is between approximately 0.05 μm and approximately 20 μm and two minor axes L 2 perpendicular to the major axis and along each of which the fusiform particle has the smallest diameter which is between approximately 0.03 μm. and approximately 15 μm, Li / L 2 ranging from approximately 1.1 to approximately 3.3. The organosilicone material with crosslinked polysiloxane structure preferably comprises, or is compounded by, units of formula (I): 5iO 2, and of formula (II): R 1 SiO 5, in which R 1 represents an organic group containing a carbon atom directly connected to the silicon atom. The organic group may be a reactive organic group or a non-reactive organic group and preferably a non-reactive organic group. The organosilicone material with a crosslinked polysiloxane structure also preferably comprises a first, a second and a third siloxane unit which are respectively formula (I): 5iO2, of formula (II): RiSiO15 and of formula (III): R2R3SiO, in which R1, R2 and R3 are any organic groups, identical or different, containing a carbon atom directly connected to an atom silicon; R2 and R3 may independently be a nonreactive organic group or an organic group not containing a reactive group or a reactive organic group or an organic group containing a reactive group. R 2 and / or R 3, however, preferably represent a reactive organic group or an organic group containing a reactive group. The non-reactive organic group may be a C 1 -C 4 alkyl group, especially a methyl, ethyl, propyl or butyl group, or a group phenyl, and preferably a methyl group. The reactive organic group may be an epoxy group, a (meth) acryloyloxy group, an alkenyl group, a mercaptoalkyl, aminoalkyl or haloalkyl group, a glyceroxy group, a ureido group or a cyano group. Preferably, the reactive organic group may be an epoxy group, a (meth) acryloyloxy group, an alkenyl group or a mercaptoalkyl or aminoalkyl group. The reactive organic group generally comprises from 2 to 6 carbon atoms, especially from 2 to 4 carbon atoms. As the epoxy group, there may be mentioned a 2-glycidoxyethyl group, a 3-glycidoxypropyl group or a 2- (3,4-epoxycyclohexyl) propyl group. As the (meth) acryloyloxy group, there may be mentioned a 3-methacryloyloxypropyl group or a 3-acryloyloxypropyl group.

As the alkenyl group, there can be mentioned a vinyl, allyl or isopropenyl group. As the mercaptoalkyl group, there may be mentioned a mercaptopropyl or mercaptoethyl group. As the aminoalkyl group, there may be mentioned 3 - [(2-aminoethyl) amino] propyl, 3-aminopropyl or N, N-dimethylaminopropyl. As the haloalkyl group, there may be mentioned a 3-chloropropyl group or a trifluoropropyl group. As the glyceroxy group, there may be mentioned a glyceroxypropyl group or a 2-glyceroxyethyl group. As the ureido group, there may be mentioned a 2-ureidoethyl group. As the cyano group, there may be mentioned a cyanopropyl or cyanoethyl group. Preferably, in the unit of formula (II), R1 represents a methyl group. Advantageously, the organosilicone material comprises units (I) and (II) in a unit (I) / unit (II) molar ratio ranging from 30/70 to 50/50, preferably from 35/65 to 45/50. / 55. Also advantageously, the organosilicone material comprises units (I), (II) and (III) so that the molar ratio of the molar sum of the first siloxane unit (I) and the second unit (II) ) on the third siloxane unit (III) is approximately between 99: 1 and 50:50, more preferably between 90:10 and 60:40. The molar ratio of the first siloxane unit (I) to the second siloxane unit (II) may preferably be between approximately 23:77 and 40:60. The fusiform microparticles as well as the processes for obtaining them are in particular described in the Japanese patent application 2003-171465 filed by Takemoto Fat & Oil. Golf balls As usable golf balls, mention may be made especially of organic silicone microparticles comprising a polysiloxane crosslinked structure, of globally spherical shape and having on their surface a multitude of recesses. More particularly, the polysiloxane crosslinked structure is a structure in which the polysiloxane units form a three-dimensional network. Preferably, said siloxane units comprise at least two types of units selected from the units of formula (1), and preferably comprise a unit of average formula (2); said formulas being the following: RimSiO (4-n) / 2 (1) R 2 'SiO (4-n) / 2 (2) in which R 1 and R 2 represent an organic group connected to the silicon atom directly by an atom of carbon ; m is an integer from 0 to 3; n ranges from 0.78 to 0.95.

The units of formula (1) more particularly represent SiO4 / 2, SiO3 / 2, R12SiO2 / 2 and R'3Si0, / 2 in which the same or different are more particularly a hydrocarbon group such as an alkyl, cycloalkyl, aryl or alkylaryl group. or aralkyl, the alkyl group having 1 to 4 carbon atoms such as methyl, ethyl or butyl, preferably methyl, the aromatic group more particularly representing a phenyl. The hydrocarbon groups may be substituted by an epoxy group, glyceroxy, a halogen atom, a ureido group, a cyano group or an amino group, and preferably a C 1 -C 4 glycidoxyalkyl group such as 2-glycidoxyethyl, 3-glycidoxypropyl group. , 2- (glycidoxycarbonyl) (C1-C4) alkyl such as 2- (glycidoxycarbonyl) ethyl, 2- (glycidoxycarbonyl) propyl, 2- (epoxycyclohexyl) (C1-C4) alkyl, such as 2- (3,4-epoxycyclohexyl) ) propyl; radicals comprising epoxy radicals being preferred as well as 2-glycidoxyethyl, 3-glycidoxypropyl.

According to a first variant, in the case where R1 represents an unsubstituted hydrocarbon group as described previously, the siloxane units represented by the formula (1) can be chosen from: 1) silicic anhydride, 2) a siloxane unit represented by Ri SiO3 / 2, such as methylsiloxane, ethylsiloxane, butylsiloxane or phenylsiloxane, 3) a siloxane unit represented by R12SiO2 / 2, such as dimethylsiloxane, diethylsiloxane, dibutylsiloxane, methylphenylsiloxane or diphenylsiloxane, or 4) one unit siloxane represented by R13 Si01 / 2, such as a trimethylsiloxane, triethylsiloxane, tributylsiloxane, dimethylphenylsiloxane or diethylphenylsiloxane unit. The methylsiloxane, dimethylsiloxane and trimethylsiloxane units are preferred. According to a second variant, in the cases where R1 represents a substituted hydrocarbon radical as described previously, the siloxane units represented by the formula (1) may advantageously be chosen from 1) a siloxane unit represented by R '5i0312, as a unit 3 glycidoxypropylsiloxane or 2-glycidoxyethylsiloxane, 2) a siloxane unit represented by R12SiO2 / 2, such as a 3-glycidoxypropylmethylsiloxane or 2-glycidoxyethylmethylsiloxane unit, or 3) a siloxane unit represented by R135i01 / 2, such as a 3-glycidoxypropyldimethylsiloxane unit or 2- glycidoxyéthyldiméthylsiloxane. In the case where the polysiloxane crosslinked structure comprises siloxane units as described above, the average formula of the siloxane units is represented by the average formula (2) indicated previously. Preferably, n in the formula (2) ranges from 0.78 to 0.95, and preferably from 0.80 to 0.90. For example, a crosslinked polysiloxane may be R 1 SiO 3/2, 2) units 5i0412, R '5i0312 consisting of units 1) SiO412, Ri2Si02 / 2 and R13 Si01 / 2, and Ri25i02 / 2, or 3) 5i0412 and Ri5iO3 / 2, the preferred being crosslinked polysiloxanes comprising 5i0412 and RiSiO3 / 2, wherein the molar ratio 5i0412 / RiSiO3 / 2 is between 5/95 and 22/78, and preferably between 10/90 and 20/80. The microparticles of organic silicone have, as indicated above, a generally spherical structure and a mean diameter ranging from 0.1 to 10 μm, preferably from 0.1 to 7 μm. Note that the average diameter is measured by the diffraction / laser scattering method. With regard to the indentations on the surface of the microparticles, their structure can be influenced by the proportion of siloxane units. When viewed from the surface of the microparticle, they can be almost circular, elliptical, in the form of wrinkle-like or irregularly shaped, or even a set of several forms. However, the microparticles comprising on their surface a multitude of almost circular structural recesses are preferred (golf balls aspect).

Microparticles of this type and the processes for obtaining them are described in particular in Japanese Patent W 38 46667 filed by TAKEMOTO OIL & FAT. According to a preferred embodiment of the invention, the solid microparticles used in the emulsion are silicone particles, and even more preferably, are particles in the form of bowls. Preferably, the total amount of solid microparticles comprising at least one curved portion and at least one rupture of the curvature of said curved portion ranges from 1 to 10%, preferably from 2 to 7% by weight relative to the total weight of the 'emulsion. OILS The emulsion according to the invention comprises two oily phases, a first oily phase comprising at least a first oil chosen from silicone oils, hydrocarbon oils or fluorinated oils and a second oily phase comprising at least a second oil immiscible with the first oil or oils, at room temperature, and at atmospheric pressure (760 mm Hg / 1.013 × 10 Pa). By "immiscible oils" within the meaning of the present invention is meant that the mixture of these two oils does not lead to a homogeneous uniphasic solution. Said mixture is made with the same amount by weight of each oil. For the purposes of the invention, the term "oils" means a compound whose viscosity is at most 200,000 cPs (200 Pa · s) at 25 ° C. Also, and preferably, at least one of the oils is selected from water-immiscible compounds (mixture made with the same amount of water).

According to a particularly advantageous embodiment of the invention, the oil or oils are chosen from water-immiscible compounds. It should be noted that the viscosities are measured according to the following protocol: The viscosity is measured at 25 ° C. 0.5 ° C. using a Haake RS600 imposed stress rheometer from Thermo Rhéo equipped with a mobile cone / plane geometry with a diameter of between 2 cm and 6 cm and an angle between 1 ° and 2 °, the choice of the mobile being a function of the viscosity to be measured (the more the formula is fluid, the larger the diameter the chosen cone is large and the angle is small). The measurement is made by imposing on the oil sample a logarithmic gradient of shear gradient E 'ranging from 101s-1 to 1000s-1, for a period of 5 minutes. The rheogram representing the evolution of the viscosity is then plotted as a function of the shearing gradient E '. The value considered is that of the viscosity at 500s-1, whether measured at this gradient or extrapolated by the plot if no experimental point corresponds to this value. More particularly, the oils are said to be "immiscible" when their mixture leads to a phase separation according to the following protocols: For oils having a viscosity of less than 10,000 cPs (10 Pa · s) at 25 ° C., both are introduced. oils to be evaluated (5 g / 5 g) at room temperature, in a conical tip plastic centrifuge tube (ref Corninge 15mL PET Centrifuge Tubes, Packaged Rack with Plug Seal Cap, Sterile (Product # 430055) that is placed in a VORTEX GENIE 2 apparatus, stirring at 10 ° for 10 seconds followed by manual overturning of the tube before returning it to the VORTEX apparatus.This cycle is repeated 3 times in succession. at room temperature for 48 hours If at least one of the oils has a viscosity greater than or equal to 10,000 cPs (10 Pa · s) at 25 ° C, then the mixture of the two oils (5 g / 5 g) an oven at 50 ° C for 30 minutes before carrying out the three agitation cycles described above. The mixture is then observed. When the mixture is separated into two phases and at the interface, the separation of the two phases is clearly defined, the phases are deemed "separated" and the oils are therefore immiscible.

In the opposite case, the mixture is observed under a phase contrast microscope at room temperature (approximately 25 ° C.). If a continuous phase and a disperse phase in the form of drops are observed, the phases are considered to be "separated" and the oils are considered immiscible.

If the observation of the mixture shows only one phase, then the phases are considered to be "non-separated" and the oils are considered to be miscible. This same protocol is used to check the miscibility of the oil with water. More particularly, the W / O emulsion according to the invention comprises at least a first oily phase containing at least one non-volatile oil, and a second oily phase containing at least one volatile or non-volatile oil. Preferably, the first and second oily phases each contain at least one non-volatile oil. By "nonvolatile" is meant an oil whose vapor pressure at room temperature (25 ° C) and atmospheric pressure is non-zero and less than 10-3 mmHg (0.13 Pa). By "volatile" is meant an oil capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. More particularly, the term "volatile oil" means an oil having a non-zero vapor pressure at ambient temperature (25 ° C.) and atmospheric pressure, in particular having a vapor pressure of from 0.13 Pa to 40,000. Pa, and preferably ranging from 1.3 Pa to 13 000 Pa, and preferably ranging from 1.3 Pa to 1300 Pa. A preferred embodiment of the invention relates to an oil / oil emulsion in which said first non-volatile oil or the second oil, preferably said first oil, is chosen from silicone oils and fluorinated oils, or mixtures thereof, and more particularly from non-phenylated non-volatile silicone oils; non-volatile phenyl silicone oils, optionally bearing at least one dimethicone fragment; fluorinated oils; or mixtures thereof. Another preferred embodiment of the invention relates to an oil / oil emulsion in which the first or second non-volatile oil, preferably the second oil, is chosen from non-volatile polar hydrocarbon oils, in particular chosen from non-volatile oils, comprising at least one free or non-free hydroxyl group, or from non-volatile oils, comprising at least two free hydroxyl groups, or from non-volatile hydrocarbon apolar oils or mixtures thereof.

First Oily Phase The first oily phase comprises at least a first non-volatile oil chosen from silicone oils, fluorinated oils, hydrocarbon oils, or mixtures thereof, and more particularly, according to a first embodiment, from non-silicone oils. non-phenylated volatiles; phenylated nonvolatile silicone oils, with or without at least one dimethicone fragment; fluorinated oils; or their mixtures. According to a second embodiment, the first oily phase comprises at least a first hydrocarbon oil.

This first oily phase may be the continuous phase or the dispersed phase. By "silicone oil" is meant an oil containing at least one silicon atom, and in particular containing Si-O groups. By "polar hydrocarbon oil" is meant an oil formed essentially, or even constituted, of carbon and hydrogen atoms, as well as of heteroatom (s) such as oxygen, nitrogen, and not containing a silicon or fluorine atom. By "fluorinated oil" is meant an oil containing at least one fluorine atom. 1. Silicone Oils Non-Phenylated Non-volatile Silicone Oils The term "non-phenyl silicone oil" or "non-phenyl silicone oil" refers to a silicone oil having no phenyl substituent.

Representative examples of such non-volatile, non-phenolic silicone oils which may be mentioned include polydimethylsiloxanes; alkyldimethicones; vinylmethylmethicones; and also silicones modified with aliphatic groups and / or with functional groups such as hydroxyl, thiol and / or amine groups. Note that "dimethicone" (INCI name) corresponds to a polydimethylsiloxane (chemical name).

In particular, these oils may be chosen from the following non-phenylated non-volatile silicone oils: polydimethylsiloxanes (PDMSs), PDMSs comprising aliphatic groups, in particular alkyl, or alkoxy groups, which are pendant and / or at the end of the silicone chain; these groups each comprising 2 to 24 carbon atoms; PDMSs comprising at least one aliphatic group and / or at least one functional group such as hydroxyl, thiol and / or amine groups; polysiloxanes modified with fatty acids; , fatty alcohols or polyoxyalkylenes, and mixtures thereof. The non-phenylated non-volatile silicone oil is preferably selected from non-volatile dimethicone oils. Preferably, these non-volatile non-phenyl silicone oils are chosen from polydimethylsiloxanes; alkyldimethicones and also PDMSs comprising at least one aliphatic group, in particular C 2 -C 24 alkyl, and / or at least one functional group such as hydroxyl, thiol and / or amine groups. The non-phenyl silicone oil may be chosen in particular from silicones of formula (I '): ## STR2 ## wherein R 1 R 3 R 5 11 X-Si O-Si O-Si-O-Si-X 116 n-25 (I') in which R1, R2, R5 and R6 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms, R3 and R4 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms, a vinyl radical, a amine radical or a hydroxyl radical, X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or an amine radical, n and p are integers chosen so as to have a fluid compound, in particular whose viscosity at 25 ° C is between 9 centistokes (cSt) (9 x 10-6 m2 / s) and 800,000 cSt (ie between 8 mPa.s and 720000 mPa. $). As non-volatile, non-phenyl silicone oils which can be used according to the invention, mention may be made of those for which: the substituents R 1 to R 6 and X represent a methyl group, and p and n are such that the viscosity is 500,000 cSt (ie 450000 mPa. $), for example the product marketed under the name SE30 by General Electric, the product marketed under the name AK 500000 by Wacker, the product marketed under the name Mirasil DM 500,000 by the company Bluestar, and the product sold under the name Dow Corning 200 Fluid 500,000 cSt (450000 mPa. $), By Dow Corning, - the substituents R1 to R6 and X represent a methyl group, and p and n are such that the viscosity is 60,000 cSt (54,000 mPa · s), for example the product marketed as Dow Corning 200 Fluid 60000 CS by Dow Corning, and the product marketed under the name Wacker Belsil DM 60 000 by the en Wacker company, - substituents R1 to R6 and X represent a methyl group, and p and n are such that the viscosity is 100 cSt (or 90 mPa. $), or 350 cSt (or 315 mPa. $), by examples as sold by Dow Corning under the name Dow Corninge 200 Fluid, 100 cSt or Dow Corninge SH 200 Fluid 100 CS; or sold by the company Wacker under the name Belsile DM 100 dimethicone, - the substituents R1 to R6 represent a methyl group, the X group represents a hydroxyl group, and n and p are such that the viscosity is 700 cSt (630 mPa . $), for example the product marketed under the name Baysilone Fluid T0.7 by the company Momentive.

Nonvolatile Phenyl Silicone Oils The term "phenyl silicone oil" or "phenylsilicon (e) e oil" means a silicone oil having at least one phenyl substituent. These phenyl silicone oils may be chosen from those which furthermore have at least one dimethicone fragment, or from those which do not have one. According to the invention, a dimethicone fragment corresponds to the following unit: -Si (CH3) 2-0-. The nonvolatile phenyl silicone oil may thus be chosen from: a) phenylsilicone oils with or without a dimethicone fragment corresponding to the following formula (I): R-Si-O II R-O-Si-R RR 11 R Si (I) wherein the monovalent or divalent R groups represent, independently of each other, a methyl or a phenyl, provided that at least one R is phenyl. Preferably, in this formula, the phenylsilicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six. b) phenylsilicone oils with or without a dimethicone fragment corresponding to the following formula (2): R-Si-O-Si-O-Si-R (II) in which the R groups represent, independently of each other, a methyl or phenyl, provided that at least one R is phenyl. Preferably, in this formula, the compound of formula (II) comprises at least three phenyl groups, for example at least four or at least five.

Mixtures of different phenylorganopolysiloxane compounds previously described may be used. Examples which may be mentioned include mixtures of triphenyl-, tetraphenyl- or pentaphenyl-organopolysiloxanes.

Among the compounds of formula (II), mention may be made more particularly of phenylsilicone oils having no dimethicone fragment corresponding to formula (II) in which at least 4 or at least 5 radicals R represent a phenyl radical, the radicals remaining representing methyl.

Such nonvolatile phenylsilicone oils are preferably trimethylpentaphenyltrisiloxane, or tetramethyltetraphenyltrisiloxane. They are in particular marketed by Dow Corning under the reference PH-1555 HRI or Dow Corning 555 Cosmetic Fluid (chemical name: 1,3,5-trimethyl-1,1,1,5,5-pentaphenyltrisiloxane; INCI name: trimethyl- pentaphenyltrisiloxane), or tetramethyltetraphenyltrisiloxane sold under the reference Dow Corning 554 Cosmetic Fluid by Dow Corning can also be used. They correspond in particular to the following formulas (III), (III '): Ph Ph Ph Me Ph Me Me-Si-O-Si-O-Si-Me Ph-Si-O-Si-O-Si-Ph 1 1 Ph Ph (III) Me Ph Me (III ') in which Me is methyl, Ph is phenyl. (IV) wherein Me is methyl, y is between 1 and 1000 and X is -CH 2 -CH (CH 3) (Ph). c) phenylsilicone oils having at least one dimethicone moiety corresponding to the following formula (IV): d) Phenylsilicone oils corresponding to formula (V) below, and mixtures thereof : R 1 R 5 R 53 -O Si Ru R 1 (V) in which: R 1 to R 10, independently of one another, are linear or cyclic or branched, preferably saturated or unsaturated, saturated or unsaturated C 1 -C 30 hydrocarbon radicals; , linear or branched, - m, n, p and q are, independently of each other, integers between 0 and 900, provided that the sum m + n + q is different from 0.

Preferably, the sum m + n + q is between 1 and 100. Preferably, the sum m + n + p + q is between 1 and 900 and preferably between 1 and 800. Preferably, q is equal to 0. Preferably, R1 to R10, independently of each other, represent a linear or branched C1-C30 alkyl radical, preferably a C1-C20, more particularly a C1-C16, or a C6-C14 aryl radical. and in particular C 10 -C 13, monocyclic or polycyclic, or an aralkyl radical preferably whose alkyl part is C 1 -C 3. Preferably, R 1 to R 10 may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical. R1 to R10 may in particular be identical, and may furthermore be a methyl radical. According to a first more particular embodiment of the formula (V), mention may be made of: i) phenylsilicone oils having or not at least one dimethicone fragment corresponding to the formula (VI) below, and mixtures thereof: Wherein R 1 to R 6, independently of one another, are saturated C 1 -C 30 hydrocarbon radicals or unsaturated, linear, cyclic or branched, preferably saturated or unsaturated, linear or branched, an aryl radical, preferably C 6 -C 14, or an aralkyl radical whose alkyl part is C 1 -C 3. m, n and p are, independently of each other, integers between 0 and 100, provided that the sum n + m is between 1 and 100. Preferably, R1 to R6, independently of one of the other, represent an alkyl radical, C1-C30, preferably C1-C20, in particular C1-C16, or a C6-C14 aryl monocyclic (preferably C6) or polycyclic and especially Cio-C14 C13, or an aralkyl radical (preferably the aryl portion is C6, the alkyl portion is C1-C3). Preferably, R 1 to R 6 may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical. R1 to R6 may in particular be identical, and may furthermore be a methyl radical. Preferably, m = 1 or 2 or 3, and / or n = 0 and / or p = 0 or 1 may be applied, in formula (VI).

According to a particular embodiment, the non-volatile phenyl silicone oil is chosen from phenyl silicone oils having at least one dimethicone fragment. Preferably, such oils correspond to compounds of formula (VI) in which: (VI) A) m = 0 and n and p are independently of one another, integers between 1 and 100. Preferably R1 to R6 are methyl radicals. According to this embodiment, the silicone oil is preferably selected from diphenyldimethicone such as Shin Etsu's KF-54, Shin Etsu's KF54HV, Shin Etsu's KF-50-300CS, KF-53 by Shin Etsu, KF- 50-100CS of Shin Etsu. B) p is between 1 and 100, the sum n + m is between 1 and 100, and n = 0. These phenylsilicone oils having or not at least one dimethicone fragment corresponding more particularly to the formula (VII) below: Me Me OR Me (VII) [Me-SiO-SiO Si O -Si-Me Me Me] in which Me is methyl and Ph is phenyl, OR 'represents a group -O SiMe3 and p is 0 or is between 1 and 1000, and m is between 1 and 1000. In particular, m and p are such that the compound (VII) is a non-volatile oil. According to a first embodiment of nonvolatile phenyl silicone having at least one dimethicone fragment, p is between 1 and 1000. m is more particularly such that the compound (VII) is a non-volatile oil. It can be used, for example, trimethylsiloxyphenyldimethicone, marketed in particular under the reference Belsil PDM 1000 by the company Wacker. According to a second embodiment of nonvolatile phenyl silicone having no dimethicone fragment, p is equal to 0. m is between 1 and 1000, and in particular is such that the compound (VII) is a nonvolatile oil 25 It may be used, for example, phenyltrimethylsiloxytrisiloxane, sold in particular under the reference Dow Corning 556 Cosmetic Grade Fluid (DC556). ii) nonvolatile phenylsilicone oils having no dimethicone moiety corresponding to the formula (VIII) below, and mixtures thereof: H3C-Si-O S 0 Si -O Si-CH I 3 Si ( CH3) 3 in which: R, independently of each other, represent a saturated or unsaturated, linear, cyclic or branched, preferably saturated or unsaturated, linear or branched C1-C30 hydrocarbon radical; more particularly, R represent a C1-C30 alkyl radical, an aryl radical, preferably a C6-C14 radical, or an aralkyl radical whose alkyl part is C1-C3. m and n are, independently of each other, integers between 0 and 100, provided that the sum n + m is between 1 and 100.

Preferably, R, independently of each other, represent a linear or branched C 1 -C 30 alkyl radical, in particular C 1 -C 20, in particular C 1 -C 16, a monocyclic or polycyclic C 6 -C 14 aryl radical and in particular especially C 10 -C 13, or an aralkyl radical, preferably the aryl part is C 6 and the alkyl part is C 1 -C 3. Preferably, the R may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical. The R may in particular be identical, and furthermore may be a methyl radical. Preferably, m = 1 or 2 or 3, and / or n = 0 and / or p = 0 or 1 may be applied in formula (VIII). According to a preferred embodiment, n is an integer between 0 and 100 and m is an integer between 1 and 100, provided that the sum n + m is between 1 and 100, in formula (VIII). Preferably R is a methyl radical. According to one embodiment, a phenylsilicone oil of formula (VIII) having a viscosity at 25 ° C of between 5 and 1500 mm 2 / s (i.e., from 5 to 1500 cSt), (VIII) and Preferably having a viscosity of between 5 and 1000 mm 2 / s (i.e. 5 to 1000 cSt) can be used. According to this embodiment, the nonvolatile phenylsilicone oil is preferably chosen from phenyltrimethicones (when n = 0) such as DC556 from Dow Corning (22.5 cSt), or from diphenylsiloxyphenyltrimethicone oil (when m and n range from 1 to 100), such as KF56 A from Shin Etsu, Silbione 70663V30 from Rhône-Poulenc (28 cSt). Values in parentheses represent viscosities at 25 ° C. (e) phenylsilicone oils with or without at least one dimethicone moiety corresponding to the following formula, and mixtures thereof: R 1 R 5 X 11 O-Si-O-Si-X R 6 R 2 P 0 Si ( IX) in which: R1, R2, R5 and R6 are, identical or different, an alkyl radical containing 1 to 6 carbon atoms, R3 and R4 are, identical or different, an alkyl radical containing from 1 to 6 carbon atoms or an aryl (preferably C 6 -C 14) radical, provided that at least one of R 3 and R 4 is a phenyl radical, X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or a radical vinyl, n and p being an integer greater than or equal to 1, chosen so as to give the oil a weight average molecular weight of less than 200 000 g / mol, preferably less than 150 000 g / mol and more preferably less at 100,000 g / mole. f) and a mixture thereof. 2. Fluorinated oils According to another embodiment, the first non-volatile oil is chosen from fluorinated oils. The fluorinated oils that may be used according to the invention may be chosen from fluorosilicone oils, fluorinated polyethers and fluorinated silicones, in particular as described in document EP-A-847752 and perfluorinated compounds. By perfluorinated compounds is meant according to the invention compounds in which all the hydrogen atoms have been substituted by fluorine atoms. According to a preferred embodiment, the first fluorinated oil according to the invention is chosen from perfluorinated oils.

As examples of perfluorinated oils that may be used in the invention, mention may be made of perfluorodecalin and perfluoperhydrophenanthrene. According to a preferred embodiment, the fluorinated oil is chosen from perfluoperhydrophenanthrenes, and in particular Fiflow® products sold by Créations Couleurs. In particular, it is possible to use the fluorinated oil whose INCI name is perfluoperhydrophenanthrene, sold under the reference FIFLOW 220 by the company F2 Chemicals. Preferably, the first oily phase comprises at least a first non-volatile oil chosen from the non-phenylated oils of formulas (I), from the phenylated oils of formula (II), in particular (III), of formula (V), in particular (VI) or (VII), and mixtures thereof. 3. Hydrocarbon oils As indicated above, a second embodiment consists in using, as the first oil phase, at least one hydrocarbon-based oil, in particular chosen from non-volatile oils comprising at most one free hydroxyl group or not comprising not, or from non-volatile oils comprising at least two free hydroxyl groups, or from non-volatile hydrocarbon oils apolar, or mixtures thereof. These oils will be described in more detail in the description of the second oily phase and can be referred to.

Second Oily Phase The second oily phase comprises at least one second nonvolatile or volatile oil, immiscible with the first oil, at room temperature. Preferably the second oily phase comprises at least a second non-volatile oil, immiscible with the first oil or oils, at room temperature. This second oily phase may be the continuous phase or the dispersed phase. The second oil or oils may advantageously be chosen from non-volatile polar hydrocarbon oils, in particular chosen from non-volatile oils comprising at most one free or non-free hydroxyl group, or from non-volatile oils comprising at least two groups. free hydroxyls, or from nonpolar hydrocarbon apolar oils, or mixtures thereof. According to a second possibility, the second oil or oils are chosen from silicone oils immiscible with the first oil or oils. The non-volatile silicone oils listed in the context of the definition of the first oily phase can be used as oil (s) of the second oily phase. Their description will not be repeated in this part of the text and it will be possible to refer to it, especially for the preferred silicones. 1. Non-volatile polar hydrocarbon oils The term "polar hydrocarbon-based oil" is intended to mean an oil formed essentially or even consisting of carbon and hydrogen atoms, as well as of heteroatom (s) such as carbon atoms. oxygen, nitrogen, and not containing a silicon atom or fluorine.

It can thus contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups. In particular, the non-volatile hydrocarbonaceous polar oil may be chosen from the list of oils below, and their mixtures: a) Non-volatile oils comprising at most one free hydroxyl group or not including the second or the second oils may be chosen from non-volatile hydrocarbon oils comprising at most one free hydroxyl group, or not including it. As examples of oils of this type, mention may be made of: i) ester oils * vegetable hydrocarbon-based oils such as liquid triglycerides of fatty acids having from 4 to 40 carbon atoms, more particularly from 4 to 24 carbon atoms. By way of examples, mention may be made of triglycerides of heptanoic or octanoic acids, jojoba oil, sesame oil, ximenia seed oil, or mixtures thereof. Synthetic glycerides such as those of capric / caprylic acids, C18-36 triglyceride acid (DUB TGI 24 from Stearinerie Dubois). Monoesters or diesters obtained from saturated or unsaturated monocarboxylic or dicarboxylic fatty acid, aromatic or otherwise, in particular comprising from 4 to 40, in particular from 4 to 24 carbon atoms, optionally comprising a free hydroxyl, on the one hand, and saturated or unsaturated monoalcohol or polyol, aromatic or otherwise, comprising from 2 to 40, in particular from 3 to 24 carbon atoms, on the other hand; the number of carbon atoms (excluding carbonyl group) being at least 12, preferably at least 16, the ester comprising at most one free hydroxyl if it contains. Examples of monoesters or diesters that may be mentioned include purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12-C18 alcohol benzoate, and octyl benzoate. 2 dodecyl, 2-hexyl ethyl palmitate, octyledodecyl neopentanoate, octy1-2 dodecyl stearate, octy1-2 dodecyl erucate, oleyl erucate, isostearyl isostearate , octanoates, decanoates or ricinoleates of alcohols or polyalcohols, preferably diols, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, 2-ethyl palmitate, hexyl, 2-hexyl-decyl laurate, 2-octyl-decyl palmitate, 2-octyldodecyl myristate, 2-diethylhexyl succinate; or their mixtures. Fatty acids, in particular C4-C22, preferably C6-C22, and in particular octanoic acid, heptanoic acid, lanolic acid and oleic acid, are also suitable. , lauric acid, stearic acid, and C3-C6 glycol, such as, for example, propylene glycol dioctanoate, propylene glycol monoisostearate, neopentyl glycol diheptanoate. hydroxylated mono- and di-esters, preferably having a total number of carbon ranging from 20 to 70, such as isostearyl lactate, octylhydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, monoesters; C1-C4 amino acids N-acylated, such as those of formula R1CONR2CHR3 (CH2) .COOR4 wherein R1 represents a C5-C21 alkyl group, R2, R3 and R4 identical or different, represent an alkyl group C1-C4, R3 may be a hydrogen atom. For example, lauroyl isopropryl sarcosinate may be mentioned. Esters of pentaerythritol and C6-C22 mono- or di-fatty acids, such as the mixture of pentaerythritol ester and isostearic, capric, caprylic and adipic acids (Supermol -L of Croda). Polyesters comprising at least three ester functions of mono- or poly-carboxylic acids, saturated, unsaturated or aromatic, linear, branched or cyclic, optionally hydroxylated, C4-C40 and respectively polyols or C2-C40 monohydric alcohols preferably C3-C40; said polyester optionally comprising at least one free hydroxyl. By way of example, mention may also be made of oils comprising three ester functions, of acid comprising three carboxylic functions, monohydroxylated, and of C2-C4 monoalcohol, in particular triethyl citrate. By way of example, mention may be made of linear fatty acid esters having a total number of carbon ranging from 35 to 70, such as pentaerythrityl tetrapelargonate (MW = 697 g / mol).

Also suitable are esters of fatty alcohol or branched fatty acids, such as in particular triisoarachidyl citrate (MW = 1033.76 g / mol), pentaerythrityl tetraisonanoate (MW = 697 g / mol), glyceryl triisostearate ( MM = 891 g / mol), pentaerythrityl tetraisostearate (MW = 1202 g / mol), polyglyceryl tetraisostearate -2 (MW = 1232 g / mol), and also those described in application EP-A-0 955 039 , such as glyceryl tri-decyl tetradecanoate (MW = 1143 g / mol) or pentaerythrityl tetra decyl tetradecanoate (MW = 1538 g / mol).

It is also possible to mention esters of aromatic acids and alcohols comprising 4 to 22 atoms such as tridecyl trimellitate (MW = 757 g / mol). The polyesters resulting from the esterification of at least one carboxylic acid (s) triglyceride (s) hydroxylated with an aliphatic monocarboxylic acid and an optionally unsaturated aliphatic dicarboxylic acid such as castor oil may be used. of succinic acid and isostearic acid sold under the reference Zénigloss by Zenitech. ii) monohydroxy fatty alcohols having 8 to 30 carbon atoms, more preferably 12 to 26 carbon atoms, saturated or unsaturated, linear or branched, such as octyl dodecanol, 2-butyloctanol, 2-hexyl decanol, 2-undecylpentadecanol, oleic alcohol; iii) saturated or unsaturated C12-C26, preferably C12-C22 fatty acids, such as oleic acid, linoleic acid, linolenic acid, and mixtures thereof; iv) di-alkyl carbonates, the 2 alkyl chains being identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC®, by Cognis; and v) copolymers of vinylpyrrolidone such as the vinylpyrrolidone / 1-hexadecene copolymer, ANTARON V-216 sold or manufactured by ISP (MW = 7300 g / mol). b) Non-volatile oils comprising at least two free hydroxyl groups: The second or second oils may be chosen from non-volatile hydrocarbon oils comprising at least two free hydroxyl groups, preferably at least three free hydroxyl groups. According to a first advantageous variant of the invention, the second oil or oils further comprise at least one ester function. As examples of suitable oils, mention may be made of: * vegetable hydrocarbon-based oils such as liquid triglycerides of fatty acids having from 4 to 40 carbon atoms and comprising at least two free hydroxyl groups, advantageously at least three groups free hydroxyl, such as castor oil; hydroxyl esters, preferably having a total number of carbon ranging from 35 to 70, such as polyglyceryl triisostearate (MW = 965 g / mol), polyglyceryl isostearate 1-2; polyglyceryl diisostearate 1-2; polyglyceryl 3-diisostearate, glycerine stearate; glycerine isostearate; or their mixtures; the diol dimer and diacid dimer esters of the general formula HO-R1 - (- 000-R2-COO-R1-) h-OH, in which: R1 represents a residue of diol dimer obtained by hydrogenation of the dilinoleic diacid, R2 represents a hydrogenated dilinoleic diacid residue, and h represents an integer ranging from 1 to 9, especially the esters of dilinoleic diacids and of dilinoleic diol dimers marketed by the company NIPPON FINE CHEMICAL under the trade name LUSPLAN DD-DA5® and DD- DA7, and polyesters obtained by condensation of dimer and / or trimer of unsaturated fatty acid and diol such as in particular dilinoleic acid and 1,4-butanediol. Mention may in particular be made of the polymer marketed by Biosynthis under the name Viscoplast 14436H (INCI name: dilinoleic acid / butanediol copolymer), or also copolymers of polyols and diacid dimers, and their esters, such as Hailucent ISDA.

According to a second advantageous variant of the invention, the second or more hydrocarbon oils are chosen from polyhydroxy alcohols, preferably of C2-C8, and more preferably of C3-C6, comprising two to three hydroxyl groups, such as glycerine. propylene glycol, pentylene glycol, 1,3-butylene glycol, dipropylene glycol, diglycerine, and mixtures thereof. 2. Apolar non-volatile hydrocarbon oils The W / O emulsion according to the invention may also comprise, as oil (s) present in the second oily phase, at least one apolar non-volatile hydrocarbon oil. These oils can be of vegetable, mineral or synthetic origin. For the purposes of the present invention, the term "apolar oil" is intended to mean an oil formed essentially or even consisting of carbon and hydrogen atoms, and not containing oxygen, nitrogen, silicon or of fluorine. Preferably, the non-volatile apolar hydrocarbon oil may be chosen from linear or branched hydrocarbons of mineral or synthetic origin such as: paraffin oil or its derivatives, squalane, isoeicosane, naphthalene oil, polybutenes such as, for example, INDOPOL H-100 (molar mass or MW = 965 g / mol), INDOPOL H-300 (MW = 1340 g / mol), INDOPOL H-1500 (MW = 2160g / mol) marketed or manufactured by the company AMOCO, polyisobutenes, hydrogenated or not, such as for example Parléam® marketed by the company NIPPON Oit FATS, PANALANE H-300 E marketed or manufactured by the company AMOCO (MW = 1340 g / mol), the Viseal 20000 marketed or manufactured by SYNTEAL (MW = 6000 g / mol), the REWOPAL PIB 1000 30 marketed or manufactured by WITCO (MW = 1000 g) / mol), or the PARLEAM LITE marketed by NOF Corporation, - decene / butene copolymers, copoly Polybutene / polyisobutene monomers, in particular Indopol L-14, hydrogenated polydecenes and polydecenes such as in particular: PURESYN 10 (MW = 723 g / mol), PURESYN 150 (MW = 9200 g / mol) marketed or 5 manufactured by the company MOBIL CHEMICALS, or the PURESYN 6 marketed by EXXONMOBIL CHEMICAL), and their mixtures. 3. Silicone or Hydrocarbon Volatile Oils The H / H emulsion according to the invention may also comprise, as oil (s) present in the second oily phase, at least one volatile silicone or hydrocarbon oil. According to the invention, these volatile oils facilitate, in particular, the application of the composition to the skin, lips or integuments. These oils may be hydrocarbon oils, silicone oils optionally comprising pendant alkyl or alkoxy groups or at the end of a silicone chain or a mixture of these oils. As the volatile silicone oil that may be used in the invention, mention may be made of linear or cyclic silicone oils having a viscosity at room temperature of less than 8 cSt and in particular having from 2 to 7 silicon atoms, these silicones optionally comprising alkyl groups or alkoxy having 1 to 10 carbon atoms. As volatile silicone oil that can be used in the invention, there may be mentioned in particular octamethylcyclo-tetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrifiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof. Hydrocarbon volatile oils that can be used in the invention include volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof and especially C8-C16 branched alkanes such as isoalkanes (also known as isoparaffins) with C8-C16 content. , isododecane, isodecane, isohexadecane and for example the oils sold under the trade names of Isopars or permetyls and mixtures thereof.

Preferably, isododecane (permetyls 99 A), isoparaffins C8-C16 as Isopar L, E, G or H, their mixtures, optionally associated with decamethyl tetrasiloxane or cyclopentasiloxane. Fluorinated volatile oils can also be used.

The emulsion according to the invention more particularly comprises from 5 to 95% by weight, preferably from 30 to 70% by weight, of the oil or oils of the first oily phase, relative to the weight of the emulsion. The emulsion according to the invention more particularly comprises from 5 to 95% by weight, preferably from 30 to 70% by weight, of the oil or oils of the second oily phase, relative to the weight of the emulsion. Preferably, the second oily phase comprises at least one non-volatile oil. According to this variant, the volatile oil content of the second oily phase represents from 0.1 to 30% by weight relative to the weight of the emulsion. According to an advantageous embodiment of the invention, the weight ratio of the oil or oils of the first oily phase relative to the oil or oils of the second oily phase represents from 5/95 to 95/5, preferably from 30/70 to 70/30. According to a first embodiment of the invention, the H / H emulsion comprises a first oily phase containing at least a first oil chosen from non-volatile silicone oils and a second oily phase containing at least a second oil chosen from oils. Nonpolar hydrocarbonaceous hydrocarbons. Preferably, the apolar oils are selected from oils having a viscosity of at least 50 cPs, preferably at least 60 cPs. According to a particularly advantageous embodiment of the invention, the non-volatile non-volatile oil (s) are chosen from hydrogenated or non-hydrogenated polydecenes, hydrogenated or non-hydrogenated polybutenes, or mixtures thereof. According to a second embodiment of the invention, the W / O emulsion comprises a first oily phase containing at least a first oil chosen from non-volatile non-volatile silicone oils or phenylated non-volatile silicone oils containing at least one fragment. dimethicone, and a second oily phase containing at least one second oil selected from nonvolatile hydrocarbon oils comprising at most one free hydroxyl group or none comprising it.

As regards non-volatile, non-phenyl silicone oils, these may preferably be chosen from silicone oils of formula (F). As regards the non-volatile phenyl silicone oils comprising at least one dimethicone fragment, the latter may be chosen from the compounds of formula (I) with radicals R such that the silicone is phenylated and comprises at least one dimethicone fragment; (II) with radicals R such that the silicone is phenylated and comprises at least one dimethicone moiety; (IV); (V) with p not zero, in particular (VI) with p not zero and in particular variants (A) and (B); (VII) with p nonzero, (IX) with radicals R such that the silicone is phenylated and comprises at least one dimethicone moiety, or mixtures thereof.

More particularly, the second oil or oils are chosen from non-volatile esters oils i), fatty alcohols ii) and mixtures thereof. According to a third embodiment of the invention, the W / O emulsion comprises a first oily phase containing at least a first oil chosen from non-volatile silicone oils, and a second oily phase containing at least a second oil chosen from non-volatile hydrocarbon oils comprising at least two free hydroxyl groups, preferably at least three free hydroxyl groups. More particularly, said non-volatile hydrocarbon oils comprise at least one carboxylic ester group. Also suitable for this variant, as the second oil (s), the nonvolatile hydrocarbon oils comprising three acid ester functions comprising three carboxylic functions, monohydroxylated, and C2-C4 monoalcohol. According to a fourth preferred embodiment of the invention, the W / O emulsion comprises a first oily phase containing at least a first oil chosen from phenylated nonvolatile silicone oils having no dimethicone fragment, and a second oily phase. containing at least one second oil chosen from non-volatile hydrocarbon oils comprising at least two free hydroxyl groups, and preferably at least three free hydroxyl groups, or from non-volatile nonpolar hydrocarbon oils, and even more particularly at least one second chosen oil. among the non-volatile hydrocarbon oils comprising at least two free hydroxyl groups, and preferably at least three free hydroxyl groups. As regards phenylated nonvolatile silicone oils having no dimethicone fragment, the latter are more particularly chosen from (I), with radicals R such that the silicone is without dimethicone fragment; (II) with radicals R such that the silicone is without dimethicone moiety, especially formulas (III) and (III '); (V) with p = 0; (VI) with p = 0; (VII) with p = 0; (VIII); (IX) with radicals R such that the silicone is without dimethicone moiety; or their mixtures. According to one particular embodiment of the invention, the non-volatile non-volatile oil (s) is (are) chosen from hydrogenated or non-hydrogenated polydecenes, hydrogenated or non-hydrogenated polybutenes and mixtures thereof. Preferably, the non-volatile nonpolar hydrocarbon oils have chosen from oils whose viscosity is at least 50 cPs, in particular at least 60 cPs. According to a fifth embodiment of the invention, the W / O emulsion comprises at least one first non-volatile polar hydrocarbon oil and at least one second volatile or non-volatile oil, preferably from non-volatile nonpolar hydrocarbon oils. Preferably, the first polar non-volatile hydrocarbon oil or oils are chosen from ester oils comprising at most one free or non-free hydroxyl group, and preferably from oils also comprising at least three ester functions. The first polar non-volatile hydrocarbon oil or oils may also be chosen from oils comprising at least two free hydroxyl groups and at least one ester function, or from polyhydric alcohols, and also mixtures thereof. The second or non-volatile non-polar oils are preferably chosen from hydrogenated or non-hydrogenated polydecenes, hydrogenated or non-hydrogenated polybutenes, hydrogenated or non-hydrogenated polyisobutenes, or mixtures thereof.

According to a sixth embodiment of the invention, the W / O emulsion comprises a first oily phase comprising at least one non-phenyl silicone nonvolatile oil and a second oily phase containing at least one phenyl silicone nonvolatile oil, whether or not a dimethicone fragment, or at least one volatile silicone oil. According to a last embodiment of the invention, the W / O emulsion comprises a first oily phase comprising at least one phenyl silicone nonvolatile oil having no dimethicone moiety, and a second oily phase containing at least one unsaturated oil. phenyl silicone volatile having at least one dimethicone moiety, or at least one volatile silicone oil. Preferably, the first phenyl silicone non-volatile oil or oils which do not possess a dimethicone fragment are chosen from compounds of formula (II). As for the second or non-volatile silicone oils having at least one dimethicone moiety, they are advantageously chosen from oils i) of formula (VI), more particularly B) with, for example, silicones of formula (VII). As indicated above, the W / O emulsion may comprise at least one volatile oil. More particularly, the first oily phase and / or the second oily phase may comprise at least one volatile oil. It should be noted that the second oily phase may comprise only volatile oils. Reference may be made to what has been detailed above concerning the nature of these oils. STRUCTURING AGENT As indicated above, the W / O emulsion according to the present invention comprises at least one structuring agent chosen from waxes, pasty compounds, polymeric thickeners, mineral thickeners and mixtures thereof. The structuring agent may be incorporated in one or the other of the oily phases of the W / O emulsion according to the invention. Preferably, the structuring agent is present in the continuous oily phase of the emulsion.

The structuring agent is more particularly chosen according to the oil or oils in which it is incorporated.

More particularly, the structuring agent is chosen so that it is compatible with the oil in which it is incorporated. WAXES The emulsion according to the invention may comprise at least one wax. More particularly, the wax is chosen so that it is compatible with the oil in which it is incorporated. Thus, at least one wax which, when mixed with at least one oil (first oil (s) or second (s) oil (s)) (wax / oil ratio) is preferably used. 10 g) at a temperature greater than or equal to the melting temperature of said wax leads to the production of a homogeneous mixture. For the purposes of the present invention, the term "wax" is intended to mean a lipophilic compound, solid at room temperature (25 ° C.), with a reversible solid / liquid state change, having a melting point greater than or equal to 30 ° C. go up to 120 ° C. The melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 30 by the company METLER. Preferably, the measurement protocol is as follows: A sample of 5 mg of wax placed in a crucible is subjected to a first temperature rise from -20 ° C. to 100 ° C., at the heating rate of 10 ° C. C / minute, then cooled from 100 ° C to -20 ° C at a cooling rate of 10 ° C / minute and finally subjected to a second temperature rise from -20 ° C to 100 ° C at a rate of heating 5 ° C / minute. During the second temperature rise, the variation of the power difference absorbed by the empty crucible and the crucible containing the wax sample as a function of temperature is measured. The melting point of the compound is the value of the temperature corresponding to the peak apex of the curve representing the variation of the difference in power absorbed as a function of the temperature.

The wax may especially have a hardness ranging from 0.05 MPa to 15 MPa, and preferably ranging from 6 MPa to 15 MPa. The hardness is determined by measuring the compression force measured at 20 ° C. using the texturometer sold under the name TA-TX2i by the company RHEO, equipped with a stainless steel cylinder with a diameter of 2 mm. moving at the measuring speed of 0.1 mm / s, and penetrating into the wax at a penetration depth of 0.3 mm.

The waxes may be hydrocarbon-based, silicone-based or fluorinated and may be of vegetable, mineral, animal and / or synthetic origin. In particular, the waxes have a melting point of greater than 30 ° C. and better still greater than 45 ° C.

Apolar wax For the purposes of the present invention, the term "apolar wax" is intended to mean a wax whose solubility parameter 8a at 25 ° C. as defined below is equal to 0 (J / cm 3) 1/2. The apolar waxes are in particular hydrocarbon waxes composed solely of carbon and hydrogen atoms and free of heteroatoms such as N, O, Si and P. In particular, by apolar wax is meant a wax which consists solely of apolar wax and not a mixture that would also include other types of waxes that are not apolar waxes. As an illustration of the apolar waxes that are suitable for the invention, there may be mentioned hydrocarbon-based waxes such as microcrystalline waxes, paraffin waxes, ozokerite, polymethylene waxes, polyethylene waxes, and microliters, in particular polyethylene waxes. As polyethylene wax, there may be mentioned PERFORMALENE 500-L POLYETHYLENE and PERFORMALENE 400 POLYETHYLENE marketed by New Phase Technologies and ASENSA SC 211 marketed by HONEYWELL. As polymethylene wax, mention may be made CIREBELLE108 marketed by Cirebelle. OZOKERITE WAX SP 1020 P may be mentioned as ozokerite. As microcrystalline waxes that may be used, mention may be made of MULTIWAX W 445® sold by the company SONNEBORN and MICROWAX HW® and BASE WAX 30540® marketed by the company PARAMELT. to be used in the W / O emulsions according to the invention as apolar wax, there may be mentioned in particular polyethylene microwaxes such as those sold under the names Micropoly 220e, 220Le and 250se by the company Micro Powders.

Polar wax For the purposes of the present invention, the term "polar wax" is intended to mean a wax whose solubility parameter 8a at 25 ° C. is different from 0 (J / cm 3) 1/2. In particular, "polar wax" means a wax whose chemical structure is formed essentially or even consisting of carbon and hydrogen atoms, and comprising at least one strongly electronegative heteroatom such as an atom of oxygen, nitrogen, silicon or phosphorus. The definition and calculation of the solubility parameters in the HANSEN three-dimensional solubility space are described in the article by C. M. Hansen: "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967). According to this Hansen space: - 81) characterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular shocks; - 8p characterizes the DEBYE interaction forces between permanent dipoles 20 as well as the KEESOM interaction forces between induced dipoles and permanent dipoles - 811 characterizes the specific interaction forces (hydrogen bond, acid / base, donor / acceptor type , etc.); - 8a is determined by the equation: 8a = (8p2 + 8h2) 1/4. The parameters 8p, 8h, 81) and 8a are expressed in (J / cm3) 1/4. The polar waxes may especially be hydrocarbon-based, fluorinated or silicone-based, and preferably hydrocarbon-based or silicone-based. By "silicone wax" is meant an oil comprising at least one silicon atom, and in particular comprising Si-O groups. By "hydrocarbon wax" is meant a wax formed essentially or even consisting of carbon and hydrogen atoms, and optionally oxygen, nitrogen, and not containing a silicon atom or of fluorine. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups. Hydrocarbon Waxes According to a first preferred embodiment, the polar wax is a hydrocarbon wax. As hydrocarbon polar wax, a wax chosen from ester waxes and alcohol waxes is particularly preferred. By "ester wax" is meant according to the invention a wax comprising at least one ester function. The ester waxes may be further hydroxylated.

By "alcohol wax" is meant according to the invention a wax comprising at least one alcohol function, that is to say comprising at least one free hydroxyl (OH) group. Ester waxes may be especially used as ester waxes, such as those chosen from: i) waxes of formula R 1 COOR 2 in which R 1 and R 2 represent linear, branched or cyclic aliphatic chains whose number of atoms varies from 10 at 50, which may contain a heteroatom such as O, N or P and whose melting point temperature varies from 25 to 120 ° C. In particular, a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group comprising 20 to 40 carbon atoms), alone or as a mixture or a C20-C40 alkyl stearate, may be used as ester wax. Such waxes are sold, for example, under the names "Kester Wax K 82 pe", "Hydroxypolyester K 82 pe", "Kester Wax K 80 pe", or "KESTER WAX K82H" by the company KOSTER KEUNEN. It is also possible to use a montanate (octacosanoate) of glycol and butylene glycol, such as the wax LICOWAX KPS FLAKES (INCI name: montanate glycol) marketed by Clariant. ii) di- (trimethylol-l, l, l, l, l propane tetrastearate, sold under the name Hest 2T-45e by the company HETERENE. iii) diester waxes of a dicarboxylic acid of general formula R3 - (- 000-R4-COO-R5), in which R3 and R5 are identical or different, preferably identical and represent a C4-C30 alkyl group (group alkyl comprising from 4 to 30 carbon atoms) and R4 represents a linear or branched C4-C30 aliphatic group (alkyl group comprising from 4 to 30 carbon atoms) which may or may not contain 1 or more unsaturations. Preferably, the C 4 -C 30 aliphatic group is linear and unsaturated. iv) We may also mention the waxes obtained by catalytic hydrogenation of animal or vegetable oils having C8-C32 linear or branched fatty chains, for example such as hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, and waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, such as those sold under the names Phytowax ricin 16L64® and 22L73® by the SOPHIM company. Such waxes are described in application FR-A-2792190. As waxes obtained by hydrogenation of olive oil esterified with stearyl alcohol, mention may be made of those sold under the name "PHYTOWAX Olive 18 L 57". v) The waxes corresponding to partial or total esters, preferably total, of a saturated, optionally hydroxylated C16-C30 carboxylic acid with glycerol. By total esters is meant that all the hydroxyl functions of glycerol are esterified.

By way of example, there may be mentioned trihydroxystearine (or glyceryl trihydroxystearate), tristearin (or glyceryl tristearate), tribehenin (or glyceryl tribehenate), alone or as a mixture. Suitable compounds include the triesters of glycerol and 12-hydroxystearic acid, or hydrogenated castor oil, such as for example Thixcin R, Thixcin E, marketed by Elementis Specialties. vi) It may also be mentioned beeswax, synthetic beeswax, polyglycerolated beeswax, carnauba wax, candellila wax, oxypropylene lanolin wax, rice bran wax, Ouricury wax, Alfa wax, cork fiber wax, sugar cane wax, Japanese wax, sumac wax, montan wax, orange wax, laurel wax , hydrogenated Jojoba wax, and mixtures thereof.

According to another embodiment, the polar wax may be an alcohol wax. As alcohol wax, there may be mentioned alcohols, preferably linear, preferably saturated, comprising from 16 to 60 carbon atoms, whose melting point is between 25 and 120 ° C. As alcohol wax, mention may be made, for example, of Performacol 550-L Alcohol wax from New Phase Technologie, stearic alcohol, cetyl alcohol, myristic alcohol, palmitic alcohol, behen alcohol, erucic alcohol, arachidyl alcohol, or mixtures thereof.

Silicone Waxes By "silicone wax" is meant an oil comprising at least one silicon atom, and especially including Si-O groups. Such commercial silicone waxes include those sold under the names Abilwax 9810 (GOLDSCHMIDT), KF910 and KF7002 (SHIN ETSU), or 176-11481 (GENERAL ELECTRIC). The silicone waxes that may be used may also be alkyl or alkoxydimethicones, as well as (C 20 -C 60) alkyl dimethicones, in particular (C 30 -C 45) alkyl dimethicones, such as the silicone wax sold under the name SF-1642 by GE-Bayer. Silicones or the ALKYLDIMETHYL C30-45 SILYL POLYPROPYLSILSESQUIOXANE under the name SW-8005® C30 WAX RESIN sold by the company Dow Corning. Mention may also be made of silicone waxes obtained by esterification with a (poly) alkoxylated silicone, such as silicone beeswax, silicone candelilla wax or silicone carnauba wax. When the emulsion comprises them, the wax content ( s) is preferably between 0.1% and 20%, preferably 0.5% and 15%, more particularly 1% and 10% by weight, relative to the total weight of the oil or oils in which 20 it (s) is / are incorporated. PASTE COMPOUNDS The emulsion according to the invention may comprise at least one pasty compound at 25 ° C. and atmospheric pressure. More particularly, the pasty compound is chosen so that it is compatible with the oil in which it is incorporated. Thus, at least one pasty compound which, when it is mixed with at least one oil (first (s) oil (s) or second (s) oil (s)) (compound pasty / oil ratio) is preferably used. 10/90; sample of 10 g) at a temperature greater than or equal to the melting temperature of said pasty compound leads to the production of a homogeneous mixture. Note that this pasty compound is immiscible with water.

For the purposes of the present invention, the term "pasty" means a reversible solid / liquid change-state compound, having in the solid state an anisotropic crystalline organization, and comprising at a temperature of 23 ° C. a liquid fraction and a solid fraction.

In other words, the starting melting temperature of the pasty compound may be less than 23 ° C. The liquid fraction of the pasty compound measured at 23 ° C. can represent 9 to 97% by weight of the pasty compound. This liquid fraction at 23 ° C is preferably between 15 and 85%, more preferably between 40 and 85% by weight. For the purposes of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in ISO 11357-3; 1999. The melting point of a pasty compound can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name "MDSC 2920" by the company TA Instruments. The measurement protocol is as follows: A sample of 5 mg of pasty compound placed in a crucible is subjected to a first temperature rise from -20 ° C to 100 ° C, at a heating rate of 10 ° C / minute. , then cooled from 100 ° C to -20 ° C at a cooling rate of 10 ° C / min and finally subjected to a second temperature rise from -20 ° C to 100 ° C at a heating rate of 5 ° C. ° C / minute. During the second temperature rise, the variation of the power difference absorbed by the empty crucible and the crucible containing the pasty fatty substance sample is measured as a function of temperature. The melting point of the pasty compound is the value of the temperature corresponding to the peak apex of the curve representing the variation of the difference in power absorbed as a function of the temperature.

The liquid fraction by weight of the pasty compound at 23 ° C. is equal to the ratio of the enthalpy of fusion consumed at 23 ° C. to the heat of fusion of the pasty compound. The enthalpy of fusion of the pasty compound is the enthalpy consumed by the latter to pass from the solid state to the liquid state. The pasty compound is said to be in the solid state when the entirety of its mass is in crystalline solid form. The pasty compound is said to be in a liquid state when all of its mass is in liquid form. The heat of fusion of the pasty compound 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 the company TA instrument with a temperature rise of 5 or 10 ° C per minute, according to ISO 11357-3; 1999. The melting enthalpy of the pasty compound is the amount of energy required to pass the pasty compound 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 it presents at 2 ° C. consisting of a liquid fraction and a liquid fraction. solid fraction. The liquid fraction of the pasty compound measured at 32 ° C is preferably 30 to 100% by weight of the pasty compound, preferably 50 to 100%, more preferably 60 to 100% by weight of the pasty compound. When the liquid fraction of the pasty compound measured at 32 ° C. is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32 ° C. The liquid fraction of the compound body measured at 32 ° C. is equal to the ratio of the enthalpy of fusion consumed at 32 ° C. on the heat of fusion of the pasty compound.

The enthalpy of fusion consumed at 32 ° C. is calculated in the same way as the heat of fusion consumed at 23 ° C. The pasty compound is more particularly chosen according to the oil or oils in which it is incorporated. Thus, at least one pasty compound which, when it is mixed with at least one oil (first (s) oil (s) or second (s) oil (s)) (compound pasty / oil ratio) is preferably used. 25/75; sample of 10 g) at a temperature greater than or equal to the melting temperature of said wax until a homogeneous mixture, which is then allowed to cool to 20 ° C., does not show phase shift of oil (s) greater than 20% by volume, more particularly 10% by volume.

The pasty compound may in particular be chosen from synthetic pasty compounds and fats of plant origin. The pasty compound (s) may be chosen in particular from: lanolin and its derivatives, such as lanolin alcohol, oxyethylenated lanolines, acetylated lanolin, lanolin esters such as isopropyl lanolate and oxypropylenated lanolines ; petroleum jelly (also known as petrolatum), polyol ethers chosen from among pentaerythritol and polyalkylene glycol C 2 -C 4 ethers, fatty alcohol and sugar ethers, and mixtures thereof. For example, mention may be made of pentaerythritol ether and polyethylene glycol comprising 5 oxyethylenated units (50E) (CTFA name: PEG-5 Pentaerythrityl Ether), pentaerythritol ether and polypropylene glycol comprising 5 oxypropylene units (5 PO). (CTFA name: PPG5 Pentaerythrityl Ether), and mixtures thereof, and more especially the PEG-5 Pentaerythrityl Ether mixture, PPG-5 Pentaerythrityl Ether and soya oil, sold under the name "Lanolide" by the company VEVY, a mixture in which the constituents found in a ratio by weight 46/46/8: 46% of PEG-5 Pentaerythrityl Ether, 46% of PPG-5 Pentaerythrityl Ether and 8% of soya oil, - polymeric or non-polymeric silicone compounds, - fluorinated compounds polymers or not, - vinyl polymers, in particular: - homopolymers and copolymers of olefins, - homopolymers and copolymers of hydrogenated dienes, - linear or branched oligomers, homo or copolymers of (m th) alkyl acrylates preferably having a C 8 -C 30 alkyl group; homo and copolymeric oligomers of vinyl esters having C 8 -C 30 alkyl groups; and homo- and copolymer oligomers of vinyl ethers having alkyl groups. at C8-C30, liposoluble polyethers resulting from the polyetherification between one or more C2-C100 diols, preferably C2-050 diols. Among the liposoluble polyethers, ethylene oxide and / or propylene oxide copolymers are especially considered with C 6 -C 30 long chain alkylene oxides, more preferably such as the weight ratio of ethylene oxide. oxide and / or propylene oxide with alkylene oxide in the copolymer is from 5:95 to 70:30. In this family, mention will be made in particular of copolymers such as long-chain alkylene oxides arranged in blocks having an average molecular weight of 1000 to 10,000, for example a polyoxyethylene / polydodecyl glycol block copolymer such as dodecanediol ethers (22). mol) and polyethylene glycol (45 0E) marketed under the tradename ELFACOS ST9 by AKZO NOBEL. esters and polyesters. Among the esters, particular mention is made of: the esters of a glycerol oligomer, in particular the diglycerol esters, in particular the adipic acid and diglycerol condensates, for which part of the hydroxyl groups of the glycerols reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid, isostearic acid and 12-hydroxystearic acid, for example the bis-diglyceryl polyacyladipate-2 marketed under the reference SOFTISAN® 649 by the company CREMER OLEO, homopolymers of vinyl ester having C8-C30 alkyl groups, such as polyvinyl laurate (in particular sold under the reference Mexomer PP by the company Chimex), propionate d arachidyl sold under the trade name Waxenol 801 by ALZO, - phytosterol esters, - triglycerides of fatty acids and their derivatives, - pentaerythritol esters, - esters of diol dimer and diol diacid mother, if appropriate, esterified on their function (s) alcohol (s) or acid (s) free (s) by acid radicals or alcohols, including dimer dilinoleate esters; such esters may in particular be chosen from the following INCI nomenclature esters: bis-behenyl / isostearyl / phytosteryl dimerdilinoleyl dimerdilinoleate (Plandool G), phytosteryl / isosteryl / cetyl / stearyl / behenyl dimerdilinoleate (Plandool H or Plandool S) and their mixtures, vegetable butters such as mango butter, such as that sold under the reference Lipex 203 by the company Aharhuskarlshamn, shea butter, in particular the one whose INCI name is Butyrospermum Parkii Butter, such as sold under the reference Sheasofte by the company Aharushkarlshamn, cupuacu butter (Rai forest RF3410 from Beraca 30 Sabara), murumuru butter (RAIN FOREST RF3710 from Beraca Sabara), cocoa butter; as well as orange wax, for example, the one marketed under the reference Orange Peel Wax by the company Koster Keunen, - vegetable oils that are totally or partially hydrogenated, for example hydrogenated soybean oil, oil hydrogenated coconut oil, hydrogenated rapeseed oil, hydrogenated vegetable oil mixtures such as the hydrogenated vegetable oil mixture of soybean, coconut, palm and rapeseed, for example the mixture sold under the name Akogele by the company Aharushkarlshamn ( INCI name Hydrogenated Vegetable Oil), the product marketed under the reference Cegesofte HF 52 from BASF (INCI name Hydrogenated Vegetable Oil), trans isomerized partially hydrogenated jojoba oil manufactured or marketed by Desert Whale under the trade name Iso-Jojoba -50e, partially hydrogenated olive oil such as, for example, the compound marketed under the reference Beurrolive p by the company Soliance, - esters of hydrogenated castor oil, such as hydrogenated castor oil dimer dilinoleate, for example RISOCAST-DA-L sold by KOKYU ALCOHOL KOGYO, hydrogenated castor oil isostearate for example the SALACOS HCISV-L 15 sold by NISSHIN OILLIO, - and mixtures thereof. Preferably, the pasty compounds which are suitable for carrying out the invention are chosen from hydrocarbon compounds and comprise, in addition to the 20 carbon atoms and hydrogen atoms, at least oxygen atoms. Thus, preferably, the pasty compounds do not therefore comprise a silicon atom or a fluorine atom. According to a preferred embodiment, the pasty compound (s) are chosen from lanolin and its derivatives, esters of glycerol oligomers, butters of plant origin, vegetable oils which are totally or partially hydrogenated, and esters of oils. hydrogenated castor oil, or mixtures thereof. When the emulsion comprises at least one pasty compound, the content of pasty compound (s) is preferably between 0.1 and 30% by weight, preferably 0.5 and 20% by weight, more particularly 1 and 10% by weight. weight, relative to the total weight of the oil or oils in which it (s) is / are incorporated.

Suitable polymeric thickeners include organopolysiloxane elastomers, semi-crystalline polymers, hydrocarbon polyamides, silicone polyamides, dextrin esters, and mixtures thereof.

More particularly, the polymeric thickener is chosen so that it is compatible with the oil in which it is incorporated. Thus, at least one polymeric thickening agent which, when it is mixed with at least one oil (first oil (s) or second (s) oil (s)) is preferably used (proportion polymeric thickening agent). / oil: 10/90; sample of 10 g) at a temperature greater than or equal to the melting temperature of said polymeric thickening agent leads to obtaining a homogeneous mixture. The choice of the polymeric thickening agent may advantageously be carried out according to the nature of the oils in the presence. For example, if the oil is hydrocarbon, it may be advantageous to choose a polymeric hydrocarbon thickening agent, if the oil is silicone, it may be advantageous to choose a silicone polymeric thickening agent. If the W / O emulsion comprises, the content of polymeric thickening agent (s), expressed as dry matter, varies more particularly from 0.1 to 40% by weight, preferably from 0.1. at 20% by weight, and even more preferably from 0.1 to 10% by weight, relative to the total weight of the oil or oils in which it (they) is / are incorporated. Organopolysiloxane Elastomer The organopolysiloxane elastomer, which can be used as polymeric thickener, also has the advantage of giving the composition according to the invention good application properties. It provides a very soft and matifying after application, particularly advantageous for application to the skin, especially for foundation compositions. It can also allow an effective filling of the hollows present on the keratin materials.

By "organopolysiloxane elastomer" or "silicone elastomer" is meant a flexible, deformable organopolysiloxane having viscoelastic properties and especially the consistency of a sponge or a flexible sphere. Its modulus of elasticity is such that this material resists deformation and has a limited capacity for extension and contraction. This material is able to recover its original shape after stretching. It is more particularly a crosslinked organopolysiloxane elastomer.

Thus, the organopolysiloxane elastomer can be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one silicon-bonded hydrogen and diorganopolysiloxane having silicon-bonded ethylenically unsaturated groups, especially in the presence of platinum catalyst; or by condensation-crosslinking dehydrogenation reaction between a hydroxyl-terminated diorganopolysiloxane and a diorganopolysiloxane containing at least one silicon-bonded hydrogen, especially in the presence of an organotin; or by crosslinking condensation reaction of a hydroxyl-terminated diorganopolysiloxane and a hydrolyzable organopolysilane; or by thermal crosslinking of organopolysiloxane, especially in the presence of organoperoxide catalyst; or by crosslinking of organopolysiloxane by high energy radiation such as gamma rays, ultraviolet rays, electron beam. Preferably, the organopolysiloxane elastomer is obtained by addition reaction crosslinking (A) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B) diorganopolysiloxane having at least two silicon-bonded ethylenic unsaturation groups. , especially in the presence (C) of platinum catalyst, as for example described in the application EP-A-295886. In particular, the organopolysiloxane elastomer may be obtained by reaction of dimethylvinylsiloxy-terminated dimethylpolysiloxane and trimethylsiloxy-terminated methylhydrogenpolysiloxane in the presence of platinum catalyst.

The compound (A) is the basic reagent for the formation of organopolysiloxane elastomer and the crosslinking is carried out by addition reaction of the compound (A) with the compound (B) in the presence of the catalyst (C). The compound (A) is in particular an organopolysiloxane having at least two hydrogen atoms bonded to distinct silicon atoms in each molecule.

The compound (A) may have any molecular structure, in particular a linear chain or branched chain structure or a cyclic structure.

The compound (A) may have a viscosity at 25 ° C ranging from 1 to 50,000 centistokes, in particular to be well miscible with the compound (B). The organic groups bonded to the silicon atoms of the compound (A) can be alkyl groups such as methyl, ethyl, propyl, butyl, octyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl, 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl, xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon groups such as an epoxy group, a carboxylate ester group, or a mercapto group. The compound (A) may thus be chosen from trimethylsiloxy-terminated methylhydrogenpolysiloxanes, trimethylsiloxy-terminated dimethylsiloxanemethylhydrogensiloxane copolymers and dimethylsiloxane-methylhydrogensiloxane cyclic copolymers. The compound (B) is advantageously a diorganopolysiloxane having at least two lower alkenyl groups (for example C2-C4); the lower alkenyl group may be selected from vinyl, allyl, and propenyl groups. These lower alkenyl groups may be located at any position of the organopolysiloxane molecule but are preferably located at the ends of the organopolysiloxane molecule. The organopolysiloxane (B) may have a branched chain, straight chain, cyclic or network structure but the linear chain structure is preferred. The compound (B) may have a viscosity ranging from the liquid state to the gum state. Preferably, the compound (B) has a viscosity of at least 100 centistokes at 25 ° C. In addition to the aforementioned alkenyl groups, the other organic groups bonded to the silicon atoms in the compound (B) may be alkyl groups such as methyl, ethyl, propyl, butyl or octyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl or 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl or xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon groups such as an epoxy group, a carboxylate ester group, or a mercapto group. The organopolysiloxane (B) can be selected from 30 methylvinylpolysiloxanes, the methylvinylsiloxane-dimethylsiloxane copolymers, dimethylpolysiloxanes comprising dimethylvinylsiloxy endings, dimethylsiloxane-methylphenylsiloxane dimethylvinylsiloxy end groups, dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane containing dimethylvinylsiloxy end groups, dimethylsiloxane-methylvinylsiloxane trimethylsiloxy end-groups, trimethylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers, dimethylvinylsiloxy-terminated methyl (3,3,3-trifluoropropyl) polysiloxane, and dimethylvinylsiloxy-terminated dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymers . In particular, the organopolysiloxane elastomer may be obtained by reaction of dimethylvinylsiloxy-terminated dimethylpolysiloxane and trimethylsiloxy-terminated methylhydrogenpolysiloxane in the presence of platinum catalyst.

Advantageously, the sum of the number of ethylenic groups per molecule of the compound (B) and the number of hydrogen atoms bonded to silicon atoms per molecule of the compound (A) is at least 5. It is advantageous that the compound (A) is added in an amount such that the molecular ratio between the total amount of hydrogen atoms bonded to silicon atoms in the compound (A) and the total amount of all ethylenically unsaturated groups in the compound (B) is in the range of 1.5 / 1 to 20/1. Compound (C) is the catalyst for the crosslinking reaction, and is especially chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black, and platinum. on support. The catalyst (C) is preferably added from 0.1 to 1000 parts by weight, more preferably from 1 to 100 parts by weight, as clean platinum metal per 1000 parts by weight of the total amount of the compounds (A) and ( B). The elastomer is advantageously a non-emulsifying elastomer.

The term "non-emulsifying" defines organopolysiloxane elastomers that do not contain a hydrophilic chain, and in particular that do not contain polyoxyalkylene (especially polyoxyethylene or polyoxypropylene) units or polyglyceryl units. Thus, according to one particular embodiment of the invention, the W / O emulsion comprises an organopolysiloxane elastomer devoid of polyoxyalkylene units and a polyglyceryl unit. In particular, the silicone elastomer used in the present invention is selected from Dimethicone Crosspolymer (INCI Name), Vinyl Dimethicone Crosspolymer (INCI Name), DimethiconeNinyl Dimethicone Crosspolymer (INCI Name), Dimethicone Crosspolymer-3 (Name 1NCI). The organopolysiloxane elastomer particles may be transported in the form of a gel consisting of an elastomeric organopolysiloxane included in at least one hydrocarbon oil and / or a silicone oil. In these gels, the organopolysiloxane particles are often non-spherical particles. Non-emulsifying elastomers are described in EP 242 219, EP 285 886, EP 765 656 and JP-A-61-194009. The silicone elastomer is generally in the form of a gel, a paste or a powder but advantageously in the form of a gel in which the silicone elastomer is dispersed in a linear silicone oil ( dimethicone) or cyclic (eg cyclopentasiloxane), advantageously in a linear silicone oil. As non-emulsifying elastomers, those sold under the names "KSG-6", "KSG-15", "KSG-16", "KSG-18", "KSG-41", "KSG-42" can more particularly be used. KSG-43, KSG-44, by Shin Etsu, DC9040, DC9041, Dow Corning, SFE 839 by General Electric. According to one particular embodiment, a silicone elastomer gel dispersed in a silicone oil chosen from a non-exhaustive list comprising cyclopentadimethylsiloxane, dimethicones, dimethylsiloxanes, methyl trimethicone, phenylmethicone, phenyldimethicone, phenyhrhnethicone, and cyclomethicone, is used. preferably a linear silicone oil selected from polydimethylsiloxanes (PDMS) or dimethicones with a viscosity at 25 ° C ranging from 1 to. 500 is at 25 ° C, optionally modified with aliphatic groups, optionally fluorinated, or with functional groups such as hydroxyl groups, thiols and / or amines. Mention may in particular be made of the following INCI name compounds: Dimethicone / vinyldimethicone crosspolymer, such as USG-105 and USG-107A from Shin Etsu; "DC9506" and "DC9701" from Dow 30 Coming, - Dimethicone / vinyl dimethicone crosspolymer (and) dimethicone, such as "KSG-6" and "KSG-16" from Shin Etsu; - Dimethicone / vinyl dimethicone crosspolymer (And) Cyclopentasiloxane, such as "KSG-15", - Cyclopentasiloxane (and) dimethicone crosspolymer, such as "DC9040", "DC9045" and "DC5930" from Dow Corning, - Dimethicone (and ) dimethicone crosspolymer, such as "DC9041" from Dow Corning, -C4-24 Alkyl dimethicone / divinyldimethicone crosspolymer, such as NuLastic Silk MA by Alzo.

As examples of silicone elastomers dispersed in a linear silicone oil that can be advantageously used according to the invention, mention may be made in particular of the following references: Dimethicone / vinyl dimethicone crosspolymer (and) dimethicone, such as "KSG-6" and "KSG" -16 "from Shin Etsu Company; dimethicone (and) dimethicone crosspolymer, such as "DC9041" from Dow Corning. According to a particularly preferred embodiment, the W / O emulsion according to the invention comprises at least one cross-linked silicone elastomer INCI "dimethicone (and) dimethicone crosspolymer", preferably with a dimethicone with a viscosity ranging from 1 to 100 cst, in particular from 1 to 10 cc at 25 ° C, such as the mixture of polydimethylsiloxane crosslinked with hexadiene / polydimethylsiloxane (5cst) sold under the name DC 9041 Dow Corning.

The organopolysiloxane elastomer particles may also be used in powder form: mention may be made of the powders sold under the names "Dow Corning 9505 Powder" and "Dow Corning 9506 Powder" by the company Dow Corning, these powders being named INCI: dimethicone / vinyl dimethicone crosspolymer.

The organopolysiloxane powder may also be coated with silsesquioxane resin, as described for example in patent U55538793. Such elastomer powder is sold under the names "KSP-100", "KSP-101", "KSP-102", "KSP-103", "KSP-104", "KSP-105" by the company Shin Etsu, and INCI name: vinyl dimethicone / methicone sil sesquioxane Crosspolymer. Semi-crystalline polymers The W / O emulsion according to the invention may comprise at least one semi-crystalline polymer. Preferably, the semi-crystalline polymer has an organic structure, and a melting temperature is greater than or equal to 30 ° C. For the purposes of the invention, the term "semi-crystalline polymer" is intended to mean polymers comprising a crystallizable part and an amorphous part and having a first-order reversible phase change temperature, in particular melting (solid-liquid transition). . The crystallizable portion is either a side chain (or pendant chain) or a sequence in the backbone. When the crystallizable portion of the semi-crystalline polymer is a sequence of the polymer backbone, this crystallizable block is of a different chemical nature from that of the amorphous sequences; in this case, the semicrystalline polymer is a block copolymer, for example of the diblock, triblock or multiblock type. When the crystallizable portion is a chain pendant to the backbone, the semi-crystalline polymer may be a homopolymer or a parent copoly. The melting temperature of the semi-crystalline polymer is preferably less than 150 ° C. The melting temperature of the semi-crystalline polymer is preferably greater than or equal to 30 ° C and less than 100 ° C. More preferably, the melting temperature of the semi-crystalline polymer is preferably greater than or equal to 30 ° C and less than 70 ° C.

The semi-crystalline polymer (s) according to the invention used are solids at ambient temperature (25 ° C.) and atmospheric pressure (760 mmHg), whose melting temperature is greater than or equal to 30 ° C. The melting point values correspond to the melting point measured using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name DSC 30 by the company METTLER, with a temperature increase of 5%. or 10 ° C per minute. (The melting point considered is the point corresponding to the temperature of the most endothermic peak of the thermogram).

The semi-crystalline polymer (s) according to the invention preferably have a melting point higher than the temperature of the keratinous support intended to receive said composition, in particular the skin or the lips. By "chain or crystallizable block" is meant, in the sense of the invention, a chain or sequence which, if it were alone, would pass from the amorphous state to the crystalline state, reversibly, depending on whether it is above or below below the melting temperature. A chain within the meaning of the invention is a group of atoms, during or lateral to the backbone of the polymer. A sequence is a group of atoms belonging to the backbone, a group constituting one of the repeating units of the polymer.

Preferably, the polymer backbone of the semi-crystalline polymers is soluble in the oily phase at a temperature above their melting point. Preferably, the crystallizable sequences or chains of the semicrystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%. Crystallizable side-chain semi-crystalline polymers are homo- or co-polymers. The semicrystalline polymers of the invention with crystallizable sequences are copolymers, sequenced or multiblocked. They can be obtained by reactive (or ethylenic) double bond monomer polymerization or by polycondensation. When the polymers of the invention are crystallizable side chain polymers, the latter are advantageously in random or statistical form. Preferably, the semi-crystalline polymers of the invention are of synthetic origin. According to a preferred embodiment, the semi-crystalline polymer is chosen from: homopolymers and copolymers comprising units resulting from the polymerization of one or more monomers bearing hydrophobic side chain (s) crystallizable (s) ), polymers bearing in the backbone at least one crystallizable block, polycondensates of polyester, aliphatic or aromatic or aliphatic / aromatic type, metallocene-catalyzed copolymers of ethylene and propylene, and acrylate copolymers. /silicone. The semicrystalline polymers that may be used in the invention may be chosen in particular from: - block copolymers of polyolefins with controlled crystallization, the monomers of which are described in EP-A-0 951 897, - polycondensates, and in particular of polyester type, aliphatic or aromatic or aliphatic / aromatic, copolymers of ethylene and propylene prepared by metallocene catalysis, homopolymers or copolymers bearing at least one crystallizable side chain and homo- or co-polymers carrying in the backbone less a crystallizable block, such as those described in US-A-5,156,911, such as the (Cio-C30) alkyl polyacrylates corresponding to Intelimer® from Landec described in the brochure "Intelimere polymers", Landec IP22 (Rev. 4 97) and for example the product Intelimer® IPA 13-1 from Landec, which is a stearyl polyacrylate with a molecular weight of about 145,000 and whose tem melting temperature is equal to 49 ° C, homopolymers or copolymers bearing at least one crystallizable side chain, in particular with fluorinated group (s), as described in document WO-A-01/19333 acrylate / silicone copolymers, such as polydimethylsiloxane grafted stearyl acrylate and acrylic acid copolymers, polydimethylsiloxane grafted stearyl methacrylate copolymers, polydimethylsiloxane grafted stearyl methacrylate and acrylic acid copolymers; copolymers of methyl methacrylate, butyl methacrylate, ethyl-2-hexyl acrylate and stearyl methacrylate with polydimethylsiloxane grafts. Mention may in particular be made of the copolymers sold by the company SHIN-ETSU under the names KP-561 (CTFA name: acrylates / dimethicone), and mixtures thereof.

Hydrocarbon Polyamide For the purposes of the invention, the term "polymer" means a compound having at least 2, preferably at least 3 and more preferably 10 repeating units.

By "polyamide" is meant in the sense of the invention a compound having at least 2, preferably at least 3 and more preferably 10 repeat units amide. By "hydrocarbon-based polyamide" is meant a polyamide formed essentially or even consisting of carbon and hydrogen atoms, and possibly of oxygen, nitrogen, and not containing a silicon or fluorine atom. . It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups. For the purposes of the invention, the term "functionalized chains" means an alkyl chain comprising one or more functional groups or reactive groups chosen in particular from hydroxyl, ether, esters, oxyalkylene or polyoxyalkylene groups.

Advantageously, this polyamide, of the emulsion according to the invention has a weight average molecular weight of less than 100,000 g / mol, especially ranging from 1000 to 100,000 g / mol, in particular ranging from 1,000 to 50,000 g / mol, and more particularly ranging from 1000 to 30 000 g / mol, preferably from 2000 to 20 000 g / mol, and better still from 2000 to 10 000 g / mol.

This polyamide is insoluble in water, especially at 25 ° C. According to a first embodiment of the invention, the polyamide is a compound (i), namely a hydrocarbon polyamide, in particular a non-silicone hydrocarbon of the following formula (Ta): ## STR2 ## Wherein n denotes an integer number of amide units such that the number of ester groups represents from 10% to 50% of the total number of ester and amide groups; R 1 is independently at each occurrence an alkyl or alkenyl group having at least 4 carbon atoms and especially 4 to 24 carbon atoms; R2 is independently at each occurrence a C4-C42 hydrocarbon group provided that 50% of the R2 groups represent a C30-C42 hydrocarbon group; R3 independently represents an organic group having at least 2 carbon atoms, hydrogen atoms and optionally one or more oxygen or nitrogen atoms; and R4 represents at each occurrence independently a hydrogen atom, a C1-C10 alkyl group or a direct bond to R3 OR to another R4 so that the nitrogen atom to which both R3 and R4 are bonded makes part of a heterocyclic structure defined by R4-N-R3, with at least 50% of R4 representing a hydrogen atom. In the particular case of the formula (Ta), the optionally functionalized terminal fatty chains are terminal chains linked to the last heteroatom, here nitrogen, of the polyamide backbone. In particular, the ester groups of formula (I), which are part of the terminal and / or pendant fatty chains, represent from 15 to 40% of the total number of ester and amide groups and better still from 20 to 35%. In addition, n advantageously represents an integer ranging from 1 to 5 and better still greater than 2. Preferably, R 1 is a C 12 to C 22 and preferably C 16 to C 22 alkyl group. Advantageously, R2 may be a hydrocarbon group, preferably a C10 to C42 alkylene group. Preferably, R2 is a divalent radical derived from acid dimer. Preferably, at least 50% and more preferably at least 75% of the R2 are groups having from 30 to 42 carbon atoms. The other R 2 are C 4 to C 19 and even C 4 to C 12 hydrogenated groups. Preferably, R3 represents a C2-C36 hydrocarbon group or a polyoxyalkylene group and R4 represents a hydrogen atom. Preferably, R3 represents a C2 to C12 hydrocarbon group, preferably C2. The hydrocarbon groups may be linear, cyclic or branched, saturated or unsaturated groups. Furthermore, the alkyl and alkylene groups can be linear or branched groups, saturated or not. Preferably, the hydrocarbon polyamide of formula (Ta) is such that n is an integer ranging from 1 to 5, preferably greater than 2, R1 is a C12 to C22 alkyl group and preferably C16 to C22, R2 is a C 10 to C 42 hydrocarbon group, preferably a divalent radical derived from an acid dimer, R 3 represents a C 2 to C 12, preferably C 2, hydrocarbon group, and R 4 represents a hydrogen atom. In general, the polyamides of formula (Ta) are in the form of polyamide mixtures, these mixtures may additionally contain a synthetic product corresponding to a compound of formula (Ta) in which n is 0, that is to say a diester. By way of example of hydrocarbon polyamides of formula (Ta) that can be used in the emulsions according to the invention, mention may be made of the commercial products sold by Arizona Chemical under the names Uniclear 80 and Uniclear 100, whose INCI name is "ethylenediamine". / stearyl dimer dilinoleate copolymer ", or Uniclear 80 V, Uniclear 100 V and Uniclear 100 VG whose INCI name is" ethylene diamine / stearyl dimer tallate copolymer ". They are sold respectively in the form of a gel containing 80% active ingredient in a mineral oil and 100% active ingredient. They have a softening point of 88 to 94 ° C. These commercial products are a mixture of copolymers of a C36 di-acid condensed on ethylene diamine, with a weight average molecular weight of about 6000 g / mol. The terminal ester groups result from the esterification of the remaining acid termini with cetyl alcohol, stearyl alcohol or mixtures thereof (also called cetylstearyl alcohol). As hydrocarbon polyamide, mention may also be made of polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and a diamine, including compounds having more than 2 carbonyl groups and 2 amine groups, carbonyl groups and amine groups. adjacent units being condensed by an amide bond. These polyamide resins are especially those marketed under the Versamid0 brand by General Mills, Inc. and Henkel Corp. (Versamid 930, 744 or 1655) or by the company Olin Mathieson Chemical Corp., under the trade name Onamid®, especially Onamid S or C. These resins have a weight average molecular weight ranging from 6000 to 9000 g / mol. For more information on these polyamides, reference may be made to US-A-3645705 and US-A-3148125. More specifically, Versamid® 930 or 744 are used.

It is also possible to use the polyamides sold by the company Arizona Chemical under the references Uni-Rez (2658, 2931, 2970, 2621, 2613, 2624, 2665, 1554, 2623, 2662) and the product sold under the reference Macromelt 6212 by the Henkel company. For more information on these polyamides, reference may be made to US-A-5500209. It is also possible to use polyamide resins such as those described in US-A-5783657 and US-A-5998570. The polyamide preferably has a softening temperature above 65 ° C and up to 190 ° C. Preferably, it has a softening temperature of from 70 to 130 ° C and more preferably from 80 to 105 ° C. In a particularly preferred manner, the polyamide used is Uniclear 100 VG whose INCI name is "ethylene diamine / stearyl dimer tallate copolymer".

Silicone Polyamide Silicone polyamides are preferably solid at room temperature (25 ° C.) and atmospheric pressure (760 mmHg). The silicone polyamides may more particularly be polymers comprising at least one unit corresponding to the general formula I: ## STR2 ## in which: G 'represents C (O) when G represents -C (O) -NH-Y-NH-, and G 'represents -NH- when G represents -NH-C (O) -YC (O) -, 2) R4, R5, R6 and R7, which may be identical or different, represent a chosen group among: - saturated or unsaturated, linear, branched or cyclic, C1 to C40, hydrocarbon groups which may contain in their chain one or more oxygen, sulfur and / or nitrogen atoms, and which may be partially substituted; or totally by fluorine atoms, - C6-C10 aryl groups, optionally substituted by one or more C1-C4 alkyl groups, polyorganosiloxane chains containing or not containing one or more oxygen, sulfur and / or nitrogen, 3) X, identical or different, represent a linear or branched alkylene di-yl group C1 to Cm, which may contain in its chain one or more oxygen and / or nitrogen atoms, 4) Y is a divalent linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene group, saturated or unsaturated, in Ci at C50, which may include one or more oxygen, sulfur and / or nitrogen atoms, and / or substitute one of the following atoms or groups of atoms: fluorine, hydroxy, C3-C8 cycloalkyl, C1 to C40 alkyl, C5 to C10 aryl, phenyl optionally substituted with 1 to 3 C1 to C3 alkyl, C1 to C3 hydroxyalkyl and C1 to C6 aminoalkyl, or Y is a group of the formula: n In which - T represents a linear or branched, saturated or unsaturated C 3 -C 24 trivalent or tetravalent hydrocarbon group optionally substituted with a polyorganosiloxane chain, and which may contain one or more atoms chosen from O, N and S, or T represents a trivalent atom chosen by N, P and Al, and R8 represents a linear or branched C1-C50 alkyl group or a polyorganosiloxane chain, which may comprise one or more ester, amide, urethane, thiocarbamate, urea, thiourea and / or sulphonamide groups which may be attached to another polymer chain or not, n is an integer ranging from 2 to 500, preferably from 2 to 200 and m is an integer ranging from 1 to 1000, preferably from 1 to 700 and better from 6 to 200. According to one embodiment of the invention, 80% of the R4, R5, R6 and R7, of the polymer are preferably chosen from methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups. In another embodiment, 80% of the R4, R5, R6 and R7 of the polymer are methyl groups. According to the invention, Y may represent various divalent groups, optionally additionally having one or two free valences to establish bonds with other units of the polymer or copolymer. Preferably, Y represents a group chosen from: a) C 1 to C 20, preferably C 1 to C 10, linear alkylene groups, b) branched alkylene groups which may comprise unsubstituted rings and unsaturations, at C 30 to C 50, ) C5-C6 cycloalkylene groups; d) phenylene groups optionally substituted with one or more C1-C40 alkyl groups; and e) C1-C20 alkylene groups having 1 to 5 amide groups; f) alkylene groups; C1 to C20, having one or more substituents selected from hydroxyl, C3-C8 cycloalkane, C1-C3 hydroxyalkyl and C1-C6 alkylamino g); polyorganosiloxane chains of the formula: R5-R4 R4-Si_ ## STR1 ## wherein R 4, R 5, R 6, R 7, T and m are as defined above. According to the invention, the silicone polymer may be a homopolymer, that is to say a polymer comprising several identical units, of formula (I). According to the invention, it is also possible to use a polymer consisting of a copolymer comprising several different units of formula (I), that is to say a polymer in which at least one of R4, R5, R6, R7, X, G, G ', Y, m and n are different in one of the patterns. According to a variant of the invention, it is also possible to use a silicone polyamide comprising in addition at least one hydrocarbon unit comprising two groups capable of establishing hydrogen interactions chosen from ester, amide, sulfonamide, carbamate, thiocarbamate, urea and urethane groups. , thiourea, oxamido, guanidino, biguanidino and their combinations. These copolymers may be block polymers, block polymers or graft polymers. In the formula (I), the alkylene group representing X or Y may optionally contain in its alkylene part at least one of the following elements: 1) 1 to 5 amide groups, urea, urethane, or carbamate, 2) a cycloalkyl group in C5 or C6, and 3) a phenylene group optionally substituted with 1 to 3 identical or different C1 to C3 alkyl groups.

In the formula (I), the alkylene groups may also be substituted by at least one member selected from the group consisting of: - a hydroxy group, - a C3 to C8 cycloalkyl group, - one to three C1 to C40 alkyl groups a phenyl group optionally substituted with one to three C 1 to C 3 alkyl groups, a C 1 to C 3 hydroxyalkyl group, and a C 1 to C 6 aminoalkyl group.

In this formula (I), Y may also represent: R8 where R8 represents a polyorganosiloxane chain, and T represents a group of formula: ## STR2 ## ## STR2 ## (CH2) b (CH2) c wherein a, b and c are independently integers from 1 to 10, and R13 is a hydrogen atom or a group such as those defined for R4, R5, R6 and R7. In the formula (I), R4, R5, R6 and R7 are preferably independently C1-C40 alkyl, linear or branched, preferably CH3, C2H5, n-C3H7 or isopropyl, polyorganosiloxane chain. or a phenyl group optionally substituted with one to three methyl or ethyl groups. According to an advantageous embodiment of the invention, the silicone polyamide comprises at least one unit of formula (III) or (IV): -R 4 -R 5 SiO x Si -XR "R, -R 4 R 5 SiO Si-X-NH Embedded image wherein R 4, R 5, R 6, R 7, X, Y, m and n are as defined above.

In these silicone polyamides of formula (III) or (IV), m ranges from 1 to 700, in particular from 15 to 500, and especially from 50 to 200, and is especially from 1 to 500, preferably from 1 to 100, and better still more preferably from 4 to 25, X is preferably a linear or branched alkylene chain having 1 to 30 carbon atoms, in particular 1 to 20 carbon atoms, especially 5 to 15 carbon atoms and more particularly 10 carbon atoms. carbon, and - Y is preferably a linear or branched alkylene chain or which may comprise rings and / or unsaturations, having from 1 to 40 carbon atoms, in particular from 1 to 20 carbon atoms, and more preferably from 2 to 6 carbon atoms, in particular 6 carbon atoms.

In the formulas (III) and (IV), the alkylene group representing X or Y may optionally contain in its alkylene part at least one of the following elements: 1 to 5 amide groups, urea, urethane or carbamate; C5 or C6 cycloalkyl group, and - a phenylene group optionally substituted with 1 to 3 identical or different C1 to C3 alkyl groups. In the formulas (III) and (IV), the alkylene groups may also be substituted with at least one member selected from the group consisting of: - a hydroxy group, - a C3-C8 cycloalkyl group, - one to three alkyl groups C1 to C40; phenyl optionally substituted with one to three C1 to C3 alkyl groups; C1 to C3 hydroxyalkyl; and C1 to C6 aminoalkyl. In these formulas (III) and (IV), Y may also represent: R8 where R8 represents a polyorganosiloxane chain, and T represents a group of formula: R13 _ (CH2) a C _ (CHA OR (CITA N (CHA (C1 -12), (0-12), wherein a, b and c are independently integers from 1 to 10, and Rn is a hydrogen atom or a group such as those defined for R4, R5, R6 and In formulas (III) and (IV), R4, R5, R6 and R7 are preferably independently C1-C40 alkyl, linear or branched, preferably CH3, C2H5, n-C3H7 or isopropyl, a polyorganosiloxane chain or a phenyl group optionally substituted with one to three methyl or ethyl groups As has been seen previously, the polymer may comprise identical or different units of formula (III) or (IV). polymer may be a polyamide containing several units of formula (III) or (IV) of different lengths, ie a polyamide corresponding to with formula (V): ## STR2 ## Wherein X, Y, n, R4 to R7 have the meanings given above, ml and m2 which are different, are selected from the range of 1 to 1000, and p is an integer from 2 to 300. In this formula, the units may be structured to form either a block copolymer, a random copolymer, or an alternating copolymer. In this copolymer, the units may be not only of different lengths but also of different chemical structures, for example having different Ys. In this case, the polymer may correspond to formula VI: ## STR1 ## in which R4 to R5 R7, X, Y, ml, m2, n and p have the meanings given above and Y1 is different from Y but selected from the groups defined for Y. As before, the different units can be structured to form either a copolymer block, either a random copolymer or an alternating copolymer. In this first embodiment of the invention, the silicone polyamide may also consist of a graft copolymer. Thus, the silicone-containing polyamide may be grafted and optionally crosslinked with silicone chains containing amide groups. Such polymers can be synthesized with trifunctional amines. In this case, the polymer may comprise at least one unit of formula (VII): ## STR5 ## wherein X 1 is CO 2 NH 2 wherein X 1 and X 2 which are the same or different have the meaning given for X in the formula (I), n is as defined in formula (I), Y and T are as defined in the formula ( I), R14 to R21 are groups selected from the same group as R4 to R7, ml and m2 are numbers in the range of 1 to 1000, and p is an integer from 2 to 500. In formula (VII), it is preferred that: p is from 1 to 25, more preferably 1 to 7, R 14 to R 2 'are methyl, T is one of the following formulas: R24 R23 C R24 In which R22 is a hydrogen atom or a group selected from the groups defined for R4 to R7, and R23, R24 and R25 are independently linear or branched alkylene groups, preferably again, in the formula: R 23 N R 24 R 25 in particular with R 23, R 24 and R 25 representing -CH 2 -CH 2 -, ml and m 2 range from 15 to 500, and more preferably from 15 to 45, X 1 and X 2 represent - (CH 2 10-, and Y is -CH2-. These silicone-grafted polyamides of formula (VII) may be copolymerized with polyamide-silicones of formula (II) to form block copolymers, alternating copolymers or random copolymers. The weight percentage of grafted silicone units (VII) in the copolymer can range from 0.5 to 30% by weight.

As noted above, the siloxane units may be in the backbone or backbone of the polymer, but they may also be present in grafted or pendant chains. In the main chain, the siloxane units may be in the form of segments as described above. In the pendant or grafted chains, the siloxane units may appear individually or in segments. According to a preferred embodiment of the invention, it is possible to use a copolymer comprising units of formula (III) or (IV) and hydrocarbon-based polyamide units. In this case, the polyamide-silicone units may be disposed at the ends of the hydrocarbon polyamide. According to a preferred embodiment, the silicone polyamide comprises units of formula III. Preferably, according to this embodiment, the groups R4, R5, R6 and R7 represent methyl groups, one of X and Y represents an alkylene group with 6 carbon atoms and the other an alkylene group with 11 carbon atoms. . n is an integer from 2 to 500, n represents the degree of polymerization DP of the polymer.

By way of example of such silicone polyamides, mention may be made of the compounds marketed by Dow Corning under the name DC 2-8179 (DP 100) and DC 28178 (DP 15) whose INCI name is "Nylon-611 / dimethicone copolymers "i.e. Nylon-611 / dimethicone copolymers.

Advantageously, the emulsion used according to the invention comprises at least one polydimethylsiloxane block polymer of general formula (I) having an index m of value about 100. The index "m" corresponds to the degree of polymerization of the silicone portion of the polymer.

More preferably, the emulsion according to the invention comprises at least one polymer comprising at least one unit of formula (III) in which m is from 50 to 200, in particular from 75 to 150, and preferably of the order of 100. .

More preferably, R4, R5, R6 and R7 independently represent a linear or branched C1-C40 alkyl group, preferably a CH3, C2H5, n-C3H7 or isopropyl group in formula (III).

As an example of a silicone polymer that can be used, mention may be made of one of the silicone polyamides obtained according to Examples 1 to 3 of US Pat. No. 5,981,680. According to one preferred embodiment, the polyamide silicone polymer marketed by Dow Corning is used. under the name DC 2-8179 (DP 100).

The silicone polymers and / or copolymers used in the emulsion of the invention advantageously have a transition temperature of the solid state in the liquid state ranging from 45 ° C. to 190 ° C. Preferably, they have a solid state transition temperature in the liquid state of from 70 to 130 ° C and more preferably from 80 ° C to 105 ° C.

Dextrin Esters The W / O emulsion according to the invention may comprise, as polymeric thickening agent, at least one dextrin ester. In particular, the W / O emulsion preferably comprises at least one ester of dextrin and fatty acid, preferably C 12 to C 24, in particular C 14 -C 18, or mixtures thereof. Preferably, the dextrin ester is a C12-C18, in particular C14-C18, fatty acid dextrin ester. Preferably, the dextrin ester is selected from dextrin myristate and / or dextrin palmitate, and mixtures thereof. According to a particular embodiment, the dextrin ester is dextrin myristate, such as that sold especially under the name Rheopearl MKL-2 by the company CHIBA FLOUR MILLING. According to a preferred embodiment, the dextrin ester is dextrin palmitate. This may for example be chosen from those sold under the names Rheopearl TL® or Rheopearl KL® or Rheopearl® KL2 by the company CHIBA FLOUR MILLING.

MINERAL THICKENING AGENTS Among the mineral thickeners suitable for the present invention include modified clays, silicas, alone or in mixture.

If the W / O emulsion comprises, the content of mineral thickening agent is advantageously between 0.1 and 20% by weight, preferably from 0.1 to 10% by weight, relative to the total weight of the oil or oils in which it (s) is / are incorporated.

The modified clays The W / O emulsion according to the invention may comprise at least one lipophilic clay. The clays can be natural or synthetic and are made lipophilic by treatment with an alkylammonium salt such as a C10-C22 ammonium chloride, for example di-stearyl dimethyl ammonium chloride. They may be chosen from bentonites, in particular hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites and vermiculites. Preferably, they are chosen from hectorites.

Preferably, the lipophilic clays used are hectorites modified with a C10 to C22 ammonium chloride, such as hectorite modified with distearyl dimethyl ammonium chloride, such as, for example, that marketed under the US Pat. denomination of Bentone 38V® by the company ELEMENTIS or bentone gel in isododecane marketed under the name BENTONE GEL ISD V® (isododecane 87% / Disteardimonium Hectorite 10% / propylene carbonate 3%) by the company ELEMENTIS. Lipophilic clay may in particular be present in a content ranging from 0.1% to 15% by weight, in particular from 0.5% to 10%, more particularly from 1% to 10% by weight relative to the total weight. oil or oils in which it (s) is / are incorporated.

Silicas The W / O emulsion according to the invention may also comprise, as thickening agent, fumed silica or silica airgel particles. a) Pyrogenic Silica Particularly suitable for the invention, the hydrophobic treated silica treated surface. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a decrease in the number of silanol groups present on the surface of the silica. In particular, it is possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be: trimethylsiloxyl groups, which are especially obtained by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called "Silica silylate" according to the CTFA (8th edition, 2000). They are for example marketed under the references Aerosil R812® by the company DEGUSSA, CAB-O-SIL TS-530® by CABOT. dimethylsilyloxyl or polydimethylsiloxane groups, which are especially obtained by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl silylate" according to the CTFA (8th edition, 2000). They are for example marketed under the references Aerosil R972®, and Aerosil R974® by the company DEGUSSA, CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by CABOT. The fumed silicas may be present in a W / O emulsion according to the present invention in a content of between 0.1 and 40% by weight, more particularly between 1 and 15% by weight and even more particularly between 2 and 10% by weight. % by weight, relative to the total weight of the oil or oils in which it (s) is / are incorporated. b) Hydrophobic silica aerogels The W / O emulsion according to the invention may also comprise, as mineral thickening agent, at least silica aerogel particles.

Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air. They are generally synthesized by sol-gel process in a liquid medium and then usually dried by extraction of a supercritical fluid, the most commonly used being supercritical CO2. This type of drying avoids the contraction of the pores and the material. The sol-gel process and the various dryings are described in detail in Brinker CJ, and Scherer GW, Sol-Gel Science: New York: Academic Press, 1990. The hydrophobic silica airgel particles used in the present invention exhibit specific surface area per unit mass (SM) ranging from 500 to 1500 m 2 / g, preferably from 600 to 1200 m 2 / g and better still from 600 to 800 m 2 / g, and a size expressed in volume average diameter (D [0 5]) ranging from 1 to 1500 μm, more preferably from 1 to 1000 μm, preferably from 1 to 100 μm, in particular from 1 to 30 μm, more preferably from 5 to 25 μm, better still from 5 to 20 μm. and even better better from 5 to 15 iam. According to one embodiment, the hydrophobic silica aerogel particles used in the present invention have a size expressed in volume mean diameter (D [0.5]) ranging from 1 to 30 μm, preferably from 5 to 25 μm. better from 5 to 20 iam and even better from 5 to 15 iam. The specific surface area per unit mass can be determined by the nitrogen absorption method called the BET method (BRUNAUER - EMMET - TELLER) described in "The Journal of the American Chemical Society", vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (Appendix D). The BET surface area corresponds to the total specific surface area of the particles under consideration. The silica airgel particle sizes can be measured by static light scattering using a MasterSizer 2000 commercial particle size analyzer from Malvern. The data is processed on the basis of Mie scattering theory. This theory, which is accurate for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" diameter of particles. This theory is particularly described in 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 have a specific surface per unit mass (SM) ranging from 600 to 800 m 2 / g.

The silica airgel particles used in the present invention may advantageously have a packed density p ranging from 0.02 g / cm 3 to 0.10 g / cm 3, preferably from 0.03 g / cm 3 to 0.08 g / cm 3. cm3, in particular ranging from 0.05 g / cm3 to 0.08 g / cm3. In the context of the present invention, this density can be assessed according to the following protocol, called the packed density: 40 g of powder are poured into a graduated test tube; then the specimen is placed on the STAV 2003 device from STAMPF VOLUMETER; the test piece is then subjected to a series of 2500 settlements (this operation is repeated until the difference in volume between two consecutive tests is less than 2%); then the final volume Vf of compacted powder is measured directly on the test piece. The packed density is determined by the ratio m / Vf, in this case 40 / Vf (Vf being expressed in cm3 and m in g). According to a preferred embodiment, the hydrophobic silica airgel particles used in the present invention. have a specific surface area per volume unit SV ranging from 5 to 60 m 2 / cm 3, preferably from 10 to 50 m 2 / cm 3 and more preferably from 15 to 40 m 2 / cm 3. The specific surface area per unit volume is given by the relation: Sv = Sm x p; where p is the packed density expressed in g / cm 3 and SM is the specific surface area per unit of mass, expressed in m 2 / g, as defined above.

Preferably, the hydrophobic silica aerogel particles according to the invention have an oil absorption capacity measured with WET POINT ranging from 5 to 18 ml / g, preferably from 6 to 15 ml / g and better still from 8 to 18 ml / g. at 12 ml / g. The absorption capacity measured at Wet Point, and denoted Wp, corresponds to the amount of oil which must be added to 100 g of particles in order to obtain a homogeneous paste. It is measured according to the so-called Wet Point method or method for determining the setting of powder oil described in standard NF T 30-022. It corresponds to the amount of oil adsorbed on the available surface of the powder and / or absorbed by the powder by measuring the Wet Point, described below: A quantity m = 2 g of powder is placed on a glass plate then the oil (isononyl isononanoate) is added dropwise. After addition of 4 to 5 drops of oil in the powder, mixing is carried out with a spatula and oil is added until the formation of oil and powder conglomerates. From this moment, the oil is added one drop at a time and then triturated with the spatula. The addition of oil is stopped when a firm and smooth paste is obtained. This paste should be spread on the glass plate without cracks or lumps. The volume Vs (expressed in ml) of oil used is then noted. The oil intake corresponds to the ratio Vs / m. The aerogels used according to the present invention are aerogels of hydrophobic silica, preferably of silylated silica (INCI name silica silylate). By "hydrophobic silica" is meant any silica whose surface is treated with silylating agents, for example by halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, in order to functionalize the OH groups by Si-Rn silyl groups, for example trimethylsilyl groups. With respect to the preparation of hydrophobic silica airgel particles surface-modified by silylation, reference can be made to US Pat. No. 7,470,725. Hydrophobic silica airgel particles that are surface-modified with trimethylsilyl groups, preferably INCI Silica silylate, will preferably be used. Examples of hydrophobic silica aerogels that can be used in the invention include, for example, the airgel sold under the name VM-2260 or VM-2270 (INCI name Silica silylate), by the company Dow Corning, whose The particles have an average size of about 1000 microns and a specific surface area per unit mass of from 600 to 800 m 2 / g. The aerogels marketed by Cabot under the references AEROGEL TLD 201, AEROGEL OGD 201, AEROGEL TLD 203, ENOVA® AEROGEL MT 1100 and ENOVA AEROGEL MT 1200 may also be mentioned. The airgel marketed under the name VM2270 will preferably be used. (INCI name Silica silylate), by the company Dow Corning, whose particles have an average size ranging from 5-15 microns and a specific surface area per unit mass ranging from 600 to 800 m2 / g. Preferably, the particles of hydrophobic silica aerogels are present in the W / O emulsion according to the invention in a dry matter content ranging from 0.1% to 8% by weight, preferably 0.2% by weight. at 5% by weight, preferably from 0.2% to 3% by weight relative to the total weight of the oil or oils in which it (they) is / are incorporated.

According to a particularly preferred embodiment of the invention, the emulsion comprises at least one structuring agent chosen from waxes, pasty compounds and mixtures thereof. According to an advantageous embodiment of the invention, the W / O emulsion comprises a first oily phase containing at least a first oil chosen from phenylated or non-phenylated nonvolatile silicone oils, a second oily phase containing at least one second oil chosen from nonvolatile hydrocarbon oils, in particular comprising at least two free hydroxyl groups, preferably at least three free hydroxyl groups, and a pasty compound chosen from lanolin and its derivatives, esters of glycerol oligomers, butters of vegetable origin, vegetable oils which are totally or partially hydrogenated, esters of hydrogenated castor oil and mixtures thereof, and more particularly esters of castor oil.

Processes The present invention further relates to processes for preparing the emulsion according to the invention. Firstly, the first oily phase is prepared, and in a second step, the second oily phase. The incorporation of the structuring agent or of each structuring agent into the oily phase in which they are to be incorporated is carried out before the actual emulsification. The mixture of the structuring agent (s) with the oily phase in question preferably takes place at a temperature greater than or equal to the melting point of the said structuring compound (s) and the homogenization is advantageously carried out at a higher temperature. or equal to this melting temperature. The mixture of the oily phase with the structuring agent (s) may take place using manual stirring or mechanical stirring of the Moritz mixer type, Rayneri stirring, Ultraturax stirring or by ultrasonic homogenization. Then, for example, continue the process for preparing the emulsion according to the variants described below. According to a first variant, the process for preparing the emulsion comprises the following stages, in this order: mixing the first oily phase and the second oily phase, at least one of these oily phases comprising at least one agent structuring, - emulsification of the mixture, - introduction of solid microparticles into the emulsion. The first oily phase and the second oily phase are mixed. The emulsification, also called emulsification, of these two oily phases leads to the creation of an interface, and more particularly a dispersion of one of the oily phases in the other oily phase. In a second step, the solid microparticles are added to the emulsion formed and then the mixture is agitated, either by means of a set of shear forces or by means of ultrasound. According to a second variant, the process for preparing the emulsion is such that the solid microparticles are introduced into the first oily phase or into the second oily phase.

In this case, the process comprises the following steps, in this order: - introduction of the solid microparticles respectively in the first oily phase or in the second oily phase, one of the two oily phases comprising at least one structuring agent, - introduction respectively the second oily phase or the first oily phase, - emulsification of the mixture.

According to this second variant, the microparticles are first introduced into one of the two oily phases, then a set of shearing forces or ultrasound is applied in order to obtain a homogeneous dispersion of said microparticles in said oily phase. The other oily phase is then added.

Note that if the oily phase in which the microparticles are introduced, comprises at least one structuring agent, this or these are added and mixed with said oily phase before the addition of the solid microparticles, as indicated above. If the second oily phase comprises at least one structuring agent and / or at least one thickening agent, then this or these compounds are incorporated and mixed with said oily phase. The oily phase thus prepared is then emulsified with the first oily phase comprising the solid microparticles, optionally one or more structuring agents.

According to a third variant, the process for preparing the emulsion comprises the following stages, in this order: - simultaneous introduction of the solid microparticles, the first oily phase and the second oily phase, - emulsification of the mixture.

According to this variant, the emulsion is obtained by mixing the solid microparticles and the two oily phases and stirring vigorously. Again, if one and / or the other oily phase comprises at least one structuring agent, this or these ingredients are previously incorporated and mixed with the oily phase concerned, according to the protocol mentioned above.

The emulsification is carried out by subjecting the mixture of the two oily phases comprising, where appropriate, at least one structuring agent, and solid microparticles, to a set of shearing forces or ultrasounds, to obtain its homogeneity. By "homogeneity" of an emulsion is meant an emulsion in which the drops of internal phases are uniformly dispersed in the continuous or external oily phase.

The droplets of phases dispersed in the emulsion may be very fine, in particular ranging from 0.1 to 10 μm, or may be larger, in particular ranging from 10 μm to 1 cm. Those skilled in the art will be able to choose the conditions and the device best suited to obtain the set of forces necessary to obtain the type of emulsion in question, in particular to obtain the size of the droplets targeted. This set of forces can be obtained by subjecting the first and second oily phases or the emulsion to manual stirring or mechanical stirring such as a Moritz mixer, Rayneri stirrer, Ultraturax stirrer or by ultrasonic homogenization. The rate of mixing or stirring to obtain a phase or a homogeneous emulsion may depend on various factors such as its composition or its volume. The various parameters of the agitation, including speed, can be determined by one skilled in the art on the basis of his general knowledge and, where appropriate, by means of some routine tests. Usually, this operation is carried out at a temperature between 10 and 50 ° C; advantageously at a temperature between 15 and 30 ° C.

In the following description and examples, unless otherwise indicated, percentages are percentages by weight and ranges of values in the form "between ... and ..." include the specified lower and upper bounds. The following examples are presented by way of illustration and not limitation of the field of the invention.

EXAMPLES EXAMPLE OF RAYNERI FORMULATION Preparation protocol: The emulsion is produced according to the following steps: In a beaker, the pasty compound is first incorporated into an oil (corresponding to a second oil as defined in the description below). above), for example castor oil. The mixture is heated for about 15 minutes at 50 ° C. with slow Rayneri stirring until the pasty compound is melted. This mixture is stirred at 1100 rpm. Another oil (corresponding to a first oil in the description above), for example the silicone oil, is then added and the stirring is continued for another 5 minutes after the addition of this other oil, the solid microparticles are then introduced. This mixture is stirred for 5 minutes still at 1100 rpm. The heating is then cut off and the mixture cooled to room temperature, namely about 22 ° C. A Pickering emulsion is thus obtained. Quantities are indicated as percentage by weight. Examples 1 to 3: Emulsions Made Using Bowl Particles Comprising the Methylsilanol / Silicate Crosslinked Polymer and Using a Paste Compound The particles used are sold under the name NLK-506 by Takemoto Oil and Fat, also known as bowls methylsilanol / silicate cross polymer. Preparation Protocol: The pasty compound is incorporated into castor oil. The mixture is heated at 50 ° C. with slow Rayneri stirring until the pasty compound is melted, for approximately 15 minutes. The mixture is stirred at 1100 rpm and then silicone oil is slowly added. Stirring is continued for 5 minutes after the incorporation of the oil. Solid particles are added and the mixture is stirred for 5 minutes. The heating is cooled to room temperature (about 22 ° C.). Raw Materials Example 1 Example 2 Example 3 100cst PDMS oil (g / 100g) (BEL SIL DM 100 sold by Wacker) 42.5 42.5 Castor oil (g / 100g) (Belsil DM 100 sold by Wacker) 42.5 42.5 42.5 Polyphenyltrimethylsiloxy dimethylsiloxane (g / 100g) 42.5 (BEL SIL PDM 1000 by WACKER) Caprylic, capric, isostearic, 10 10 stearic, hydrostearic and adipic fatty acid esters of glycerol (g / 100 g) (SOFTISAN 649 sold by CREMER OLEO) Hydrogenated castor oil isostearate (g / 100g) (SALA COS HCISV-L sold by NISSHIN OILLIO) 10 Silicone resin bowls microparticles (NLK-506 sold by Takemoto Oil and Fat) 5 5 5 Total 100 100 100 It is observed under the microscope DMLB100 Leica with objective x10 that Pickering emulsions are well obtained.

Said emulsion is stable for 15 days at 23 ° C. Nor is there any phase shift of an oil. EXAMPLES 4 AND 5: Emulsions Produced Using Bowl Particles Comprising the Methylsilanol / Silicate Crosslinked Polymer and Using a Wax The particles used are sold under the name NLK-506 by Takemoto Oil and Fat, also known as methylsilanol / silicate cross polymer. Protocol of preparation: - One incorporates wax in the castor oil. The mixture is heated to 90 ° C.-92 ° C. for carnauba wax or 105 ° C. for the wax mixture of long-chain fatty alcohols and hydrocarbon with slow Rayneri stirring until the wax melts and is then stirred. minutes, stirring at 1100 rpm and slowly adding silicone oil. Stirring is carried out for 10-15 minutes after the incorporation of the oil. The solid particles are added and the mixture is stirred for 15 minutes. The heating is stopped and allowed to cool to room temperature (about 22 ° C.). Raw Materials Example 4 Example 5 100cst PDMS oil (g / 100g) (BEL SIL DM 100 sold by Wacker) 45 45 Castor oil (g / 100g) 45 45 (Codex sold by Interchimie) Poly phenyltrimethylsiloxy dimethylsiloxane (g / 100g) (BEL SIL PDM 1000 by WACKER) Carnauba Wax (g / 100g) (CARNAUBA WAX # 1 FLAKES NF SP 63 sold by STRAHL & PITSCH - CERAUBA T1 sold by BAERLOCHER) 5 Blend of long chain linear alcohol (C30-050) and hydrocarbon at the same number of carbon (80/20) (g / 100 g) (DOW CORNING 2-8178 GELLANT sold by Dow Corning) 5 solid particles (g / 100 g) 5 5 microparticles of silicone resin bowls (NLK-506 sold by Takemoto Oil and Fat) Total 100 100 The emulsion is stable for 15 days at 23 ° C. EXAMPLE 6 Emulsions Made Using Bowl Particles Comprising the Methylsilanol / Silicate Crosslinked Polymer and Using a Thickening Agent The particles used are sold under the name NLK-506 by Takemoto Oil and Fat, also known as methylsilanol / silicate bowls. cross polymer. Protocol of preparation: - Thickening agent is incorporated in castor oil. The mixture is heated at 75 ° C. with slow Rayneri stirring until the thickening agent is melted and then stirred for 15 minutes. The mixture is stirred at 1100 rpm and then the silicone oil is slowly added. The mixture is stirred for 10-15 minutes after the incorporation of the oil. Solid particles are added and the mixture is stirred for 15 minutes. The heating is stopped and allowed to cool to room temperature (about 22 ° C.). PDMS 100cst (g / 100g) (BEL SIL DM 100 sold by Wacker) 45 Castor oil (g / 100g) 45 (Codex sold by Interchimie) Dextrin palmitate (g / 100g) 5 (RHEOPEARL KL2 sold by Chiba Flour milling) Solid particles (g / 100 g) Silicon resin bowls microparticles (NLK-506 sold by Takemoto Oil and Fat) Total 100 The emulsions obtained in Examples 1 to 6 above have appropriate stability properties. Thus, obtaining Pickering H / H emulsions was verified by microscope. Moreover, for all the emulsions obtained in Examples 1 to 6, it was observed that they were stable, in other words no phase shift of the oils was observed.

EXAMPLE 7 Lipstick In this example, two pasty compounds and an oil having an OH function (diisostearyl malate and castor oil) are used. Raw materials Example 7 Hydrocarbon phase Pentaerythritol tetraisostearate (CRODAMOL PTIS-LQ- (MII ) sold by CRODA) 6.9 Castor oil (g / 100g) 7.3 (Codex sold by Interchimie) Diisostearyl malate 6.8 Acid (C18-C36) triglyceride 12.8 Polybutene 12.8 (Indopol H100 sold by Ineos) Copolymer vinylpyrrolidone / hexadecene copolymer 5 (Antaron V-216 sold by ISP) Bis-diglyceryl polyacyladipate-2 (Softisan 649 sold by Cremer Oleo) 6.1 Silicone phase Trimethylsiloxyphenyl dimethicone (Belsil PDM 1000 sold by Wacker) 29.7 microparticles Solid particles (g / 100g) 3.1 Silicon resin bowls (NLK-506 sold by Takemoto Oil and Fat) Texturizers Hydroxystearic acid 1.7 Polyethylene 1 (Arsensa SC 211 sold by Honneywell Specialty Chemicals) Trihydroxyst 1 dyestuff dye 5,8 Total 100 Example 8: Lipstick In this example, the hydrocarbon phase comprises a pasty compound having an OH function. Raw materials Example 8 Hydrocarbon phase Polybutene 12.8 (Ineos Indopol H100) Pentaerythritol tetraisostearate (CRODAMOL PTIS-LQ- (MII) by CRODA) 32.5 Bis-behenyl / isostearyl / phytostearyl dimer dilinoleyl dimer 12 dilinoleate (Plandool-G sold by Nippon Fine Chemical) Silicone phase Trimethylsiloxyphenyl dimethicone (Be / si / PDM 1000 sold by Wacker) 29.7 microparticles Solid particles (g / 100g) 2 Silicone resin bowls microparticles (NLK-506 sold by Takemoto Oil and Fat) Texturants Hydroxystearic acid 1.7 Polyethylene 1 (Arsensa SC 211 sold by Honneywell Specialty Chemicals) Trihydroxystearin 2.5 dyestuff dyestuffs 5.8 Total 100 The following test is carried out in order to evaluate the stability of the compositions of lipstick according to the examples 7 and 8 above. The two compositions are centrifuged for 1 minute at 450 g. There is no instability. In particular, the dyestuffs do not sediment. In addition, no oil salting is observed. In addition, the compositions of Examples 7 and 8 have a very good thermal stability. Thus, no modification of the compositions was visually observed even after 5 months at room temperature, at 4 ° C., at 47 ° C. and during a temperature cycle. Finally, each of the compositions gives a homogeneous, low tack deposit with a very good gloss level (evaluated by means of a SAMBA polarimetric camera and a SET-M-0738-CHRO-10 Chromosphere as described in FIG. application FR 2 829 344).

Claims (30)

REVENDICATIONS1. Oil / oil emulsion comprising at least: a first oily phase comprising at least a first non-volatile oil chosen from silicone oils, hydrocarbon oils and fluorinated oils; a second oily phase comprising at least one second non-volatile or volatile oil; immiscible with the first oil or oils at 25 ° C, at least one structuring agent chosen from waxes, pasty compounds, polymeric thickeners, mineral thickeners and mixtures thereof, and solid microparticles having at least one a curved portion and at least one curvature break of said curved portion. The oil / oil emulsion of claim 1, wherein the solid microparticles comprise a plurality of curvatures. 3. Oil / oil emulsion according to claim 1 or 2, wherein the solid microparticles comprise at least one concave portion and at least one convex portion. 4. Oil / oil emulsion according to any one of the preceding claims, wherein the microparticles have a shape selected from the type of "bowls", "golf balls", "polytopes". The oil / oil emulsion of claim 1, wherein the solid microparticles comprise a single curvature. 6. Oil / oil emulsion according to claim 5, wherein the solid microparticles are fusiform, hemispherical microparticles. An oil / oil emulsion according to any one of the preceding claims, wherein the microparticles are such that their largest dimension is from 0.1 to 100 μm, preferably from 0.1 to 50 μm, and still preferred from 0.5 to 20 8. Oil / oil emulsion according to any one of the preceding claims, wherein the total amount of solid microparticles comprising at least one curved portion and at least one rupture of the curvature of said curved portion, vade 1 to 10% by weight, preferably from 2 to 7% by weight, relative to the total weight of the emulsion. 9. Oil / oil emulsion according to any one of the preceding claims, wherein said first oil or second non-volatile oil, preferably said first oil, is selected from silicone oils, fluorinated oils or mixtures thereof and more particularly from non-volatile, non-phenyl silicone oils; phenylated nonvolatile silicone oils, with or without at least one dimethicone fragment; fluorinated oils; or their mixtures. 10. Oil / oil emulsion according to any one of the preceding claims, in which the first or second non-volatile oil, preferably the second oil, is chosen from non-volatile polar hydrocarbon oils, in particular chosen from non-volatile oils. comprising at most one free or non-free hydroxyl group, or of non-volatile oils comprising at least two free hydroxyl groups; or from non-volatile hydrocarbon apolar oils, or mixtures thereof. 11. Oil / oil emulsion according to any one of the preceding claims, wherein the first oily phase contains at least a first oil selected from non-volatile silicone oils and the second oily phase contains at least one second oil selected from hydrocarbon oils. non-volatile apolar 12. Oil / oil emulsion according to any one of claims 1 to 10, wherein the first oily phase contains at least a first oil selected from non-volatile silicone oils non-phenylated or phenylated nonvolatile silicone oils having at least one fragment dimethicone, and the second oily phase contains at least a second oil selected from nonvolatile hydrocarbon oils comprising at most one free hydroxyl group or not including. 13. Oil / oil emulsion according to any one of claims 1 to 10, wherein the first oily phase contains at least a first oil selected from non-volatile silicone oils, and the second oily phase contains at least a second oil selected from non-volatile hydrocarbon oils comprising at least two free hydroxyl groups, preferably at least three free hydroxyl groups. 14. Oil / oil emulsion according to any one of claims 1 to 10, wherein the first oily phase contains at least a first oil selected from phenylated nonvolatile silicone oils having no dimethicone moiety, and the second oily phase contains at least one second oil chosen from non-volatile hydrocarbon oils comprising at least two free hydroxyl groups, and preferably at least three free hydroxyl groups, or from non-volatile nonpolar hydrocarbon oils. 15. Oil / oil emulsion according to any one of claims 1 to 10, wherein the first oily phase contains at least a first oil selected from polar non-volatile hydrocarbon oils, and the second oily phase contains at least a second oil chosen among nonpolar hydrocarbon oils apolar. 16. Oil / oil emulsion according to any one of claims 1 to 10, wherein the first oily phase contains at least a first oil selected from the non-volatile oil oils non-phenylated, and the second oil phase contains at least a second oil chosen from phenylated nonvolatile silicone oils with or without at least one dimethicone fragment, or at least one volatile silicone oil. 17. Oil / oil emulsion according to any one of claims 1 to 10, wherein the first oily phase contains at least a first oil selected from phenylated nonvolatile silicone oils having no dimethicone moiety, and the second oily phase contains at least one second oil chosen from phenylated nonvolatile silicone oils having at least one dimethicone fragment, or at least one volatile silicone oil. 18. Oil / oil emulsion according to any one of the preceding claims, wherein the content of the oil or oils of the first oily phase represents from 5 to 95% by weight, preferably from 30 to 70% by weight, relative to to the weight of the emulsion. An oil / oil emulsion according to any one of the preceding claims, wherein the content of the oil or oils of the second oil phase is from 5 to 95% by weight, preferably from 30 to 70% by weight, based on to the weight of the emulsion. 20. Oil / oil emulsion according to any one of the preceding claims, wherein the weight ratio of the oil or oils of the first oily phase relative to the oil or oils of the second oily phase represents from 5/95 to 95/95 5, preferably from 30/70 to 70/30. 21. oil / oil emulsion according to any one of the preceding claims, wherein the waxes are hydrocarbon-based or fluorinated or of plant, animal and / or synthetic origin and in particular chosen from (i) apolar waxes such as hydrocarbon waxes such as microcrystalline waxes, paraffin waxes, ozokerite, polymethylene waxes, polyethylene waxes, polyethylene micro-waxes and (ii) polar waxes such as hydrocarbon waxes such as ester waxes or alcohol waxes or else such that silicone waxes such as alkyl or alkoxydimethicones, as well as (C20-C60) alkyldimethicones, in particular (C30-C45) alkyldimethicones or silicone waxes obtained by esterification with a (poly) alkoxylated silicone such as silicone beeswax , silicone candelilla wax and siliconized carnauba wax. 22. Emulsion oil / oil according to any one of the preceding claims, characterized in that it comprises a wax content (s) of between 0.1 and 20%, in particular between 0.5 and 15%, and by example between 1 and 10% by weight, relative to the total weight of the oil or oils in which it (they) is / are incorporated (s). 23. Oil / oil emulsion according to any one of the preceding claims, in which the pasty compounds are chosen from (i) lanolin and its derivatives such as lanolin alcohol, oxyethylenated lanolines, acetylated lanolin, lanolin such as, for example, isopropyl lanolate and oxypropylenated lanolins (ii) petroleum jelly, (iii) polyol ethers, (iv) polymeric or non-polymeric silicone compounds, (v) polymeric or non-polymeric fluorinated compounds, (vi) ) vinyl polymers, (vii) liposoluble polyethers resulting from the polyetherification between one or more C2-C100, preferably C2-050 diols, (viii) esters and polyesters such as esters of a glycerol oligomer, homopolymers of vinyl ester having C8-C30 alkyl groups, arachidyl proprionate, phytosterol esters, fatty acid triglycerides and derivatives thereof, pentaerythritol esters, di-di-ester esters and diacid dimer, butters of vegetable origin, vegetable oils which are substantially or partially hydrogenated, esters of hydrogenated castor oil and mixtures thereof. 24. Oil / oil emulsion according to any one of the preceding claims, characterized in that it comprises a content of pasty compound (s) of between 0.1 and 30%, in particular between 0.5 and 20%, and for example between 1 and 10% by weight, relative to the total weight of the oil or oil in which it (they) is / are incorporated (s). 25. Oil / oil emulsion according to any one of the preceding claims, in which the polymeric thickening agent is chosen from organopolysiloxane elastomers, semi-crystalline polymers, hydrocarbon polyamides, silicone polyamides, dextrin esters, as well as their mixtures, the organopolysiloxane elastomers being in particular chosen from crosslinked organopolysiloxane elastomers, advantageously non-emulsifying, the semicrystalline polymers being chosen in particular from (i) homopolymers and copolymers comprising units resulting from the polymerization of one or more monomers bearing crystallizable hydrophobic side chain (s), (ii) polymers carrying at least one crystallizable block in the backbone, (iii) polyester, aliphatic or aromatic or aliphatic / polycondensates aromatic, (iv) copolymers of ethylene and propylene prepared by catal metallocene, and (v) acrylate / silicone copolymers. 26. Oil / oil emulsion according to any one of the preceding claims, characterized in that it comprises a content of polymeric thickening agent (s) of between 0.1 and 40%, in particular between 0 and , 1 and 20%, and for example between 0.1 and 10% by weight, relative to the total weight of the oil or oils in which it (they) is / are incorporated (s). 27. The oil / oil emulsion as claimed in any one of the preceding claims, in which the mineral thickening agent is chosen from modified clays, silicas such as fumed silica and hydrophobic silica aerogels, and mixtures thereof. 28. Oil / oil emulsion according to any one of the preceding claims, characterized in that it comprises a content of mineral thickening agent (s) between 0.1 and 20%, in particular between 0, 1 and 10%, relative to the total weight of the oil or oil in which it (s) is / are incorporated (s). 29. Cosmetic composition comprising, in a physiologically acceptable medium, at least one oil / oil emulsion according to any one of the preceding claims. 30. Use of solid microparticles having at least one curved portion and at least one curvature rupture of said curved portion for stabilizing an H / H emulsion comprising at least a first oily phase comprising at least a first non-volatile oil chosen from silicone oils , hydrocarbon oils and fluorinated oils, at least a second oily phase comprising at least a second non-volatile or volatile oil immiscible with the first oil or oils at 25 ° C, and at least one structuring agent chosen from waxes, pasty compounds, polymeric thickeners, mineral thickeners and mixtures thereof.