FR3025094A1 - GEL / GEL COMPOSITION COMPRISING A UV FILTER AND A HYDROPHOBIC SILICA AEROGEL - Google Patents

Abstract

The present invention relates to a composition, in particular a cosmetic composition for makeup and / or care of keratin materials, comprising: at least one aqueous phase gelled with at least one non-starch hydrophilic gelling agent, at least one oily phase gelled with at least one a lipophilic gelling agent selected from hydrophobic silica aerogels; said phases forming a macroscopically homogeneous mixture therein; said composition further comprising at least one UV filter.

Description

The object of the present invention is to propose, for the field of sun protection and more particularly for the field of care and / or make-up compositions for keratinous substances, a new galenic product which is particularly interesting with regard to its technical performances and sensory sensations. it provides the user during its application on them and in particular on the skin. By "keratin materials" is meant in particular the skin, the lips, and also the keratinous fibers such as the hair, in particular the skin and / or the hair, and preferably the skin. It is known that radiation with wavelengths between 280 nm and 400 nm allows tanning of the human epidermis and that wavelength radiations of between 280 and 320 nm, known as UV rays, B interfere with the development of the natural tan. Exposure is also likely to induce an alteration of the biomechanical properties of the epidermis which results in the appearance of wrinkles leading to premature aging of the skin.

It is also known that UV-A rays of wavelengths between 320 and 400 nm penetrate deeper into the skin than UV-B rays. UV-A rays cause immediate and persistent browning of the skin. Daily exposure to UVA rays, even for short periods of time, under normal conditions can lead to degradation of collagen and elastin fibers which results in a modification of the micro-relief of the skin, the appearance of wrinkles and irregular pigmentation (brown spots, heterogeneity of complexion). Many photoprotective compositions have been proposed to date to remedy the effects induced by UVA and / or UVB radiation. They usually contain fat-soluble and water-soluble organic UV filters that work by UV absorption according to their own chemical nature. It is known that the formulation of emulsions with high levels of filters, necessary to achieve high levels of filtering efficiency, does not lend itself to a quick and easy elaboration of a varied range of compositions and textures. Thus, in a given emulsified system, it is often difficult to integrate high-grade UV filters without altering their stability. It is then necessary to re-adjust the formula and in particular to reformulate the emulsified system.

Moreover, it is known that the filtering formulations have uncomfortable and even uncomfortable sensory aspects masking the freshness and comfort of the formulas. The weak point of filtering emulsions with a high degree of protection is often an important sensation of fat and stickiness, and therefore a lack of lightness of the textures obtained, but also a shiny appearance on the skin. It is thus difficult to reconcile in the same composition opposing technical performances, such as a high level of UV protection that implies a greasy and sticky finish on the skin and a pleasant sensory, attributed amongst other things to the sensation of freshness. . There remains therefore a need for UV sunscreen compositions which are stable, effective in photo-protection and which do not have the disadvantages presented above, in particular which provide a pleasant sensory including a feeling of freshness. Unexpectedly and advantageously, the inventors have shown that this need can be met by means of the photoprotective compositions according to the present invention. Thus, according to one of its aspects, the present invention is directed to a composition, in particular a cosmetic composition for makeup and / or care of keratin materials, comprising: at least one aqueous phase gelled with at least one non-starch hydrophilic gelling agent, At least one oily phase gelled with at least one lipophilic gelling agent chosen from hydrophobic silica aerogels; said phases forming a macroscopically homogeneous mixture therein; said composition further comprising at least one UV filter. Advantageously, the UV-screening agent (s) are present in whole or in part, and preferably only, in the gelled aqueous phase or are present in whole or in part, and preferably only, in the gelled oily phase. Against all expectations, and as can be seen from the examples appearing below, the inventors have found that the formulation of a UV filter in a gel-gel architecture as defined above makes it possible to obtain a composition which makes it possible to provide freshness and lightness even when said composition contains a high level of UV filters. In addition, the gel-gel architecture as defined above makes it possible to maintain the photo-protection properties and leads to stable compositions, in particular without the appearance of phase shift. Compositions, called gel-gel, are already proposed in the cosmetics field. This type of formulation combines a gelled aqueous phase with a gelled oily phase. Thus, gel / gel formulations are described in Almeida et al., Pharmaceutical Development and Technology, 2008, 13: 487, Tables 1 and 2, page 488; WO 99/65455; PI 0405758-9; WO 99/62497; JP 2005-112834 and WO 2008/081175. However, to the inventors' knowledge, this type of composition does not at the present time make it possible to guarantee all the essential properties expected in the cosmetic field, such as a pleasant texture during gripping of the product, a sticky deposit reduced, comfortable and homogeneous especially for makeup, or a stability in time of the formulation. Application WO 2013/093869 also discloses compositions comprising at least: a gelled aqueous phase containing at least 3% by weight relative to its total weight of particles of at least one (C 1 -C 4) carboxyalkyl; starch and whose particle size varies from 25 to 300 μm, and - an oily phase gelled with at least one texturizing agent which may be a hydrophobic silica airgel, with one of said phases constituting the continuous phase of said composition in which the other phase is uniformly dispersed. As specified above, the inventors have found that the use of UV filters in a multiphasic composition according to the invention leads to good photoprotective properties and stability.

Thus, a composition according to the invention exhibits a very good stability both in terms of visual stability (no phase shift) and photoprotective properties, while providing a feeling of freshness and lightness to the user at the application. Finally, the composition is easy to apply to the surface of the keratin material that is targeted. According to another of its aspects, the subject of the invention is also a process for the preparation of a composition, in particular a cosmetic composition for makeup and / or care of keratin materials, in particular the skin, in particular the face, and / or or lips, and / or keratin fibers, in particular hair, comprising at least one step of mixing: an aqueous phase gelled with at least one non-starch hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent chosen from hydrophobic silica aerogels; said phases forming a macroscopically homogeneous mixture therein; said composition further comprising at least one UV filter.

According to an alternative embodiment, this process may advantageously comprise a step of mixing at least two, preferably three or more gelled phases. For obvious reasons, the number of gelled aqueous phases and gelled oily phases to be considered for forming a composition according to the invention may vary for each of the two types of phase beyond two. Advantageously, the mixing of the phases can be carried out at ambient temperature. However, the method of the invention may include, if necessary, a step of heating the mixture.

According to a particular embodiment, the gelled phases representative of the same type of architecture are gelled by a different gelling agent. According to an alternative embodiment, the final formula can be manufactured without following a particular order of introduction of the various constituents and in some cases an "all-in-one" manufacture can be carried out.

Multiphase formulas can thus be developed. According to another of its aspects, the subject of the invention is also a cosmetic process for makeup and / or care of keratinous substances, in particular of the skin of the body and / or of the face, and / or keratin fibers, in particular the hair comprising at least one step of applying to said keratinous material a composition according to the invention. According to another of its aspects, the subject of the invention is also a cosmetic process for making up and / or caring for keratin materials, in particular skin 3025094 5 of the body and / or face, and / or keratinous fibers , in particular the hair, comprising at least the application on said keratin materials of a macroscopically homogeneous composition obtained by extemporaneous mixing, before application or at the time of application to said keratinous material, of at least one aqueous gel phase gelled by at least one non-starch hydrophilic gelling agent, and at least one oily phase gelled with at least one lipophilic gelling agent chosen from hydrophobic silica aerogels, said composition further comprising at least one UV filter. The invention further relates, in another of its aspects, to a cosmetic process for limiting the darkening of the skin, and / or to improving the color and / or homogeneity of the complexion, including the application on the surface of the keratin material of a composition according to the invention. It also relates to a cosmetic process for preventing and / or treating the signs of aging of a keratinous material comprising the application on the surface of the keratin material of a composition according to the invention. By "UV filter" is meant any organic compound (comprising at least carbon and hydrogen atoms) or any inorganic compound (not comprising carbon atoms) capable of filtering by absorption and / or diffusion and / or reflection UV radiation ranging from 280 nm to 400 nm and which does not have sufficient coverage to produce a color on the surface of a ketatinic material by application of a composition containing it. Composition First of all, it is important to note that a composition according to the invention is different from an emulsion. An emulsion generally consists of an oily liquid phase and an aqueous liquid phase. It is a dispersion of droplets of one of the two liquid phases in the other. The size of the droplets forming the dispersed phase of the emulsion is typically of the order of one micrometer (0.1 to 100 μm). In addition, an emulsion requires the presence of a surfactant or an emulsifier to ensure its stability.

In contrast, a composition according to the invention consists of a macroscopically homogeneous mixture of two immiscible gelled phases. These two phases both have a gel / gel-like texture. This texture is reflected in particular visually by a consistent and / or creamy appearance.

The term "macroscopically homogeneous mixture" means a mixture in which each of the gelled phases can not be individualized with the naked eye. More precisely, in a composition according to the invention, the gelled aqueous phase and the gelled oily phase interpenetrate and thus form a stable and consistent product. This consistency is achieved by mixing interpenetrating macro domains.

These interpenetrating macrodomains are not measurable objects. Thus, under the microscope, the composition according to the invention is very different from an emulsion. A composition according to the invention can not be characterized as having a "meaning", ie an O / W or E / H direction. Thus, a composition according to the invention has a gel-like consistency.

The stability of the composition can be ensured without the mandatory presence of a surfactant. Therefore, a cosmetic composition according to the invention does not necessarily require surfactant or silicone emulsifier to ensure its stability. It is known from the state of the art to observe the intrinsic nature of a mixture of aqueous and oily gels in a gel / gel composition, for example, by introducing a coloring material into the aqueous gelled phase. either in the lipophilic gelled phase, before the formation of the gel / gel-type composition. During the visual inspection, in a gel / gel composition, the coloring matter appears to be uniformly dispersed, even if the dye is present only in the gelled aqueous phase or in the gelled oily phase. In fact, if two different dyes of different colors are introduced into the oil phase and the aqueous phase, respectively, before the formation of the gel / gel composition, the two colors can be observed as uniformly dispersed throughout the composition of the composition. gel / gel type. This is different from an emulsion in which, if a water-soluble or oil-soluble dye is introduced into the aqueous and oily phases, respectively, before forming the emulsion, only the color of the emulsion will be observed. dye present in the outer phase (Remington: The Science and Practice of Pharmacy, 19th Edition (1995), Chapter 21, page 282).

It is also known to distinguish a gel / gel composition from an emulsion by performing a "drop test". This test consists of demonstrating the bicontinuous nature of a gel / gel composition. Indeed, as mentioned above, the consistency of a composition is obtained thanks to the interpenetration of the aqueous and oily gelled domains. Therefore, the bi-continuous nature of a gel / gel composition can be evidenced by a simple test with hydrophilic and hydrophobic solvents respectively. This test consists in depositing, on the one hand, a drop of a hydrophilic solvent on a first sample of the tested composition, and, on the other hand, a drop of a hydrophobic solvent on a second sample of the same composition tested, and to analyze the behavior of the two drops of solvents. In the case of an O / W emulsion, the drop of hydrophilic solvent diffuses into the sample and the drop of hydrophobic solvent remains on the surface of the sample. In the case of an W / O emulsion, the drop of hydrophilic solvent remains on the surface of the sample and the drop of hydrophobic solvent diffuses throughout the sample. Finally, in the case of a gel / gel composition (bi-continuous system), the hydrophilic and hydrophobic drops diffuse throughout the sample. In the case of the present invention, the test that will be preferred for distinguishing a gel / gel composition from an emulsion is a dilution test. Indeed, in a gel / gel composition, the aqueous and oily gelled domains interpenetrate and form a consistent and stable composition, in which the behavior in water and in oil is different from the behavior of an emulsion. Therefore, the behavior during a dilution of a gel / gel composition (bi-continuous system) can be compared to that of an emulsion. More specifically, the dilution test consists in putting 40 g of product and 160 g of dilution solvent (water or oil) in a beaker. The dilution is carried out with controlled stirring to avoid any emulsification phenomenon. In particular, this is done using a planetary mixer: Speed Mixer TM DAC400FVZ. The mixer speed is set at 1500 rpm for 4 minutes. Finally, observation of the resulting sample is performed using an optical microscope at a magnification of x 100 (x 10 x 10). It may be noted that oils such as Parleam® and Xiameter PMX-200 Silicone Fluid 5CS® marketed by Dow Corning are suitable as a diluting solvent in the same way as one of the oils contained in the composition.

In the case of a composition of the gel / gel type (bicontinuous system), when it is diluted in oil or in water, a heterogeneous appearance is always observed. When a gel / gel composition (bicontinuous system) is diluted in water, pieces of oily gel are observed in suspension and when a gel / gel composition (bicontinuous system) is diluted in from the oil, pieces of aqueous gel in suspension are observed. On the contrary, during the dilution, the emulsions exhibit a different behavior. An O / W emulsion, when diluted in an aqueous solvent, gradually reduces without having a heterogeneous and lumpy appearance. This same O / W emulsion, when diluted with the oil, has a heterogeneous appearance (O / W emulsion pieces suspended in the oil). W / O emulsion, when diluted with an aqueous solvent, has a heterogeneous appearance (W / O emulsion pieces suspended in water). This same W / O emulsion, when diluted in the oil, gradually reduces without presenting a heterogeneous and lumpy appearance.

According to the present invention, the aqueous gelled phase and the oily gelled phase forming a composition according to the invention are present in a weight ratio ranging from 95/5 to 5/95. More preferably, the aqueous phase and the oily phase are present in a weight ratio ranging from 20/80 to 80/20 and even more preferably ranging from 30/70 to 70/30, and more preferably from 30/70 to 80/20.

The ratio between the two gelled phases is adjusted according to the desired cosmetic properties. Thus, in the case of a care or makeup composition, in particular the face, it will be advantageous to promote an aqueous gelled phase / oily gelled phase weight ratio greater than or equal to 1, in particular ranging from 50/50 to 90 Preferably, a composition according to the invention can be in the form of a creamy gel having a minimum stress below which it does not flow. unless subjected to external mechanical stress. Advantageously, a composition according to the invention may therefore be in the form of a creamy gel having a minimum stress below which it does not flow unless subjected to external mechanical stress.

As is apparent from the following a composition according to the invention may have a minimum threshold stress of 1.5 Pa and in particular greater than 10 Pa. It may also advantageously have a modulus of rigidity G * of at least 400. Pa, and preferably greater than 1000 Pa.

According to an advantageous variant embodiment, the gelled phases considered for forming a composition according to the invention may respectively have a threshold stress greater than 1.5 Pa, and preferably greater than 10 Pa. The characterization of the threshold stresses is carried out by means of rheology measurements in oscillation. A methodology is proposed in the exemplification chapter 10 of this text. In general, the corresponding measurements are carried out at 25 ° C. using an imposed stress rheometer, RS600 HAAKE, equipped with a plane-plane measuring body (diameter 60 mm) provided with a device anti-evaporation (bell). For each measurement, the sample is gently set up and measurements begin 5 minutes after the sample has been placed in the gap (2 mm). The tested composition is then subjected to a stress ramp of 10-2 at 102 Pa at a frequency set at 1 Hz. A composition according to the invention may also have a certain elasticity. This elasticity can be characterized by a modulus of rigidity G * which below this minimum stress threshold can be at least 400 Pa, and preferably greater than 1000 Pa. The G * value of a composition can be obtained by subjecting the composition considered at a stress ramp of 10-2 at 102 Pa at a frequency set at 1 Hz. A. HYDROPHILIC GELIFIER NON AMYLACE For the purposes of the present invention, the term "hydrophilic gelling agent" is intended to mean a compound capable of gelling the phase aqueous compositions according to the invention. The term "non-starch hydrophilic gelling agent" in the sense of the present invention, a hydrophilic gelling agent which is different from a starch. The hydrophilic gelling agent and is therefore present in the aqueous phase of the composition.

The gelling agent may be water-soluble or water-dispersible. As specified above, the aqueous phase of a composition according to the invention is gelled with at least one hydrophilic gelling agent.

The hydrophilic gelling agent may be chosen from synthetic polymeric gelling agents, natural or non-starch polymeric gelling agents, in particular non-starch polysaccharides, mixed silicates and pyrogenic silicas, and mixtures thereof.

Preferably, the hydrophilic gelling agent may be selected from synthetic polymeric gelling agents. I. Natural or non-starch polymeric gelling agents Polymeric hydrophilic gelling agents suitable for the invention may be natural or of natural origin. For the purposes of the invention, the expression "of natural origin" means polymeric gelling agents obtained by modifying natural polymeric gelling agents. These gelling agents may be particulate or non-particulate. More specifically, these gelling agents fall within the category of polysaccharides.

Non-starch polysaccharides In a general manner, the non-starch polysaccharides may be chosen from polysaccharides prepared by microorganisms; polysaccharides isolated from algae, polysaccharides from higher plants, such as homogeneous polysaccharides, in particular celluloses and its derivatives or fructans, heterogeneous polysaccharides such as gums arabic, galactomannans, glucomannans, pectins, and their derivatives; and their mixtures. In particular, the polysaccharides may be chosen from fructans, gellanes, glucans, amylose, amylopectin, glycogen, pullulan, dextrans, celluloses and their derivatives, in particular methylcelluloses, hydroxyalkylcelluloses and ethylhydroxyethylcelluloses. and carboxymethylcelluloses, mannans, xylans, lignins, arabans, galactans, galacturonans, alginate compounds, chitin, chitosans, glucoronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acids and pectins, arabinogalactans, carrageenans, agars, glycosaminoglucans, gum arabic, tragacanth gums, ghatti gums, karaya gums, locust bean gums, galactomannans such as guar gums and their non-ionic derivatives, in particular hydroxypropyl guar, and ionic, biopolysaccharide gums of microbial origin, in particular scleroglucan or xanthan gums, mucopolysaccharides, and in particular chondroitin sulphates and mixtures thereof.

These polysaccharides may be chemically modified, in particular by urea, urethane groups, or by hydrolysis, oxidation, esterification, etherification, sulfation, phosphatation, amination, amidation or alkylation, or by several of these modifications. The derivatives obtained can be anionic, cationic, amphoteric or nonionic. Advantageously, the polysaccharides may be chosen from carrageenans, in particular kappa-carrageenan, gellan gum, agar-agar, xanthan gum, and alginate-based compounds, in particular alginate. sodium, saroglucan gum, guar gum, inulin, pullulan, and mixtures thereof.

In general, compounds of this type which can be used in the present invention are chosen from those described in particular in "Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, 1982, Volume 3, pp. 896-900, and Vol. 15, pp 439-458 ", in" Polymers in Nature, by EA Mc GREGOR and CT GREENWOOD, John Wiley & Sons Editions, Chapter 6, pp. 240-328, 1980 ", in the book by Robert L. DAVIDSON entitled "Handbook of Water Soluble Gums and Resins" edited by Mc Graw Hill Book Company (1980) and in the Industrial Gums "Polysaccharides and their Derivatives", Edited by Roy L. WHISTLER, Second Edition, Edition Academic Press Inc. " Such a gelling agent may be used in a proportion of 0.1% to 8% by weight of dry matter relative to the total weight of the aqueous phase, in particular from 0.1% to 6% by weight, preferably from 0% to , 5% and 2.5% by weight, in particular about 1%, or about 1.5% by weight relative to the total weight of the aqueous phase. More specifically, these polysaccharides suitable for the invention can be distinguished according to whether they are derived from microorganisms, algae or higher plants, and are detailed below.

3025094 12 Polysaccharides Produced by Xanthan Microorganisms Xanthan is a heteropolysaccharide produced on an industrial scale by the aerobic fermentation of the bacterium Xanthomonas campestris. Its structure consists of a main chain of β (1,4) -linked β-D-glucoses, similar to cellulose. One out of every two glucose molecules has a trisaccharide side chain consisting of α-Mannose, β-D-glucuronic acid and terminal β-D-mannose. The internal mannose residue is generally acetylated on carbon 6. About 30% of the end mannose residues carry a pyruvate group bound in chelated form between carbons 4 and 6.

The glucuronic acids and the charged pyruvic acids are ionizable, and therefore responsible for the anionic nature of xanthan (negative charge up to pH 1). The contents of the pyruvate and acetate residues vary according to the strain of bacteria, the fermentation process, the conditions after fermentation and the purification steps. These groups can be neutralized in commercial products with Na +, K + or Ca2 + ions (SATIA Company, 1986). The neutralized form can be converted to an acid form by ion exchange or by dialysis of an acidic solution. The xanthan gums have a molecular weight of between 1,000,000 and 50,000,000 and a viscosity of between 0.6 and 1.65 Pa.s for an aqueous composition containing 1% of xanthan gum (measured at 25 ° C. using a viscometer). Brookfield, type 20 LVT at 60 rpm). The xanthan gums are represented for example by the products sold under the names Rhodicare by the company Rhodia Chimie, under the name Satiaxanetm by the company Cargill Texturizing Solutions (for the food, cosmetic and pharmaceutical industry), under the name 25 NOVAXANTM by the company ADM, and under the names Kelzan® and Keltrol® by the company CP-Kelco. Pullulan Pullulan is a polysaccharide consisting of maltotriose units, known as a (1,4) -a (1,6) -glucan. Three units of glucose in maltotriose are connected by a glycosidic linkage to a (1,4), while the consecutive maltotriose units are connected to each other by a glycosidic linkage to a (1,6).

The pullulan is for example produced under the reference Pullulan PF 20 by the Hayashibara group in Japan. Dextran and Dextran Sulfate Dextran is a neutral polysaccharide without a charged, biologically inert group prepared by fermentation of beet sugar containing only hydroxyl groups. It is possible to obtain from the native dextran by hydrolysis and purification, dextran fractions of different molecular weights. Dextran may in particular be in the form of dextran sulfate. Dextran is represented, for example, by the products sold under the name Dextran or Dextran T by the company Pharmacosmos, under the name Dextran 40 powder or Dextran 70 powder by the company Meito Sangyo Co. Dextran sulphate is marketed by the company PK Chemical A / S under the name Dextran sulphate. Succinoglycan Succinoglycan is an extracellular polymer produced by bacterial fermentation, of high molecular weight and consisting of repeated units of octasaccharides (repetition of 8 sugars). Succinoglycans are, for example, sold under the name Rheozan by Rhodia. Scleroglucan Scleroglucan is a nonionic branched homopolysaccharide consisting of 25 units of 3-D glucan. The molecules consist of a main linear chain formed of D-glucose units linked by P (1,3) bonds and of which one in three is linked to a lateral D-glucose unit via a P (1,6) bond. A more complete description of scleroglucans and their preparation can be found in US 3,301,848.

Scleroglucan is for example sold under the name AMIGEL by the company ALBAN MULLER, or under the name ACTIGUMTM CS by Cargill.

3025094 14 Gellan gum Gellan gum is an anionic linear heteropolyoside based on oligoside units composed of 4 monoses (tetra-oside). D-glucose, L-rhamnose and D-glucuronic acid in 2: 1: 1 ratios are present in the gellan gum as monomeric elements. It is for example sold under the name KELCOGEL CG LA by the company CP KELCO.

Polysaccharides Isolated from Galactan Algae The polysaccharide according to the invention may be a galactan, in particular chosen from agar or carrageenans. Carrageenans are anionic polysaccharides constituting the cell walls of various red algae (Rhodophyceae) belonging to the families Gigartinacae, Hypneaceae, Furcellariaceae and Polyideaceae. They are generally obtained by hot aqueous extraction from natural strains of said algae. These linear polymers, formed by disaccharide units, are composed of two D-galactopyranose units alternately linked by α (1,3) and 13 (1,4) bonds. These are highly sulphated polysaccharides (20-50%) and the α-D-galactopyranosyl residues may be in the form of 3,6-anhydro. Depending on the number and position of ester-sulfate groups on the repeating disaccharide of the molecule, there are several types of carrageenans namely: kappa-carrageenans which have an ester-sulfate group, iotacarraghénanes which have two ester-sulfate groups and lambda carrageenans which have three ester sulfate groups. Carrageenans consist essentially of potassium, sodium, magnesium, triethanolamine and / or calcium salts and sulfate esters of polysaccharides. Carrageenans are sold especially by the company Seppic under the name Solagum®, by the company Gelymar under the name Carragel®, Carralact® and Carrasol® by the company Cargill under the names SATIAGELTM and 3025094 15 SATIAGUMTm, and by CP-Kelco under the name GENULACTA®, GENUGEL® and GENUVI SC 0®. Galactans Agar type are galactose polysaccharides contained in the cell wall of some of these species of red algae (rhodophycea). They are formed of a polymer group whose base skeleton is a chain f3 (1,3) D-galactopyranose and a (1,4) L3-6 anhydrogalactose, these units repeating regularly and alternately. The differences within the agar family are due to the presence or absence of methyl or carboxyethylated solvate groups. These hybrid structures are generally present in variable percentage, depending on the species of algae and the harvest season. Agar-agar is a mixture of polysaccharides (agarose and agaropectin) of high molecular weight, between 40,000 and 300,000 g.mo1-1. It is obtained by producing algae extraction juices, usually by autoclaving, and treating these juices which include about 2% agar-agar, in order to extract it.

The agar is for example produced by the group B & V Agar Producers, under the name Gold Agar, Agarite and Grand Agar by the company Hispanagar, and under the names Agar-Agar, QSA (Quick Soluble Agar), and Puragar by the company. Setexam. Furcellarane Furcellaran is obtained commercially from red algae Furcellaria fasztigiata. Furcellarane is for example produced by the company East-Agar. Alginate Compound For the purposes of the invention, the term "alginate-based compound" means alginic acid, alginic acid derivatives and alginic acid salts (alginates) or derivatives thereof. . Preferably, the alginate compound is water soluble. Alginic acid, a natural substance derived from brown algae or certain bacteria, is a polyuronic acid composed of 2 uronic acids linked by (1,4) glycosidic linkages: PD-manuronic acid (M) and the acid α-glucuronic (G). Alginic acid is capable of forming water-soluble salts (alginates) with alkali metals such as sodium, potassium, lithium, substituted amine 3025094 16 and ammonium cations such as methylamine, ethanolamine and the like. , diethanolamine, triethanolamine. These alginates are water-soluble in aqueous medium at a pH of 4 but dissociate in alginic acid at a pH below 4. This (s) compound (s) based on alginate is (are) capable (s) to crosslink in the presence At least one crosslinking agent, by formation of ionic bonds between said (s) compound (s) based on alginate and said (s) agent (s) crosslinking. The formation of multiple crosslinks between several molecules of the said alginate-based compound (s) causes the formation of a water-insoluble gel. Alginate-based compounds having a weight average molecular weight of from 10,000 to 1,000,000, preferably from 15,000 to 500,000, and preferably from 20,000 to 250,000, are preferably used. In a preferred embodiment, the alginate compound is alginic acid and / or a salt thereof. Advantageously, the alginate compound is an alginate salt, and preferably sodium alginate. The alginate-based compound may be chemically modified, in particular by urea, urethane groups, or by reaction of hydrolysis, oxidation, esterification, etherification, sulfation, phosphatation, amination, amidation, alkylation, or by several of these modifications.

The derivatives obtained can be anionic, cationic, amphoteric or nonionic. The alginate-based compounds that are suitable for the invention can be represented, for example, by the products sold under the names Kelcosol, Satigaline, Cecalgum ™ or Algogel ™ by the company Cargill products, under the name Protanal ™ by the company FMC Biopolymer. under the name GRINDSTED® Alginate by the company Danisco, under the name KIMICA ALGIN by the company KIMICA, and under the names Manucol® and Manugel® by the company ISP.

Upper Polysaccharides This class of polysaccharides can be divided into homogeneous polysaccharides (a single species of oses) and heterogeneous compounds of several types of monosaccharides. A) Homogeneous polysaccharides and their derivatives The polysaccharide according to the invention may be chosen from celluloses and derivatives or fructans.

Cellulose and derivatives The polysaccharide according to the invention may also be a cellulose or a derivative thereof in particular ethers or cellulose esters (eg methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylpropylcellulose, cellulose acetate cellulose nitrate, nitrocellulose). The invention may also contain a cellulosic associative polymer. Cellulosic compound is understood to mean, according to the invention, any polysaccharide compound having in its structure linear chains of anhydroglucopyranose (AGU) residues united by glycoside bonds f3 (1,4). The repeating unit is the cellobiose dimer. The AGUs are in chair conformation and have 3 hydroxyl functions: 2 secondary alcohols (in position 2 and 3) and a primary alcohol (in position 6). The polymers thus formed combine with each other by intermolecular links of the hydrogen bonding type, thus conferring a fibrillar structure on the cellulose (approximately 1500 molecules per fiber).

The degree of polymerization differs greatly depending on the origin of the cellulose; its value can vary from a few hundred to a few tens of thousands. The cellulose has the following chemical structure: The hydroxyl groups of the cellulose may react partially or totally with different chemical reagents to give cellulose derivatives having own properties. The cellulose derivatives may be anionic, cationic, amphoteric or nonionic. Among these derivatives, there are cellulose ethers, cellulose esters and cellulose ether esters. Among the nonionic cellulose ethers, mention may be made of alkylcelluloses such as methylcelluloses and ethylcelluloses; hydroxyalkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses and hydroxypropylcelluloses; mixed hydroxyalkyl-alkylcellulose celluloses such as hydroxypropylmethylcelluloses, hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses and hydroxybutyl-methylcelluloses. Among the anionic cellulose ethers, mention may be made of carboxyalkylcelluloses and their salts. By way of example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses and carboxymethylhydroxyethylcelluloses and their sodium salts. Among the cationic cellulose ethers, mention may be made of quaternized hydroxyethylcelluloses which may or may not be crosslinked.

The quaternizer may be especially glycidyltrimethylammonium chloride or a fatty amine such as laurylamine or stearylamine. Another cationic cellulose ether that may be mentioned is hydroxyethylcellulosehydroxypropyltrimethylammonium. The quaternized cellulose derivatives are, in particular: quaternized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof ; The quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof. The alkyl radicals carried by the above-quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. Examples of C8-C30 fatty chain quaternized alkylhydroxyethylcelluloses are the products QUATRISOFT LM 200, QUATRISOFT LM-X 5229-18-A, QUATRISOFT LM-X 529-18B (C12 alkyl) and QUATRISOFT LM- X 529-8 (C18 alkyl) marketed by the company AMERCHOL and the products CRODACEL QM, CRODACEL QL (C12 alkyl) and CRODACEL QS (C18 alkyl) marketed by the company CRODA. Among the cellulose derivatives, mention may also be made of: - celluloses modified with groups comprising at least one fatty chain, for example hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl groups, in particular with C8- C22, arylalkyl, alkylaryl, such as NATROSOL PLUS GRADE 330 CS (C16 alkyls) sold by AQUALON, and 20 - celluloses modified with polyalkylene glycol ether alkyl phenol groups, such as the product AMERCELL POLYMER HM- 1500 (polyethylene glycol (15) nonyl phenol ether) sold by the company Amerchol. Among the cellulose esters, there are the inorganic esters of cellulose (cellulose nitrates, sulphates, or phosphates, etc.), the cellulose organic esters (monoacetates, triacetates, amidopropionates, acetate butyrates, cellulose acetate propionates or acetatetrimellitates). .) and mixed organic / inorganic cellulose esters such as cellulose acetate-butyrate sulphates and cellulose acetate propionates. Among the cellulose ether esters, mention may be made of hydroxypropyl methylcellulose phthalates and ethylcellulose sulphates.

The cellulosic compounds of the invention may be selected from unsubstituted celluloses and substituted celluloses.

The celluloses and derivatives are represented for example by the products sold under the names Avicel® (microcrystalline cellulose, MCC) by the company FMC Biopolymers, under the name Cekol (carboxymethylcellulose) by the company Noviant (CP-Kelco), under the name Akucell AF (sodium carboxymethylcellulose) denomination by Akzo Nobel, under the name MethocelTM (cellulose ethers) and EthocelTM (ethylcellulose) by the company DOW, under the trade names Aqualon® (carboxymethylcellulose and sodium carboxymethylcellulose), Benecel® (methylcellulose) BlanoseTM (carboxymethylcellulose), Culminal® (methylcellulose, hydroxypropyl methylcellulose), Klucel® (hydroxypropylcellulose), Polyoxy surf (cetyl hydroxyethylcellulose) and Natrosol® CS (hydroxyethylcellulose) by Hercules Aqualon. Fructosans The polysaccharide according to the invention may in particular be a fructosan selected from among inulin and its derivatives (in particular dicarboxy and carboxymethyl inulins). Fructans or fructosans are oligosaccharides or polysaccharides comprising a sequence of anhydrofructose units optionally associated with a plurality of different saccharide residues of fructose. The fructans can be linear or branched. The fructans can be products obtained directly from a plant or microbial source or products whose chain length has been modified (increased or reduced) by fractionation, synthesis or hydrolysis in particular enzymatic. The fructans generally have a degree of polymerization of from 2 to about 1000, and preferably from 2 to about 60. There are 3 groups of fructans. The first group corresponds to products whose fructose units are mostly linked by (3 (2,1) bonds.) These are essentially linear fructans than inulin, while the second group corresponds to linear fructoses. Fructose units are essentially linked by (3 (2,6) bonds.) These products are levans.

The third group corresponds to mixed fructans, that is to say having sequences (3 (2,6) and (3 (2,1)) which are essentially branched fructans than graminans.

Preferred fructans in the compositions according to the invention are inulins. Inulin can be obtained for example from chicory, dahlia or Jerusalem artichoke, preferably from chicory. In particular, the polysaccharide, especially inulin, has a degree of polymerization of from 2 to about 1000 and preferably from 2 to about 60, and a degree of substitution of less than 2 based on a fructose unit. The inulin used for this invention is represented, for example, by the products sold under the name Beneo ™ Inulin by the company Orafti and under the name Frutafit® by the company Sensus. B) Heterogeneous Polysaccharides and Their Derivatives The polysaccharides that may be used according to the invention may be gums, for example cassia gum, karaya gum, konjac gum, tragacanth gum, tara gum, acacia gum or arabic gum.

Gum arabic Gum arabic is a highly branched acidic polysaccharide which is in the form of mixtures of potassium, magnesium and calcium salts. The monomeric elements of the free acid (arabic acid) are D-galactose, L-arabinose, L-rhamnose and D-glucuronic acid. Galactomannans (guar, carob, fenugreek, tara gum) and derivatives (phosphated guar, hydroxypropyl guar ...) Galactomannans are nonionic polysaccharides extracted from the albumen 25 of leguminous seeds of which they constitute the reserve carbohydrate. Galactomannans are macromolecules consisting of a main chain of F3 (1,4) -linked D-mannopyranose units, bearing lateral branches consisting of a single unit D-galactopyranose linked in a (1,6) to the chain main. The different galactomannans are distinguished on the one hand by the proportion of α-D-galactopyranose units present in the polymer, and on the other hand by significant differences in terms of distribution of the galactose units along the mannose chain.

The mannose / galactose ratio (M / G) is of the order of 2 for guar gum, 3 for tara gum and 4 for locust bean gum. The galactomannans have the following chemical structure: ## STR1 ## The guar gum is characterized by a mannose: galactose ratio of about 2: 1. The galactose group is regularly distributed along the the mannose chain.

The guar gums which can be used according to the invention can be nonionic, cationic or anionic. According to the invention, chemically modified or unmodified nonionic guar gums can be used. The unmodified nonionic guar gums are, for example, the products sold under the name Vidogum GH, Vidogum G and Vidocrem by the company Unipektin and under the name Jaguar by the company Rhodia, under the name Meypro® Guar by the company Danisco. under the name VISCOGUMTM by the company Cargill, and under the name Supercol® guar gum by the company Aqualon. The hydrolysed nonionic guar gums that may be used according to the invention are, for example, represented by the products sold under the name Meyprodor® 20 by Danisco. The modified nonionic guar gums which can be used according to the invention are preferably modified with hydroxyC 1 -C 6 groups, among which, by way of example, hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups may be mentioned.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are, for example, sold under the trade names Jaguar HP 60, Jaguar HP 105 and Jaguar HP 120 (hydroxypropyl guar), by the company Rhodia, or under the name N HP-Hance® (hydroxypropyl guar) by AQUALON. The cationic galactomannan gums preferably have a cationic charge density less than or equal to 1.5 meq / g and more particularly between 0.1 and 1 meq / g. The charge density can be determined according to the Kjeldahl method. It generally corresponds to a pH of the order of 3 to 9.

In general, for the purposes of the present invention, the term "cationic galactomannan gum" means any galactomannan gum containing cationic groups and / or ionizable groups into cationic groups. Preferred cationic groups are chosen from those comprising primary, secondary, tertiary and / or quaternary amine groups.

The cationic galactomannan gums used generally have a weight average molecular weight of between about 500 and 5 × 10 6, and preferably between about 103 and 3 × 10 6. The cationic galactomannan gums that can be used according to the present invention are, for example, gums comprising cationic trialkyl (C 1 -C 4) ammonium groups. Preferably, 2% to 30% by number of the hydroxyl functions of these gums carry cationic trialkylammonium groups. Among these trialkylammonium groups, there may be mentioned very particularly trimethylammonium and triethylammonium groups. Even more preferably, these groups represent from 5% to 20% by weight of the total weight of the modified galactomannan gum. According to the invention, the cationic galactomannan gum is preferably a guar gum comprising hydroxypropyltrimethylammonium groups, that is to say a guar gum modified for example with 2,3-epoxypropyltrimethylammonium chloride.

These galactomannan gums, in particular of guar gums modified with cationic groups, are products already known in themselves and are for example described in patents US Pat. Nos. 3,589,578 and 4,031,307. Such products are also 302,5094 24 sold. especially under the trade names of Jaguar EXCEL, Jaguar C13 S, Jaguar C 15, Jaguar C 17 and Jaguar C162 (Guar Hydroxypropyltrimonium Chloride) by the company Rhodia, under the name Amilan® Guar (Guar Hydroxypropyltrimonium Chloride) by the company Degussa, and under the name N-Hance® 3000 (Guar 5 Hydroxypropyltrimonium Chloride) by the company Aqualon. The anionic guar gums that may be used according to the invention are polymers containing groups derived from carboxylic, sulfonic, sulphene, phosphoric, phosphonic acid or pyruvic acid. Preferably, the anionic group is a carboxylic acid group. The anionic group may also be in the form of an acid salt, in particular a salt of sodium, calcium, lithium or potassium. The anionic guar gums that can be used according to the invention are preferably carboxymethyl guar derivatives (carboxymethyl guar or carboxymethyl hydroxypropyl guar).

15 Carob Locust bean gum is extracted from carob seed (Ceratonia siliqua). The unmodified carob gum that can be used in this invention is sold, for example, under the name ViscogumTM by the company Cargill, under the name Vidogum L by the company Unipektin, under the name Grinsted® LBG by the company Danisco. The chemically modified carob gums which can be used in this invention can be represented, for example, by the cationic carob sold under the name Catinal CLB (carob Hydroxypropyltrimonium Chloride) by the company Toho. TARA gum The Tara gum that can be used in the context of this invention is sold, for example, under the name Vidogum SP by the company Unipektin.

Glucomannans (Konjac gum) Glucomannan is a high molecular weight polysaccharide (500,000 <Mglucomannan <2,000,000), composed of D-mannose units and D-glucose with a branch every 50 or 60 units approx. It is found in wood but is also the main constituent of Konjac gum. Konjac (Amorphophallus konjac) is a plant of the family Araceae. The products that can be used according to the invention are for example sold under the name Propol® and Rheolex® by the company Shimizu.

LM and HM Pectins, and Derivatives Pectins are linear polymers of α-D-galacturonic acid (at least 65%) linked at the 1- and 4-positions, with a certain proportion of carboxylic groups esterified with a methanol group. About 20% of the sugars constituting the pectin molecule are neutral sugars (L-rhamnose, D-glucose, D-galactose, L-arabinose, D-xylose). The residues of L-rhamnose are found in all the pectins, integrated in the main chain in positions 1,2. Uronic acid molecules have carboxyl functions. This function gives the pectins the ability to exchange ions when they are in C00- form. Bivalent ions (especially calcium) have the ability to form ionic bridges between two carboxyl groups of two different pectin molecules. In the natural state, a certain proportion of the carboxylic groups are esterified with a methanol group. The degree of natural esterification of a pectin can vary between 70% (apple, lemon) and 10% (strawberry) depending on the source used. From 25 pectins of high degree of esterification, it is possible to hydrolyze the -COOCH 3 groups, in order to obtain weakly esterified pectins. Depending on the proportion of methyl or non-methylated monomers, the chain is therefore more or less acidic. HM pectins (High methoxy) having a degree of esterification greater than 50% and LM (Low Methoxy) pectins having a degree of esterification of less than 50% are thus defined.

In the case of amidated pectins, the -OCH3 group is substituted with a -M-12 group.

The pectins are in particular sold by Cargill under the name UnipectineTM, by the company CP-Kelco under the name GENU, by Danisco under the name GRINSTED Pectin.

Other Polysaccharides Among the other polysaccharides that can be used according to the invention, mention may also be made of chitin (Poly N-acetyl-D-glucosamine, (3 (1,4) -2-acetamido-2-deoxy-D-glucose), chitosan and derivatives (chitosan-beta-glycerophosphate, carboxymethylchitine, etc.) such as those sold by France-Chitin, glycosaminoglycans (GAG) such as hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate and preferably hyaluronic acid, xylans (or arabinoxylans) and derivatives The arabinoxylans are polymers of xylose and arabinose, all grouped under the name "pentosans".

Xylans consist of a main chain of P (1,4) -linked D-xylose units on which three substituents are found (Rouau & Thibault, 1987): acid units, α-arabinofuranose units side chains which may contain arabinose, xylose, galactose and glucuronic acid. According to this variant, the polysaccharide is preferably hyaluronic acid, or one of its salts, such as the sodium salt (sodium hyaluronate). II. Synthetic Polymer Gelling Agents For the purposes of the invention, the term synthetic means that the polymer is neither naturally extant nor derived from a polymer of natural origin. The synthetic polymeric hydrophilic gelling agent according to the invention may be particulate or non-particulate. For the purposes of the invention, the term "particulate" means that the polymer is in the form of particles, preferably spherical.

As will be apparent from the following, the polymeric hydrophilic gelling agent is advantageously chosen from crosslinked acrylic homopolymers or copolymers; associative polymers, in particular associative polymers of the polyurethane type; polyacrylamides and polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, crosslinked and / or neutralized; carboxyvinyl polymers, modified or otherwise, and mixtures thereof, in particular as defined below.

II.A. Particulate synthetic polymer gelling agents They are preferably chosen from crosslinked polymers. It may in particular be crosslinked homopolymers or acrylic copolymers, preferably partially neutralized or neutralized, which are in particulate form.

According to one embodiment, the particulate gelling agent according to the present invention is chosen from crosslinked sodium polyacrylates. Preferably, it has, in the dry or non-hydrated state, an average size of less than or equal to 100 μm, preferably less than or equal to 50 μm. The average particle size is the mass average diameter measured by laser particle size or other equivalent method known to those skilled in the art. Thus, preferably, the particulate gelling agent according to the present invention is chosen from crosslinked sodium polyacrylates, preferably in the form of particles having a mean size (or average diameter) less than or equal to 100 microns, more preferably in the form of particles. spherical.

By way of example of crosslinked sodium polyacrylates, mention may be made of those sold under the names Octacare X100, X110 and RM100 by the company Avecia, those sold under the names Flocare GB300 and Flosorb 500 by the company SNF, those marketed under the names Luquasorb 1003, Luquasorb 1010, Luquasorb 1280 and Luquasorb 1110 by BASF, those sold under the names Water Lock G400 and G430 (INCI name: Acrylamide / Sodium acrylate copolymer) by the company Grain Processing. Cross-linked polyacrylate microspheres such as, for example, those marketed under the name AQUAKEEP® 10 SH NF proposed by the company Sumitomo Seika may also be mentioned.

Such gelling agents may be used in amounts of 0.1% to 5% by weight of dry matter relative to the total weight of the aqueous phase, in particular from 0.5% to 30% by weight, and in particular from about 0.8% to 1.7% by weight based on the total weight of the aqueous phase. II.B. Non-particulate synthetic polymeric gelling agents This family of gelling agents can be detailed in the following sub-families: 1. Associative polymers, 2. Polyacrylamides and polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, crosslinked and / or neutralized, and 3. Modified or unmodified carboxyvinyl polymers.

H.B.1 Associative Polymers For the purposes of the present invention, the term "associative polymer" means any amphiphilic polymer comprising in its structure at least one fatty chain and at least one hydrophilic portion. The associative polymers according to the present invention may be anionic, cationic, nonionic or amphoteric. Associative Anionic Polymers Among the associative anionic polymers, mention may be made of those comprising at least one hydrophilic unit, and at least one fatty-chain allyl ether unit, more particularly from those whose hydrophilic unit consists of an ethylenically unsaturated anionic monomer. , more particularly with a vinyl carboxylic acid and more particularly with an acrylic acid, a methacrylic acid or mixtures thereof, and whose fatty-chain allyl ether unit corresponds to the following monomer of formula (I): CH 2 = C (R) In which R 'denotes H or CH3, B denotes the ethyleneoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl and arylalkyl radicals; , aryl, alkylaryl, cycloalkyl, comprising 8 to 30 carbon atoms, preferably 10 to 24, and more particularly 12 to 18 carbon atoms. Anionic amphiphilic polymers of this type are described and prepared according to an emulsion polymerization process in patent EP 0 216 479.

Among the associative anionic polymers, mention may also be made of terpolymers of C30-C38 maleic anhydride / α-olefin / alkyl maleate, such as the maleic anhydride / C30-C38 olefin copolymer / maleate copolymer product. isopropyl sold under the name Performa V 1608 by the company Newphase Technologies.

Among the anionic associative polymers, there may be mentioned according to a preferred embodiment, copolymers comprising among their monomers an α, β-monoethylenically unsaturated carboxylic acid and an α, β-monoethylenically unsaturated carboxylic acid ester and Preferably, these compounds also comprise, as monomer, an α, β-monoethylenically unsaturated carboxylic acid ester of C 1 -C 4 alcohol, for example of this type of compound. mention may be made of Aculyn 22® sold by Rohm and Haas, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer (comprising 20 OE units) or Aculyn 28® (methacrylic acid / acrylate terpolymer). Ethylene / Behenyl methacrylate oxyethylene (250E) As associative anionic polymers, mention may also be made of anionic polymers comprising at least one hydrophilic unit of AC acid type. unsaturated olefinic carboxylic acid, and at least one hydrophobic unit exclusively of the (C 10 -C 30) alkyl ester of unsaturated carboxylic acid. By way of example, mention may be made of the anionic polymers described and prepared according to US Pat. Nos. 3,915,921 and 4,509,949. Associated anionic polymers that may also be mentioned are anionic terpolymers. The anionic terpolymer used according to the invention is a linear or connected and / or crosslinked terpolymer of at least one monomer (1) carrying an acid function in free form, partially or totally salified with a nonionic monomer (2). chosen from NN, dimethylacrylamide and 2-hydroxyethyl acrylate and at least one polyoxyethylenated alkyl acrylate monomer (3) of formula (I) below: R1 1-oon (I) 3025094 30 in which R1 represents an atom of hydrogen, R represents a linear or branched C2-C8 alkyl radical and n represents a number ranging from 1 to 10. "Connected polymer" denotes a nonlinear polymer which has pendant chains so as to obtain, when this Polymer is dissolved in water, a high state of entanglement leading to very high viscosities, low speed gradient. The term "crosslinked polymer" denotes a non-linear polymer in the form of a three-dimensional network which is insoluble in water but swellable with water and leads to the production of a chemical gel.

The acid function of the monomer (1) is in particular the sulphonic acid, phosphonic acid function, said functions being in free form, partially or totally salified. The monomer (1) may be selected from styrene sulfonic acid, ethylsulfonic acid or 2-methyl-2 - [(1-oxo-2-propenyl] amino] 1-propanesulfonic acid (also called Acryloyldimethyltaurate) under free form, partially or totally salified.It is present in the anionic terpolymer preferably in molar proportions of between 5% and 95 mol% and more particularly between 10% and 90 mol% .The monomer (1) will be more particularly the 2-methyl-2 - [(1-oxo-2-propenyl] amino] 1-propanesulfonic acid in free, partially or totally salified form The acid function in partially or totally salified form will preferably be an alkali metal salt such as a sodium or potassium salt, an ammonium salt, an aminoalcohol salt such as a monoethanolamine salt or an amino acid salt such as a salt of lysine.

The monomer (2) is preferably present in the anionic terpolymer in molar proportions of between 4.9% and 90% molar and more particularly between 9.5% and 85% molar and even more particularly between 19.5% and 75% molar. In the formula (I), as an example of linear C8-C16 alkyl radical, mention may be made of octyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl.

In the formula (I), as an example of a branched C8-C16 alkyl radical, mention may be made of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, 3025094 and 4-methylpentyl. methylmethyl, 6-methylheptyl, 15-methylpentadecyl, 16-methylheptadecyl, 2-hexyloctyl. According to one particular form of the invention, in formula (I), R denotes a C 12 -C 16 alkyl radical.

According to one particular form of the invention, in formula (I), n ranges from 3 to 5. Tetraethoxylated lauryl acrylate will be used more particularly as monomer of formula (I). The monomer (3) of formula (I) is preferably present in the anionic terpolymer in molar proportions of between 0.1% and 10% by mole and more preferably between 0.5% and 5% by mole. According to a particular embodiment of the invention, the anionic terpolymer is crosslinked and / or connected by a diethylenic or polyethylenic compound in the proportion expressed relative to the total amount of monomers used, from 0.005% to 1% molar and from preferably from 0.01% to 0.5% molar and more particularly from 0.01% to 0.25% molar. The crosslinking agent and / or the branching agent is preferably chosen from ethylene glycol dimethacrylate, diallyloxoacetic acid or a salt thereof, such as sodium diallyloxyacetate, tetraallyloxyethane or ethylene glycol diacrylate. diallyl urea, triallyl amine, trimethylol propanetriacrylate, methylenebis (acrylamide) or mixtures thereof. The anionic terpolymer may contain additives such as complexing agents, transfer agents, chain-limiting agents. Anionic terpolymer of 2-methyl-2 - [(1-oxo-2-propenyl] amino] -1-propanesulfonic acid partially or totally salified in the form of the ammonium salt, N, N-dimethylacrylamide and of lauryl acrylate tetraethoxylated and crosslinked with trimethylol propanetriacrylate, INCI Polyacrylate Crosspolymer-6 name such as the product sold under the trade name Sepimax Zen® by the company Seppic.

Cationic Associative Polymers As cationic associative polymers, mention may be made of polyacrylates with amine side groups. The polyacrylates with amino side groups, quaternized or otherwise, have, for example, hydrophobic groups of the steareth type (polyoxyethylenated stearyl alcohol (20)). Examples of aminated side chain polyacrylates include polymers 8781-121B or 9492-103 from National Starch.

Nonionic Associative Polymers The nonionic associative polymers may be chosen from: copolymers of vinylpyrrolidone and hydrophobic fatty-chain monomers; copolymers of methacrylates or of C1-C6 alkyl acrylates and of 15 amphiphilic monomers comprising at least one fatty chain; copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, such as, for example, polyethylene glycol methacrylate / lauryl methacrylate copolymer; associative polyurethanes.

The associative polyurethanes are nonionic block copolymers comprising, in the chain, both hydrophilic sequences of a most often polyoxyethylenated nature (the polyurethanes may then be called polyurethane polyethers) and hydrophobic sequences which may be aliphatic sequences alone and / or cycloaliphatic and / or aromatic chains.

In particular, these polymers comprise at least two hydrocarbon-based lipophilic chains having from C6 to C30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains may be pendant chains or chains at the end of the hydrophilic sequence. In particular, it is possible that one or more pendant chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one or both ends of a hydrophilic block. The associative polyurethanes can be sequenced in the form of triblock or multiblock. The hydrophobic sequences can therefore be at each end of the chain 3025094 33 (for example: hydrophilic central block triblock copolymer) or distributed both at the ends and in the chain (multiblock copolymer for example). These polymers may also be graft or star. Preferably, the associative polyurethanes are triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups. In general, the associative polyurethanes comprise a urethane bond between the hydrophilic sequences, hence the origin of the name. According to a preferred embodiment, a nonionic associative polymer of the polyurethane type is used as a gelling agent.

By way of examples of nonionic polyurethane polyurethanes with a fatty chain which can be used in the invention, it is also possible to use Rheolate® FX 1100 (Steareth100 / PEG 136 / HDI (hexamethyl diisocyanate) copolymer), Rheolate® 205 to function as urea sold by Elementis or Rheolates® 208, 204 or 212, and Acrysol® RM 184 or Acrysol® RM 2020.

Mention may also be made of the C12-C14 alkyl chain product Elfacos® T210 and the C16-18 alkyl chain product Elfacos® T212 (PPG-14 Palmeth-60 Hexyl Dicarbamate) from Akzo. The DW 1206B® product from Rohm & Haas with a C20 alkyl chain and a urethane linkage, proposed at 20% solids content in water, can also be used.

It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of example of such polymers, mention may be made of Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by Elementis. It is also possible to use the product DW 1206F and DW 1206J proposed by Rohm & Haas.

The associative polyurethanes which can be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen, Colloid Polym. Sci., 271, 380-389 (1993). Even more particularly, according to the invention, it is also possible to use an associative polyurethane that can be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide. (ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate.

Such polyether polyurethanes are sold in particular by Rohm & Haas under the names Aculyn® 46 and Aculyn® 44. Aculyn 46® is a polyethylene glycol polycondensate containing 150 or 180 moles of oxide. ethylene, stearyl alcohol and methylene bis (4-cyclohexyl isocyanate) (SMDI), 15% by weight in a matrix of maltodextrin (4%) and water (81%), and Aculyn® 44 is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylene bis (4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and of water (26%). It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of example of such polymers, mention may be made of SER AD FX1010, SER AD FX1035 and SER AD 1070 from Elementis, Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by Elementis. . It is also possible to use Aculyn® 44, Aculyn® 46, DW 1206F and DW 1206J products, as well as Acrysol® RM 184 from Rohm & Haas, or even Borchi Gel LW 44 from Borchers, and their mixtures. Amphoteric Associative Polymers Among the associative amphoteric polymers of the invention, mention may be made of amphoteric, crosslinked or non-crosslinked, branched or non-branched polymers, obtainable by the copolymerization of: 1) at least one monomer of formula Or (IVb): embedded image wherein R5, which may be identical or different, represent a hydrogen atom or a methyl radical, R6, R7 and R8, which may be identical or different, represents a linear or branched alkyl radical having from 1 to 30 carbon atoms; Z represents an NH group or an oxygen atom; (IVa) (IVb) 3025094 n is an integer from 2 to 5; A- is an anion derived from an organic or inorganic acid, such as a methosulphate anion or a halide such as chloride or bromide; 2) at least one monomer of formula (V): R - C CRio-CO-Z1 (V) 9 in which R9 and R10, which may be identical or different, represent a hydrogen atom or a methyl radical; Z1 represents an OH group or an NHC (CH3) 2CH2SO3H group; 3) of at least one monomer of formula (VI): wherein R 9 and R 10, which may be identical or different, represent a hydrogen atom or a methyl radical; X denotes a hydrogen atom; oxygen or nitrogen and R11 denotes a linear or branched alkyl radical having from 1 to 30 carbon atoms; 4) optionally at least one crosslinking agent or branching agent; at least one of the monomers of formula (IVa), (IVb) or (VI) comprising at least one fatty chain having from 8 to 30 carbon atoms and said compounds of the monomers of formula (IVa), (IVb), (V) and (VI) may be quaternized for example by a C1-C4 alkyl halide or a C1-C4 dialkyl sulphate. The monomers of formula (IVa) and (IVb) of the present invention are preferably selected from the group consisting of: - dimethylaminoethylmethacrylate, dimethylaminoethylacrylate, diethylaminoethylmethacrylate, diethylaminoethylacrylate, dimethylaminopropylmethacrylate, dimethylaminopropylacrylate, dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, optionally quaternized for example with a C1-C4 alkyl halide or a C1-C4 dialkyl sulphate. More particularly, the monomer of formula (IVa) is chosen from acrylamidopropyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.

The compounds of formula (V) of the present invention are preferably selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, 2-methylcrotonic acid, 2-acrylamido-2-methylpropanesulphonic acid and 2-methacrylamido-2-methylpropanesulphonic acid. More particularly, the monomer of formula (V) is acrylic acid. The monomers of formula (VI) of the present invention are preferably selected from the group consisting of C12-C22 and more particularly C16-C18 alkyl acrylates or methacrylates. The crosslinking or branching agent is preferably chosen from N, N'-methylenebisacrylamide, triallylmethylammonium chloride, allyl methacrylate, n-methylolacrylamide, polyethylene glycol dimethacrylate, and the like. ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate and allyl sucrose. The polymers according to the invention may also contain other monomers such as nonionic monomers and in particular such as C1-C4 alkyl acrylates or methacrylates.

The ratio of the number of cationic charges / anionic charges in these amphoteric polymers is preferably equal to about 1. The weight average molecular weights of the associative amphoteric polymers have a weight average molecular weight of greater than 500, preferably of between 10,000. and 10,000,000, and even more preferably between 100,000 and 800,000. Preferably, the associative amphoteric polymers of the invention contain from 1% to 99% of moles, more preferably from 20% to 95% of moles and even more preferably from 25% to 10% by weight. % to 75% of moles of compound (s) of formula (IVa) or (IVb). They also preferably contain from 1% to 80% by moles, more preferably from 5% to 80% by moles and even more preferably from 25% to 75% by moles of compound (s) of formula (V). The content of compound (s) of formula (VI) is preferably between 0.1% and 70% by moles, more preferably between 1% to 50% by moles and even more preferably between 1% and 10% by moles. The crosslinking or branching agent when present is preferably between 0.0001% and 1% moles and more preferably between 0.0001% and 0.1% moles.

Preferably, the molar ratio between the compound (s) of formula (IVa) or (IVb) and the compound (s) of formula (V) varies from 20:80 to 95: 5, and more preferably from 25:75 to 75:25. The amphoteric associative polymers according to the invention are for example described in the patent application WO 98/44012. The amphoteric polymers that are particularly preferred according to the invention are chosen from acrylic acid / acrylamidopropyltrimethylammonium chloride / stearyl methacrylate copolymers. According to a preferred embodiment, the associative polymer is chosen from nonionic associative polymers and more particularly from associative polyurethanes, such as Steareth-100 / PEG-136 / HDI Copolymer sold under the name Rheolate FX 1100 by Elementis. Such an associative polymer is advantageously used in a proportion of 0.1% to 8% by weight of dry matter and preferably between 0.5% and 4% by weight relative to the total weight of the aqueous phase. Polyacrylamides and cross-linked and / or neutralized 2-methylpropanesulfonic acid polymers and copolymers The polymers used which are suitable as aqueous gelling agents for the invention may be homopolymers or copolymers, crosslinked or non-crosslinked, comprising at least the acrylamido-2-methylpropanesulphonic acid monomer (AMPS®), in form partially or totally neutralized with a mineral base other than ammonia such as sodium hydroxide or potassium hydroxide. They are preferably neutralized completely or substantially completely neutralized, that is to say neutralized to at least 90%. These AMPS® polymers according to the invention may be crosslinked or non-crosslinked. When the polymers are crosslinked, the crosslinking agents may be chosen from the olefinic polyunsaturated compounds commonly used for the crosslinking of polymers obtained by radical polymerization. Examples of crosslinking agents that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, di (meth) acrylate and the like. ethylene glycol or tetraethylene glycol, trimethylol propane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetra-allyloxyethane, trimethylolpropane diallylether allyl (meth) acrylate, allyl ethers of alcohols of the series of sugars, or other allyl- or vinyl-ethers of polyfunctional alcohols, and allylic esters of phosphoric acid derivatives and or vinylphosphonic, or mixtures of these compounds. According to a preferred embodiment of the invention, the crosslinking agent is chosen from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA). The degree of crosslinking generally ranges from 0.01% to 10% by moles and more particularly from 0.2% to 2% by moles relative to the polymer. The AMPS® polymers that are suitable for the invention are water-soluble or water-dispersible. They are in this case: either "homopolymers" containing only AMPS monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above; or copolymers obtained from AMPS® and one or more hydrophilic or hydrophobic ethylenically unsaturated monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above. When said copolymers comprise hydrophobic ethylenically unsaturated monomers, the latter do not comprise a fatty chain and are preferably present in small amounts. For the purposes of the present invention, the term "fatty chain" means any hydrocarbon chain comprising at least 7 carbon atoms.

By "water-soluble or water-dispersible" is meant polymers which, introduced in an aqueous phase at 25 ° C., at a mass concentration equal to 1%, make it possible to obtain a macroscopically homogeneous and transparent solution. ie having a maximum light transmittance value at a wavelength of 500 nm, through a 1 cm thick sample, at least 60%, preferably at least 70%.

The "homopolymers" according to the invention are preferably crosslinked and neutralized, and they can be obtained according to the preparation process comprising the following steps: (a) the monomer, such as AMPS in free form, is dispersed or dissolved In a solution of t-butanol or water and tert-butanol; (b) the solution or dispersion of monomer obtained in (a) is neutralized with one or more inorganic or organic bases, preferably ammonia NI-13, in an amount which makes it possible to obtain a degree of neutralization of the sulphonic acid functional groups polymer ranging from 90% to 100%; (C) is added to the solution or dispersion obtained in (b), the crosslinking monomer (s) (d) is carried out a conventional radical polymerization in the presence of free radical initiators at a temperature ranging from 10 ° C to 150 ° C ° C; the precipitating polymer in the tert-butanol solution or dispersion.

The water-soluble or water-dispersible copolymers of AMPS® according to the invention contain water-soluble ethylenically unsaturated monomers, hydrophobic monomers or mixtures thereof. The water-soluble comonomers may be ionic or nonionic. Among the ionic water-soluble comonomers, there may be mentioned for example the following compounds and their salts: - (meth) acrylic acid, - styrene sulphonic acid, - vinylsulfonic acid and (meth) allylsulphonic acid vinyl phophonic acid, maleic acid, itaconic acid, crotonic acid, the water-soluble vinyl monomers of formula (A) below: 11, C = R 'CO) 1 (30) in which: 3025094 - Ri is chosen from H, -CH3, -C2H5 or -C3H7; - Xi is chosen from: - alkyl oxides of -0R2 type where R2 is a hydrocarbon radical, linear or branched, saturated or unsaturated , having from 1 to 6 carbon atoms, substituted with at least one sulphonic group (-SO3-) and / or sulphate (-SO4-) and / or phosphate (-PO4H2-). Examples which may be mentioned are: (meth) acrylamide, N-vinylacetamide and N-methyl-N-vinylacetamide, N-vinylformamide and N-methyl-N-vinylformamide; maleic anhydride, vinylamine, N-vinyllactams containing a cyclic alkyl group having from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam, alcohol vinylic compound of formula CH 2 = CHOH, - the water-soluble vinyl monomers of formula (B) below: H 2 C = c R 3 co x 2 in which: R 3 is chosen from H, -CH 3, -C 2 H 5 or -C 3 H 7; X2 is chosen from alkyl oxides of the -OR4 type in which R4 is a linear or branched, saturated or unsaturated hydrocarbon radical containing from 1 to 6 carbons, optionally substituted by a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxy group (-OH); ether. Examples include glycidyl (meth) acrylate, hydroxyethyl methacrylate, and ethylene glycol, diethylene glycol or polyalkylene glycol (meth) acrylates. Among the hydrophobic comonomers without fatty chain, there may be mentioned for example: styrene and its derivatives such as 4-butylstyrene, alpha-methylstyrene and vinyltoluene; vinyl acetate of formula CH2 = CH-OCOCH3; Vinyl ethers of formula CH2 = CHOR wherein R is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 6 carbons; (B) 3025094 41 - acrylonitrile; caprolactone; vinyl chloride and vinylidene chloride; - Silicone derivatives, leading after polymerization to silicone polymers such as methacryloxypropyltris (trimethylsiloxy) silane and silicone methacrylamides; the hydrophobic vinyl monomers of formula (C) below: H 2 C = CR 4 CO in which: R 4 is chosen from H, -CH 3, -C 2 H 5 or -C 3 I-17; - X3 is chosen from: - alkyl oxides of -0R5 type where R5 is a hydrocarbon radical, linear or branched, saturated or unsaturated, having 1 to 6 carbon atoms. For example, methyl methacrylate, ethyl methacrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl acrylate and isobornyl acrylate, and 2-hexyl ethyl acrylate. The water-soluble or water-dispersible AMPS® polymers of the invention preferably have a molar mass ranging from 50,000 g / mol to 10,000,000 g / mol, preferably from 80,000 g / mol to 8,000,000 g / mol, and even more preferably from 100,000 to 7,000,000 g / mole. As water-soluble or water-dispersible homopolymers of AMPS that are suitable for the invention, mention may be made, for example, of cross-linked or non-crosslinked polymers of sodium acrylamido-2-methylpropane sulphonate such as that used in the commercial product Simulgel 800 (CTFA name: Sodium Polyacryloyldimethyl Taurate), crosslinked polymers of ammonium acrylamido-2-methyl propane sulfonate (INCI name: Ammonium polyacryldimethyltauramide) as those described in EP 0 815 928 B1 and such as the product sold under the trade name Hostacerin AMPS ® by the company Clariant. As hydrosoluble or water-dispersible homopolymers of preferred AMPS according to the invention, mention may be made of crosslinked polymers of ammonium acrylamido-2-methyl propane sulphonate. (C) 3025094 As water-soluble or water-dispersible copolymers of AMPS in accordance with the invention, mention may be made, for example, of: crosslinked acrylamide / sodium acrylamido-2-methyl propane sulfonate copolymers such as that used in the commercial product SEPIGEL 305 (CTFA name: polyacrylamide / C13-C14 Isoparaffin / Laureth-7) or that used in the commercial product sold under the name Simulgel 600 (CTFA name: Acrylamide / Sodium acryloyldimethyltaurate / Isohexadecane / Polysorbate-80) by the company Seppic; copolymers of AMPS® and of vinylpyrrolidone or of vinylformamide, such as that used in the commercial product sold under the name Aristoflex AVC® by the company Clariant (CTFA name: Ammonium Acryloyldimethyltaurate / VP Copolymer) but neutralized with sodium hydroxide or potash; copolymers of AMPS® and of sodium acrylate, for example the AMPS / sodium acrylate copolymer such as that used in the commercial product sold under the name Simulgel EG® by Seppic or under the trade name Sepinov EM (CTFA name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer); copolymers of AMPS® and of hydroxyethyl acrylate, for example the AMPSe / hydroxyethyl acrylate copolymer, such as that used in the commercial product sold under the name Simulgel NS® by the company Seppic (CTFA name: 20 Hydroxyethyl Acrylate / Sodium Acryloyldimethyltaurate copolymer (And) Squalane (And) Polysorbate 60) or as the product marketed under the name Copolymer Acrylamido-2-methylpropane Sodium sulfonate / Hydroxyethylacrylate as the commercial product Sepinov EMT 10 (INCI name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyl taurate copolymer ).

As water-soluble or water-dispersible copolymers of preferred AMPS according to the invention, there may be mentioned copolymers of AMPS® and hydroxyethyl acrylate. In general, an aqueous phase according to the invention may comprise from 0.1% to 12% by weight of dry matter, preferably from 0.3% to 10% by weight and more preferably from 0.5% to 8% by weight of polyacrylamide (s) and / or polymer (s) and copolymer (s) of 2-acrylamido-2-methylpropanesulphonic acid, crosslinked and / or neutralized relative to its total weight .

Modified or Unmodified Carboxyvinyl Polymers The modified or unmodified carboxyvinyl polymers may be copolymers resulting from the polymerization of at least one monomer (a) chosen from α, β-ethylenically unsaturated carboxylic acids or their esters. with at least one ethylenically unsaturated monomer (b) having a hydrophobic group. By "copolymers" is meant both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers such as terpolymers obtained from three kinds of monomers.

Their chemical structure more particularly comprises at least one hydrophilic unit and at least one hydrophobic unit. Hydrophobic group or unit means a hydrocarbon radical, saturated or unsaturated, linear or branched, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms, and more preferably from 18 to 30 carbon atoms. Preferably, these copolymers are chosen from copolymers resulting from the polymerization of: at least one monomer of formula (1) below: ## STR1 ## in which R1 denotes H or CH3; or C2H5, i.e., acrylic acid, methacrylic acid or ethacrylic acid monomers, and - at least one unsaturated carboxylic acid (C 10 -C 30) alkyl ester monomer corresponding to the monomer of formula (2) wherein R 2 is H or CH 3 or C 2 H 5 (ie acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH 3 (units methacrylates), R3 denoting a C1-C30 alkyl radical, and preferably a C1-C22 alkyl radical. The (C 10 -C 30) alkyl esters of unsaturated carboxylic acids are preferably chosen from lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, acrylate and the like. dodecyl, and the corresponding methacrylates, such as (2) lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate, and mixtures thereof. According to a preferred embodiment, these polymers are crosslinked. Among this type of copolymer, more particularly polymers derived from the polymerization of a monomer mixture comprising: - essentially acrylic acid; - an ester of formula (2) described above and in which R2 designates H or CH 3, R 3 denoting an alkyl radical having from 12 to 22 carbon atoms, and a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide. Among this type of copolymer, use will more particularly be made of 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0% to 6% by weight of crosslinking polymerizable monomer, or those consisting of 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of alkyl acrylate, C10-C3o (hydrophobic unit), and 0.1% to 0.6% by weight of crosslinking polymerizable monomer such as those described above. Among the above polymers, acrylate / Cio-C30-alkylacrylate copolymers (INCI name: Acrylates / C10-30 Alkyl acrylate crosspolymer), such as the products sold by Lubrizol under the US Pat. trade names Pemulen TR-1, Pemulen TR-2, Carbopol 1382, Carbopol EDT 2020, Carbopol Ultrez Polymer and even more preferably Pemulen TR-2.

Among the modified or unmodified carboxyvinyl polymers, mention may also be made of sodium polyacrylates such as those sold under the name Cosmedia SP® containing 90% of dry matter and 10% of water, or Cosmedia SPL® in inverse emulsion containing about 60 % of dry matter, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by Cognis.

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

The modified or unmodified carboxyvinyl polymers may also be chosen from crosslinked (meth) acrylic acid homopolymers. By "(meth) acrylic" within the meaning of the present application, the term "acrylic or methacrylic".

By way of example, mention may be made of those sold by Lubrizol under the trade names Carbopol, 910, 934, 940, 941, 934, 980, 981, 2984, 5984, Carbopol Ultrez Polymer, or by 3V-Sigma under the names Carbopol. Synthalen® K, Synthalen® L, or Synthalen® M. Among the carboxyvinyl polymers that may or may not be modified, mention may in particular be made of Carbopol (CTFA name: carbomer) and Pemulen (CTFA name: Acrylates / Cio-3o alkyl acrylate). crosspolymer) marketed by Lubrizol. The carboxyvinyl polymers, modified or not, may be present in a proportion of 0.1% to 10% by weight of dry matter relative to the weight of the aqueous phase, in particular of 0.3% to 8% by weight, preferably 0.4 to 6% based on the weight of the aqueous phase. Advantageously, a composition according to the invention comprises at least one synthetic polymeric gelling agent, preferably a synthetic polymeric hydrophilic gelling agent chosen from cross-linked and / or neutralized 2-acrylamido-2-methylpropanesulphonic acid polymers and copolymers and carboxyvinyl polymers. modified or not. According to a preferred variant, the synthetic polymeric hydrophilic gelling agent is chosen from the cross-linked polymers of ammonium acrylamido-2-methyl propane sulfonate, the copolymers of AMPS® and of hydroxyethyl acrylate, and the acrylate / Cio-C30-copolymers. alkylacrylate and crosslinked (meth) acrylic acid homopolymers. Preferably, the synthetic polymeric hydrophilic gelling agent is chosen from copolymers of AMPS® and of hydroxyethyl acrylate.

III. Other hydrophilic gelling agents These gelling agents are more particularly chosen from mixed silicates and pyrogenic silicas.

3025094 46 MA. Mixed Silicate For the purposes of the present invention, mixed silicate is understood to mean all silicates of natural or synthetic origin containing several (two or more) types of cation chosen from alkali metals (for example Na, Li, K) or alkaline metals. -terrous (eg Be, Mg, Ca), transition metals and aluminum. According to a particular embodiment, the mixed silicate or silicates are in the form of solid particles containing at least 10% by weight of at least one silicate relative to the total weight of the particles. In the remainder of the present disclosure, these particles are referred to as "silicate particles". Preferably, the silicate particles contain less than 1% by weight of aluminum relative to the total weight of the particles. Even more preferably, they contain from 0% to 1% by weight of aluminum relative to the total weight of the particles.

Preferably, the silicate particles contain at least 50% by weight of silicate, more preferably at least 70% by weight based on the total weight of the particles. Particles containing at least 90% by weight of silicates, based on the total weight of the particles, are particularly preferred. In particular, it is a silicate or a mixture of alkali or alkaline earth metal silicates, aluminum or iron. Preferably, it is sodium silicate, magnesium and / or litium. To guarantee good cosmetic properties, these silicates are generally in a finely divided form, and in particular in the form of particles having an average size ranging from 2 nm to 1 μm (from 2 nm to 1000 nm), and preferably from 5 nm to 600 nm, and even more preferably 20 to 250 nm. The silicate particles may have any shape, for example the shape of spheres, flakes, needles, platelets, disks, sheets, or totally random forms. Preferably, the silicate particles are in the form of disks or sheets.

Also, the term "average size" of the particles means the average number size of the largest dimension (length) that can be measured between two diametrically opposed points of an individual particle. The size can be determined, for example, by transmission electron microscopy, or from the measurement of the specific surface area by the BET method, or else by means of a laser granulometer. When the particles are in the form of discs or sheets, they generally have a thickness of from about 0.5 nm to 5 nm. The silicate particles may consist of an alloy with oxides of metals or metalloids, obtained for example by thermal melting of its various constituents. When the particles further comprise such a metal or metalloid oxide, it is preferably selected from silicon, boron or aluminum oxide. According to one particular embodiment of the invention, the silicates are phyllosilicates, namely silicates having a structure in which the SiO4 tetrahedra are organized into sheets between which the metal cations are enclosed.

The mixed silicates suitable for the invention may be chosen for example from montmorillonites, hectorites, bentonites, beidellite, saponites. According to a preferred embodiment of the invention, the mixed silicates used are more particularly chosen from hectorites and bentonites, and even better from laponites.

A particularly preferred family of silicates in the compositions of the present invention is therefore the laponites. Laponites are silicates of magnesium, sodium and possibly lithium, having a layered structure similar to that of montmorillonites. Lapponite is the synthetic form of the natural mineral called "hectorite". The synthetic origin of this family of silicates presents a considerable advantage over the natural form because it allows a good control of the composition of the product. In addition, laponites have the advantage of having a much smaller particle size than natural hectorite and bentonite. As laponites, there may be mentioned in particular the products sold under the following names: Laponite® XLS, Laponite® XLG, Laponite® RD, Laponite® 30 RDS, LAPONITE® XL21 (these products are sodium and magnesium silicates and silicates of sodium, lithium and magnesium) by Rockwood Additives Limited.

Such gelling agents may be used in a proportion of 0.1% to 8% by weight of dry matter relative to the total weight of the aqueous phase, in particular from 0.1% to 5% by weight, and in particular from 0.5% to 3% by weight relative to the total weight of the aqueous phase.

5 MB. Hydrophilic pyrogenic silica The pyrogenic silicas according to the present invention are hydrophilic. The pyrogenic hydrophilic silicas are obtained by pyrolysis in continuous flame at 1000 ° C. of silicon tetrachloride (SiC14) in the presence of hydrogen and oxygen. Among the hydrophilic silicas of hydrophilic nature that can be used according to the present invention, mention may be made in particular of those sold by Degussa or Evonik Degussa under the trade names AEROSIL® 90, 130, 150, 200, 300 and 380, or by CABOT. under the name Carbosil H5. Such gelling agents may be used in amounts of 0.1% to 10% by weight relative to the total weight of the aqueous phase, in particular from 0.1% to 5% by weight, and in particular from 0.1% to 5% by weight. 0.5% to 3% by weight relative to the total weight of the aqueous phase. In a particular embodiment, the composition according to the present invention may further comprise at least one additional hydrophilic gelling agent chosen from amylaceous polysaccharides. The starchy additional gelling agent is water-soluble or water-dispersible. Representative of this category may be especially mentioned, native starches and modified starches. Native starches The starches which can be used in the present invention are more particularly macromolecules in the form of polymers consisting of elementary units which are anhydroglucose (dextrose) units, linked by α (1,4) bonds, of chemical formula (C6E11005). The number of these motifs and their assembly make it possible to distinguish amylose, a molecule formed from about 600 to 1000 molecules of linearly chain-linked glucose, and amylopectin, a branched polymer around every 25 glucose residues (a (1, The total chain can make between 10,000 and 100,000 glucose residues Starch is described in particular in "KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 3rd edition, volume 21, pages 492-507, Wiley Interscience, 1983". The relative proportions of amylose and amylopectin, as well as their degree of polymerization, vary according to the botanical origin of the starches.On average, a sample of native starch is approximately 25% amylose and 75% amylopectin.

Sometimes, there is presence of phytoglycogen (between 0% and 20% starch), an analogue of amylopectin but branched every 10 to 15 glucose residues. The starch can be in the form of semi-crystalline granules: amylopectin is organized in sheets, amylose forms a less well-organized amorphous zone between the different layers.

The amylose is organized into a right helix with six glucoses per turn. It dissociates into assimilable glucose under the action of enzymes, amylases, more easily if it is in the form of amylopectin. Indeed, helical formation does not promote the accessibility of starch to enzymes. The starches are generally in the form of a white powder insoluble in cold water, the size of the elementary particles is from 3 to 100 microns. By treating it with hot water, we obtain the poisoning. It is used in the industry for its thickener and gelling properties. The starch molecules used in the present invention may be of botanical origin cereals or tubers. Thus, the starches are for example chosen from starches of maize, rice, cassava, tapioca, barley, potato, wheat, sorghum, pea. The native starches are represented for example by the products sold under the names C * AmilogelTM, Cargill Ge1TM, C * Ge1TM, Cargill GumTM, DryGe1TM, C * Pharm Ge1TM by the company Cargill under the name Amidon de mais by the company Roquette and under the name Tapioca Pure by the company National Starch.

Modified starches The modified starches used in the composition of the invention may be modified by one or more of the following reactions: pre-gelatinization, degradation (acid hydrolysis, oxidation, dextrinization), substitution (esterification, etherification), crosslinking (esterification ), bleaching. More particularly, these reactions can be carried out as follows: pre-gelatinization by bursting the starch granules (eg drying and cooking in a drying drum); - acid hydrolysis resulting in a very rapid retrogressive cooling; oxidation by strong oxidants (alkaline medium, in the presence of sodium hypochlorite NaOCl for example) leading to depolymerization of the starch molecule and to the introduction of carboxyl groups into the starch molecule (mainly oxidation of the C6 hydroxyl group); dextrinisation in an acid medium at high temperature (hydrolysis then repolymerization); crosslinking by functional agents capable of reacting with the hydroxyl groups of the starch molecules which will thus be bonded together (for example with glyceryl and / or phosphate groups); alkaline esterification for the grafting of functional groups, especially C1-C6 acyl (acetyl), hydroxyalkyl C1-C6 (hydroxyethyl, hydroxypropyl), carboxymethyl, octenylsuccinic.

In particular, it is possible to obtain, by means of crosslinking with phosphorus compounds, mono-starch phosphates (of the Am-O-PO- (OX) 2 type), diamidon phosphates (of the Am-O-PO- (OX) -O- type). Am) or even triamidon (of the type Am-O-PO- (O-Am) 2) or mixtures thereof. X denotes, in particular, alkali metals (for example sodium or potassium), alkaline earth metals (for example calcium, magnesium), ammonia salts, amine salts such as those of monoethanolamine, diethanolamine, triethanolamine, and the like. , 3-aminopropanedio1-1,2, ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine, citrulline. The phosphorus compounds may be, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate. According to the invention, it is also possible to use amphoteric starches, these amphoteric starches contain one or more anionic groups and one or more cationic groups. The anionic and cationic groups may be bonded to the same reactive site of the starch molecule or to different reactive sites, preferably they are bonded to the same reactive site. The anionic groups may be of carboxylic, phosphate or sulfate type and preferably carboxylic. The cationic groups may be of primary, secondary, tertiary or quaternary amine type. The amphoteric starches are chosen in particular from compounds of the following formulas: ## STR2 ## CH-CH-COOM St-O- (CH 2) FNN CH-CH-COOM IIR 'R (I) COOM R 1 I CH -CH-COOM St Embedded image in which: - St-O represents a molecule of -O - (CH 2) FNR "R 'R" St-O - -COOM R' R "St-O - CH-CI-ICOOM (IV) starch; R, identical or different, represents a hydrogen atom or a methyl radical; R ', which is identical or different, represents a hydrogen atom, a methyl radical or a -COOH group; n is an integer; equal to 2 or 3; M, identical or different, denotes a hydrogen atom, an alkali metal or alkaline earth metal such as Na, K, Li, NH 4, a quaternary ammonium or an organic amine; R "represents an atom hydrogen or an alkyl radical having 1 to 18 carbon atoms. These compounds are described in US Pat. Nos. 5,455,340 and 4,017,460. The starch molecules can be derived from all plant sources of starch such as, in particular, corn, potato, oats, rice, tapioca, sorghum, barley or wheat. It is also possible to use the hydrolysates of the starches mentioned above.

The modified starches are represented for example by the products sold under the names C * Tex-Instant (pre-gelatinized adipate), C * StabiTex-Instant (pre-gelatinized phosphate), C * PolarTex-Instant (pre-gelatinized hydroxypropyl) , C * Set (acid hydrolysis, oxidation), C * size (oxidation), C * BatterCrisp (oxidation), C * DrySet (dextrinization), C * TexTM (acetylated diamidon adipate), C * PolarTexTM (diamidon phosphate) hydroxypropyl), C * StabiTexTM (diamidon phosphate, acetylated diamidon phosphate) by the company Cargill, diamidon phosphates or compounds rich in diamidon phosphate, such as the product proposed under the references PREJEL VA-70-T AGGL (phosphate of hydroxypropylated manioc gelatinized diamidon) or PREJEL TK1 (gelatinized cassioformed diamidon phosphate) or PREJEL 200 (gelatinized manioc acetyl diamidon phosphate) by the company AVEBE or STRUCTURE ZEA of NATIONAL STARCH (cornstarch phosphate gelatin) nized).

By way of examples of oxidized starches, use will be made especially of those sold under the name C * size of the company Cargill. The native or modified starches described above may advantageously be used in a proportion of 0.1% to 8% by weight of dry matter, and preferably of approximately 1% by weight, relative to the total weight of the product. aqueous phase. Particulate starches As particulate starches, mention may be made in particular of: starches grafted with an acrylic polymer (homopolymer or copolymer) and in particular with sodium polyacrylate, for example those sold under the name Sanfresh ST-100 ™ by Sanyo Chemical Industries or Makimousse 25, Makimousse 12 by the company Daito Kasei (INCI name Sodium Polyacrylate Starch); Hydrolysed starches grafted with an acrylic polymer (homopolymer or copolymer) and especially acryloacrylamide / sodium acrylate copolymer, for instance those sold under the names Water Lock A-240, A-180, B204 and D-223, A -100, C-200, D-223, by Grain Processing (INCI name: Starch / acrylamide / sodium acrylate copolymer); Polymers based on starch, gum and cellulose derivative, such as that containing starch and sodium carboxymethylcellulose, such as for example that sold under the name Lysorb 220 by the company Lysac.

Particularly suitable are the (C 1 -C 4) carboxyalkyl starches, hereinafter referred to as "carboxyalkyl starch". These compounds are obtained by grafting carboxyalkyl groups on one or more alcohol functions of the starch, in particular by reaction of starch and sodium monochloroacetate in an alkaline medium.

The carboxyalkyl groups are generally attached via an ether function, more particularly to carbon 1. The degree of carboxyalkyl substitution of the (C 1 -C 4) carboxyalkyl of starch is preferably from 0.1 to 1, and 3025094 more particularly from 0.15 to 0.5. The degree of substitution is defined according to the present invention as the average number of hydroxyl groups substituted by an ester or ether group per monosaccharide unit of the polysaccharide. The carboxyalkyl starches are advantageously used in the form of salts and especially of alkali metal or alkaline earth metal salts such as Na, K, Li, NH 4, a quaternary ammonium or an organic amine such as mono, di or triethanolamine. The (C 1 -C 4) carboxyalkyl starches are advantageously in the context of the present invention carboxymethyl starches. The carboxymethyl starches preferably comprise units of the following formula: embedded image in which X, whether or not covalently bonded to the carboxylic unit, denotes a hydrogen atom, an alkali metal or alkaline earth metal, such as Na, K, Li, NH4, a quaternary ammonium or an organic amine such as for example such as mono, di or triethanolamine.

Preferably, X denotes an Na + cation. The carboxyalkyl starches which can be used according to the present invention are preferably the non-pregelatinized carboxyalkyl starches. The carboxyalkyl starches which can be used according to the present invention are preferably cross-linked carboxyalkyl starches, partially or totally. In general, a crosslinked carboxyalkyl starch has, in contrast to an uncrosslinked carboxyalkyl starch, an increased, controllable viscosity and increased stability. The crosslinking thus makes it possible to reduce the syneresis phenomena and to increase the resistance of the gel to shearing effects. The carboxyalkyl starches considered according to the invention are more particularly potato carboxyalkyl starches. Thus, the carboxyalkyl starches which can be used according to the present invention are preferably sodium salts of carboxyalkyl starch, in particular a sodium salt of potato carboxymethyl starch 3025094 sold in particular under the name PRIMOJEL by the company DMV International or GLYCOLYS® and GLYCOLYS® LV by the Roquette Company. According to a particular mode, use will be made of potato carboxymethyl starches sold in particular under the name GLYCOLYS® by the Roquette Company.

As previously stated, the starch-containing carboxyalkyl (C 1 -C 4) particles are present in the compositions according to the invention in an inflated and unexploded form. This swelling may be characterized by a swelling power Q which may advantageously be between 10 and 30 ml / g, preferably between 15 and 25 ml (volume of absorbed liquid) / g of dry particulate material.

Thus, the size of the swollen carboxyalkyl starch particles used according to the present invention generally ranges from 25 to 300 μm. For example, PRIMOJEL® gel containing 10% by weight of potato carboxyalkyl starch and sodium salt in water, contains more than 80% of swollen particles of this starch having a diameter greater than 50 microns, and more particularly greater than 50 microns. at 100 microns.

According to a preferred embodiment of the invention, these particles are used for the preparation of the compositions according to the invention, in this swollen particulate state. To do this, these particles are advantageously used in the form of an aqueous gel either prepared beforehand or already commercially available. The gels considered according to the invention are advantageously translucent. For example, a carboxymethyl starch gel such as PRIMOJEL® which is at a concentration of 10% by weight can be adjusted to the required concentration before being used to prepare the expected cosmetic composition. Such a particulate starch can be used in a proportion of 0.1% to 5% by weight of dry matter relative to the total weight of the aqueous phase, preferably between 0.5% and 2.5% by weight, and in particular about 1.5% by weight, based on the total weight of the aqueous phase.

For the purposes of the present invention, the term "lipophilic gelling agent" is intended to mean a compound capable of gelling the oily phase of the compositions according to the invention. The gelling agent is therefore lipophilic present in the oily phase of the composition. As is apparent from the following, the lipophilic gelling agent is chosen from hydrophobic silica aerogels. A. Hydrophobic Silica Aerogels Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air. They are generally synthesized 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 a specific surface 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 as mean diameter by volume (D [ 0.5]) ranging from 1 to 1500 μm, more preferably from 1 to 1000 μm, preferably from 1 to 100 μm, more preferably from 1 to 30 μm, more preferably from 5 to 25 μm, more preferably from 5 to 20 μm. lm 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. more preferably 5 to 20 iam and even more preferably 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 sizes of silica airgel particles can be measured by static light scattering using a commercial MasterSizer 2000 type granulometer 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 described in particular in Van de Hulst, HC, "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957. According to an advantageous embodiment, the airgel particles of hydrophobic silica used in the present invention have a specific surface per unit mass (SM) ranging from 600 to 800 m2 / 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 / 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 STF 2003 machine 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 better still 15 to 40 m2 / cm3.

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 airgel particles according to the invention have an oil absorption capacity measured at Wet Point ranging from 5 to 18 ml / g, preferably from 6 to 15 ml / g and more preferably from 6 to 15 ml / g. 8 to 12 ml / g.

The absorption capacity measured at Wet Point, and denoted by Wp, corresponds to the amount of oil that 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 of determining the setting of powder oil described in standard NF T 30-022. It corresponds to the quantity 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 and then the oil (isononyl isononanoate) is added dropwise. After adding 4-5 drops of oil to the powder, the mixture is mixed 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). "Hydrophobic silica" means any silica whose surface is treated with silylating agents, for example with 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 marketed under the name VM-2260 or VM-2270 (INCI name: Silica silylate), by the company Dow Corning, of which 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. Mention may also be made of aerogels marketed by Cabot under the references Aerogel TLD 201, Aerogel OGD 201, Aerogel TLD 203, ENOVA® 5 Aerogel MT 1100 and ENOVA Aerogel MT 1200. The airgel marketed under the name VM2270 will preferably be used. (INCI name Silica silylate), by Dow Corning, whose particles have an average size ranging from 5-15 microns and a specific surface per unit mass ranging from 600 to 800 m2 / g.

Such an airgel advantageously promotes the resistance of the deposit to sebum and sweat. Preferably, the particles of hydrophobic silica aerogels are present in the composition according to the invention in a dry matter content ranging from 0.1% to 30% by weight, preferably from 0.2% to 20% by weight. weight, preferably from 0.2% to 10% by weight relative to the total weight of the oily phase. B Additional lipophilic gelling agent (s) The composition according to the present invention may further comprise at least one additional lipophilic gelling agent.

The additional gelling agent is liposoluble or lipodispersible. The additional lipophilic gelling agent is advantageously chosen from additional particulate gelling agents that are different from hydrophobic silica aerogels, organopolysiloxane elastomers, semi-crystalline polymers, dextrin esters, hydrogen-bonded polymers, hydrocarbon block copolymers and mixtures thereof. Preferably, the additional lipophilic gelling agent is chosen from modified clays, organopolysiloxane elastomers and their mixtures. I. Additional Particle Gelling Agents The additional particulate gelling agent used in the composition according to the invention is in the form of particles, preferably spherical.

Representative of the additional lipophilic particulate gelling agents that are suitable for the invention may be especially cited waxes, polar and apolar, modified clays, silicas such as pyrogenic silicas.

Waxes The term "wax" as used in the context of the present invention generally means a lipophilic compound, solid at room temperature (25 ° C.), a reversible solid / liquid state change, having a melting point. greater than or equal to 30 ° C up to 200 ° C and especially up to 120 ° C.

Within the meaning of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in the ISO 11357-3 standard; 1999. The melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name "MDSC 2920" by the company TA Instruments.

The measurement protocol is as follows: A sample of 5 mg of wax placed in a crucible is subjected to a first temperature rise 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 / minute and finally subjected to a second temperature rise from -20 ° C to 100 ° C at a heating rate of 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 apex of the peak of the curve representing the variation of the difference in power absorbed as a function of temperature. The waxes that may be used in the compositions according to the invention are chosen from waxes, solid, at room temperature of animal, vegetable, mineral or synthetic origin, and mixtures thereof. For the purposes of the invention, the waxes may be those used generally in the cosmetic or dermatological fields. They may in particular be polar or apolar, silicone and / or fluorinated hydrocarbon compounds, optionally comprising ester or hydroxyl functions. They can also be of natural or synthetic origin. a) Apolar waxes For the purposes of the present invention, the term "apolar wax" is intended to mean a wax whose solubility parameter at 25 ° C. as defined below, δa is equal to 0 (J / cm 3). 4. The definition and calculation of the solubility parameters in Hansen's three-dimensional solubility space are described in the article by C. M. Hansen: "The three dimensionna) solubdiC parameters" J. Paint Technol. 39, 105 (1967).

According to this Hansen space: δp characterizes the London dispersion forces resulting from the formation of dipoles induced during molecular shocks; δp characterizes the Debye interaction forces between permanent dipoles as well as the Keesom interaction forces between induced dipoles and permanent dipoles; --H characterizes the specific interaction forces (hydrogen bond, acid / base, donor / acceptor type, etc.); - 15a is determined by the equation: δa = ((Sp2 8h2) 1/4 The parameters δp, δh, 15D and δa are expressed in (J / cm3) 1/4, apolar waxes are in particular waxes hydrocarbon compounds consisting solely of carbon and hydrogen atoms and free from heteroatoms such as N, O, Si and P. The apolar waxes are chosen from microcrystalline waxes, paraffin waxes, ozokerite, waxes, and the like. polyethylene, and mixtures thereof As ozokerite mention may be made of Ozokerite Wax SP 1020 P.

Microcrystalline waxes that may be used include Multiwax W 445® sold by Sonneborn, Microwax HW® and Base Wax 30540® sold by Paramelt, and Cerewax® No. 3 sold by Baerlocher. Suitable microwaxes which can be used in the compositions according to the invention as apolar wax include polyethylene microwaxes such as those sold under the names Micropoly 200®, 220®, 220L® and 2505® by the company. Micro Powders.

As polyethylene wax, there may be mentioned Performalene 500-L Polyethylene and Performalene 400 Polyethylene marketed by New Phase Technologies, Asensa ° SC 211 sold by Honeywell. B) Polar waxes For the purposes of the present invention, the term "polar wax" means a wax whose solubility parameter at 25 ° C. a is different from 0 (J / cm 3) 1/4. In particular, "polar wax" is understood to mean a wax whose chemical structure is formed essentially or even consisting of carbon atoms and of hydrogen, and comprising at least one highly electronegative heteroatom such as an atom of oxygen, nitrogen, silicon or phosphorus. The polar waxes may especially be hydrocarbon, fluorinated or silicone. Preferably, the polar waxes may be hydrocarbon-based.

By "hydrocarbon wax" is meant a wax formed essentially, or even constituted, of carbon and hydrogen atoms, and possibly of oxygen, nitrogen, and not containing a silicon atom or of fluorine. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups. By "ester wax" is meant according to the invention a wax comprising at least one ester function. 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 used especially as: - ester waxes such as those chosen from: i) waxes of formula RiCOOR 2 in which R 1 and R 2 represent linear, branched or cyclic aliphatic chains whose number of atoms varies from 10 to 50, which may contain a heteroatom such as O, N or P and whose melting point temperature varies from 25 to 120 ° C. ii) di- (1,1,1-trimethylolpropane) tetrastearate, sold under the name Hest 2T-4S by the company Heterene. iii) diester waxes of a dicarboxylic acid of general formula R3 - (- OCOR4-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 C4-C30 aliphatic group (linear or branched alkyl group comprising 4 to 30 carbon atoms) which may or may not contain one or more unsaturations, and preferably 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. V) beeswax, synthetic beeswax, polyglycerolated beeswax, carnauba wax, candelilla wax, oxypropylene lanolin wax, rice bran wax, wax Ouricury, Alfa wax, cork fiber wax, sugar cane wax, Japanese wax, sumac wax, montan wax, orange wax, laurel wax, wax of hydrogenated Jojoba, sunflower wax, lemon wax, olive wax, berry wax. According to another embodiment, the polar wax may be an alcohol wax. 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. As alcohol wax, mention may be made, for example, of the wax C30-50 Alcohols Performacol® 550 Alcohol 20 marketed by the company New Phase Technologie, stearyl alcohol, cetyl alcohol. It is also possible to use silicone waxes, which may advantageously be substituted polysiloxanes, preferably at a low melting point. By "silicone wax" is meant an oil comprising at least one silicon atom, and in particular comprising Si-O groups. Among the commercial silicone waxes of this type, mention may be made in particular of those sold under the names Abilwax 9800, 9801 or 9810 (Goldschmidt), KF910 and KF7002 (Shin Etsu), or 176-1118-3 and 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 the company GE-Bayer. Silicones or C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane 3025094 64 under the name SW-8005® C30 Resin Wax sold by the company Dow Corning. The waxes, within the meaning of the invention, may be those used generally in the cosmetic or dermatological fields. They may in particular be polar or apolar, silicone hydrocarbon-based and / or fluorinated, optionally comprising ester or hydroxyl functions. They can also be of natural or synthetic origin. In the context of the present invention, mention may be made, as particularly advantageous waxes, of polyethylene waxes, jojoba wax, carnauba wax, candelilla wax and silicone waxes, in particular candelilla wax. They may be present in the oily phase in a proportion of 0.5% to 30% by weight relative to the weight of the oily phase, for example between 5% and 20% of the oily phase, and more particularly from 2% to 15% by weight. % by weight relative to the weight of the oily phase.

The modified clays The composition according to the invention may comprise at least one lipophilic clay. The clays can be natural or synthetic and are rendered lipophilic by treatment with an alkylammonium salt such as a C 10 -C 22 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, vermiculites and zeolites.

Preferably they are selected from hectorites. Preferably, the lipophilic clays used are hectorites modified with a C 10 -C 22 ammonium chloride, such as hectorite modified with distearyl dimethyl ammonium chloride such as, for example, that sold under the name Bentone 38V® by Elementis or bentone gel in isododecane sold under the name Bentone Gel ISD V® (Isododecane 87% / Disteardimonium Hectorite 10% / Propylene carbonate 3%) by Elementis.

The lipophilic clay may in particular be present in a content ranging from 0.1% to 25% by weight, in particular from 0.5% to 20%, more particularly from 1% to 18% by weight relative to the total weight. oily phase.

Pyrogenic Silicas The oily phase of a composition according to the invention may also comprise, as gelling agent, fumed 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 obtained in particular 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 Degussa, CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by Cabot.

The fumed silicas may be present in a composition according to the present invention at 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, based on the total weight of the oily phase.

II. Organopolysiloxane Elastomer The organopolysiloxane elastomer, which can be used as a lipophilic gelling agent, has the advantage of giving the composition according to the invention good application properties. It provides a very soft and matifying after application, especially advantageous for application on the skin. 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 soft 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 a dehydrogenation-dehydrogenation condensation 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 ethylenically unsaturated groups bonded to a silicon. silicon, especially in the presence (C) of platinum catalyst, as for example described in 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 separate 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) may 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, dimethylsiloxane-methylhydrogensiloxane trimethylsiloxy endblock copolymers and cyclic dimethylsiloxane-methylhydrogensiloxane copolymers.

The compound (B) is advantageously a diorganopolysiloxane having at least two lower alkenyl groups (for example C 2 -C 4); the lower alkenyl group may be chosen 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 xyllyl; 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) may be selected from 5 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 dimethylsiloxanemethyl (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 the groups ethylenically unsaturated 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 acidketone 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 a particular embodiment of the invention, the composition comprises an organopolysiloxane elastomer devoid of polyoxyalkylene units and polyglyceryl units. In particular, the silicone elastomer used in the present invention is selected from Dimethicone Crosspolymer (INCI Name), Vinyl Dimethicone Crosspolymer (INCI Name), Dimethicone / Vinyl Dimethicone Crosspolymer (INCI Name), Dimethicone Crosspolymer-3 (INCI Name ). 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 especially described in EP 242 219, EP 285 886, EP 765 656 and in 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 the company Shin Etsu, "DC9040", "DC9041", by the company Dow Corning, "SFE 839" by the company 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, phenyltrimethicone, and cyclomethicone, is used. preferably a linear silicone oil chosen from polydimethylsiloxanes (PDMS) or dimethicones with a viscosity at 25 ° C. ranging from 1 to 500 cst at 25 ° C., optionally modified with aliphatic groups, optionally 3025094 fluorinated, or with functional groups such as than hydroxyl groups, thiols and / or amines. Mention may in particular be made of the following INCI name compounds: Dimethicone / Vinyl Dimethicone Crosspolymer, such as USG-105 and USG-107A from Shin Etsu; "DC9506" and "DC9701" from Dow Corning, - 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; Dimethicone (and) Dimethicone Crosspolymer, such as Dow Corning EL-9240 Silicone Elastomer Blend from Dow Corning (a mixture of polydimethylsiloxane cross-linked with hexadiene / polydimethyl siloxane (2 cSt)); - C4-24 Alkyl Dimethicone / DivinylDimethicone Crosspolymer, such as NuLastic Silk MA by the company Alzo.

As examples of silicone elastomers dispersed in a linear silicone oil which 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; and Dimethicone (and) Dimethicone Crosspolymer, such as Dow Corning EL-9240 Silicone Elastomer Blend from Dow Corning (Hexadiene / Polydimethylsiloxane crosslinked polydimethylsiloxane (2 cSt)). PHENYL TRIMETHICONE (and) DIMETHICONE (and) PHENYL VINYL DIMETHICONE CROSSPOLYMER (INCI name) such as KSG 18A sold by the company Shin ETSU). The organopolysiloxane elastomer particles can also be used in the form of a powder, in particular 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 have the following properties: for INCI name: dimethicone / vinyl dimethicone crosspolymer. The organopolysiloxane powder may also be coated with silsesquioxane resin as described, for example, in US Pat. No. 5,538,793. Such elastomer powders are sold under the names "KSP-100", "KSP-101", "KSP102", "KSP-103", "KSP-104", "KSP-105" by the company Shin Etsu, INCI: vinyl dimethicone / methicone silsesquioxane Crosspolymer. Examples of organopolysiloxane powders coated with silsesquioxane resin that may advantageously be used according to the invention include organopolysiloxane elastomers of the INCI name VINYL DIMETHICONE / METHICONE SILSESQUIOANE CROSSPOLYMER, such as those sold under the trade reference "KSP-100" of US Pat. Shin Etsu company.

As the preferred lipophilic gelling agent of the organopolysiloxane elastomer type, cross-linked organopolysiloxane elastomers may be mentioned especially chosen from Dimethicone Crosspolymer (INCI name), Dimethicone (and) Dimethicone Crosspolymer (INCI name), Vinyl Dimethicone Crosspolymer. (INCI name), Dimethicone / Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone Crosspolymer-3 (INCI name), VINYL DIMETHICONE / METHICONE SILSESQUIOANE CROSSPOLYMER, DIPHENYL XY PHENYL TRIMETHICONE (and) DIMETHICONE (and) PHENYL VINYL DIMETHICONE CROSSPOLYMER (INCI name) and in particular the Dimethicone Crosspolymer (INCI name) The organopolysiloxane elastomer may be present in a composition of the present invention at a content of between 0.1% and 70% by weight. Dry matter in particular between 0.2% and 60% by weight, relative to the total weight of the oily phase. III. Semi-crystalline polymers The composition 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 greater than or equal to 30 ° C. For the purposes of the invention, the term "semicrystalline polymer" means polymers having a crystallizable portion and an amorphous portion 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 copolymer. 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 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 room temperature (25 ° C.) and atmospheric pressure (760 mmHg), the melting point of which is greater than or equal to 30 ° C. The melting point values correspond to the melting point measured using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name DSC 30 by the Mettler company, with a temperature rise 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 and the lips. According to the invention, the semi-crystalline polymers are advantageously soluble in the fatty phase, in particular at least 1% by weight, at a temperature above their melting temperature. Apart from the crystallizable chains or blocks, the sequences of the polymers are amorphous. For the purposes of the invention, the term "chain or crystallizable block" means 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 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 fatty 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 having crystallizable blocks are block copolymers or multiblock copolymers. 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 carrying a hydrophobic side chain (s) cri stalli sand (s), polymers containing in the backbone at least one crystallizable block, polyester polycondensates, aliphatic or aromatic or aliphatic / aromatic, metallocene-catalyzed ethylene-propylene copolymers, and acrylate / silicone copolymers. 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 0 951 897, - polycondensates, and in particular of polyester, aliphatic or aromatic or aliphatic / aromatic, - copolymers of ethylene and propylene prepared by metallocene catalysis, - homo- or co-polymers carrying at least one crystallizable side chain and homo- or co-polymers bearing in the skeleton at least a crystallizable block, such as those described in US Pat. No. 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 at melting temperature is 49 ° C., the homo- or co-polymers bearing at least one crystallizable side chain, in particular with fluorinated group (s), as described in document WO 01/19333, acrylate / silicone copolymers, such as copolymers of acrylic acid and polydimethylsiloxane grafted stearyl acrylate, polydimethylsiloxane grafted stearyl methacrylate copolymers, and 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 3025094 (CTFA name: acrylates / dimethicone), KP-541 (CTFA name: acrylates / dimethicone and isopropyl alcohol), KP-545 (name CTFA: acrylates / dimethicone and cyclopentasiloxane), and mixtures thereof. Preferably, the amount of semicrystalline polymer (s), preferably selected from semicrystalline crystallizable side chain polymers, is from 0.1% to 30% by weight of dry matter relative to the total weight of the oily phase, for example from 0.2% to 25% by weight, better still from 0.5% to 20%, or else from 0.5% to 12% by weight, relative to the total weight of the oily phase.

IV. Dextrin Esters The composition according to the invention may comprise, as lipophilic gelling agent, at least one dextrin ester. In particular, the composition preferably comprises at least one ester of dextrin and fatty acid, preferably C 12 to C 24, in particular C 14 to 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. In a particularly preferred manner, the oily phase of a composition according to the invention may comprise from 0.1% to 30% by weight of ester (s) of dextrin, preferably from 0.2% to 25% and preferably from 0.5% to 18% by weight, based on the total weight of the oily phase.

V. Hydrogen-Bonded Polymers As a representative of the hydrogen-bonded polymers that are suitable for the invention, polyamides and in particular hydrocarbon polyamides and silicone polyamides can be very particularly mentioned.

Polyamides The oily phase of a composition according to the invention may comprise at least one polyamide chosen from hydrocarbon polyamides, silicone polyamides, and mixtures thereof.

For the purposes of the invention, the term "polyamide" means a compound having at least 2 amide repeating units, preferably at least 3 amide repeating units and more preferably 10 amide repeating units. a) Hydrocarbon Polyamide A "hydrocarbon-based polyamide" is understood to mean a polyamide formed essentially or even consisting of carbon and hydrogen atoms, and possibly oxygen, nitrogen, and non-carbon atoms. silicon atom 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 chain" means an alkyl chain comprising one or more functional groups or reactive groups chosen especially from hydroxyl, ether, esters, oxyalkylene or polyoxyalkylene groups. Advantageously, this polyamide of the composition according to the invention has a weight average molecular weight of less than 100,000 g / mol, in particular ranging from 1000 to 100,000 g / mol, in particular less than 50,000 g / mol, in particular ranging from 1,000 to 50,000 g / mol, and more particularly from 1,000 to 30,000 g / mol, preferably from 2,000 to 20,000 g / mol, and more preferably from 2,000 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 used is a polyamide of formula (I): ## STR2 ## in which X represents a group -N (Ri) 2 or a group -OR in which R1 is a linear or branched Cg to C22 alkyl radical, which may be the same or different from each other, R2 is a di-C28-C42 dimer residue, R3 is an ethylene diamine radical, n is between 2 and 5; 5 and mixtures thereof. According to one particular embodiment, the polyamide used is an amide-terminated polyamide of formula (Ia): X + CR-2 -NH-R NH II ## STR1 ## in which X represents a group -N (R 1) 2 in wherein R1 is a linear or branched Cg-C22 alkyl radical, which may be the same or different from each other, R2 is a C28-C42 diacid dimer residue, R3 is an ethylene diamine radical, n is included between 2 and 5; and their mixtures. The oily phase of a composition according to the invention may furthermore additionally comprise, in this case, at least one additional polyamide of formula (Ib) ## STR2 ## wherein X represents a group -OR 'in which R1 is a linear or branched Cg to C22, preferably C16 to C22, alkyl radical which may be the same or different from each other; R2 is a dibasic diacid residue; C28-C42, R3 is an ethylene diamine radical, n is between 2 and 5, such as the commercial products sold by Arizona Chemical under the names Uniclear 80 and Uniclear 100 or Uniclear 80 V, Uniclear 100 V and Uniclear 100 VG, whose INCI name is "ethylenediamine / stearyl dimer dilinoleate copolymer". B) Silicone Polyamide Silicone polyamides are preferably solid at room temperature (25 ° C.) and atmospheric pressure (760 mmHg). The silicone polyamides may preferentially be polymers comprising at least one unit of formula (III) or (IV): ## STR2 ## in which x -R` SiO Si X Ni: c Y 0 (W) -R4, R5, R6 and R7, which may be identical or different, represent a group chosen from: linear or branched or cyclic hydrocarbon groups, in C1 to C40, saturated or unsaturated, which may contain in their chain a or several oxygen, sulfur and / or nitrogen atoms, and which may be substituted in part or totally by fluorine atoms, - C 6 -C 10 aryl groups, optionally substituted with one or more C 1 -C 6 alkyl groups. C4, - the polyorganosiloxane chains containing or not one or more oxygen, sulfur and / or nitrogen atoms, - the X, identical or different, represent a linear or branched C1 to C30 alkylene di-yl group; , which may contain in its chain one or more oxygen atoms and / or nitrogen, Y is a divalent linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene, saturated or unsaturated, C1 to C50 group, which may comprise one or more oxygen, sulfur and / or nitrogen atoms and / or substituted by one of the following atoms or groups of atoms: fluorine, hydroxy, C3-C8 cycloalkyl, C1-C40 alkyl, C5-C10 aryl, phenyl optionally substituted with 1 to 3 C1 to C3 alkyl, C1 to C3 hydroxyalkyl and C1 to C6 alkylamines, or Y is a group corresponding to the formula: R8 _T // 5 where - T represents a linear or branched trivalent or tetravalent hydrocarbon group saturated or unsaturated C3-C24 optionally substituted by a polyorganosiloxane chain, and which may contain one or more atoms selected from O, N and S, or T represents a trivalent atom selected from N, P and Al, and 10-R8 represents a C1 to C50 alkyl group, linear ire or branched, or a polyorganosiloxane chain, which may comprise one or more ester, amide, urethane, thiocarbamate, urea, thiourea and / or sulfonamide groups which may or may not be linked to another chain of the polymer, n is an integer ranging from 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 more preferably from 6 to 200. According to one particular embodiment, the silicone polyamide comprises at least one a 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 C1-alkyl group; at C40, linear or branched, 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.

The compounds sold by the company Dow Corning under the name DC 2-8179 (DP 100) and DC 2-8178 (DP 15) whose INCI name is "Nylon611 / dimethicone copolymers", that is to say Nylon-611 / dimethicone copolymers. The silicone polymers and / or copolymers 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. Preferably, the total content of polyamide (s) and / or polyamide (s) silicone (s) is between 0.1% and 30% by weight, preferably between 1% and 20% by weight, so preferred between 1% and 12% by weight, expressed as dry matter relative to the total weight of the oily phase. HYDROCARBON SEQUENCE COPOLYMER As representative of lipophilic gelling agents may be further mentioned other polymeric gelling agents that are the hydrocarbon block copolymers also called block copolymers. The polymeric gelling agent is capable of thickening or gelling the hydrocarbon phase of the composition.

By "amorphous polymer" is meant a polymer which does not have a crystalline form. The polymeric gelling agent is preferably also film-forming, that is to say that it is capable of forming a film when it is applied to the skin and / or the lips. The hydrocarbon-based block copolymer may in particular be a diblock, triblock, multiblock, radial or star copolymer, or mixtures thereof. Such hydrocarbon-based block copolymers are described in application US-A-2002/005562 and in US-A-5 221 534. The copolymer may have at least one block whose glass transition temperature is preferably less than 20 ° C. preferably less than or equal to 0 ° C, preferably less than or equal to -20 ° C, more preferably less than or equal to -40 ° C. The glass transition temperature of said block may be between -150 ° C. and 20 ° C., in particular between -100 ° C. and 0 ° C. The hydrocarbon block copolymer present in the composition according to the invention is an amorphous copolymer formed by polymerization of an olefin. The olefin may in particular be an ethylenically unsaturated elastomeric monomer. As an example of an olefin, mention may be made of ethylenic carbide monomers, especially having one or two ethylenic unsaturations, having from 2 to 5 carbon atoms, such as ethylene, propylene, butadiene or isoprene, or pentadiene. Advantageously, the hydrocarbon-based block copolymer is an amorphous block copolymer of styrene and olefin.

Particularly preferred are block copolymers comprising at least one styrene block and at least one block comprising units selected from butadiene, ethylene, propylene, butylene, isoprene or a mixture thereof. According to a preferred embodiment, the hydrocarbon block copolymer is hydrogenated to reduce residual ethylenic unsaturations after polymerization of the monomers. In particular, the hydrocarbon-based block copolymer is a copolymer, optionally hydrogenated, with styrene blocks and with ethylene / C 3 -C 4 alkylene blocks. According to a preferred embodiment, the composition according to the invention comprises at least one diblock copolymer, preferably hydrogenated, preferably chosen from styrene-ethylene / propylene copolymers, styrene-ethylene / butadiene copolymers, copolymers of styrene-ethylene / butylene. Diblock polymers are in particular sold under the name Kraton® G1701E by Kraton Polymers. Advantageously, a diblock copolymer such as those described above, in particular a diblock copolymer of styrene-ethylene / propylene, or a mixture of diblock as described above, is used as polymeric gellant. Thus, according to a preferred embodiment, a composition according to the invention comprises, as lipophilic gelling agent, at least one hydrocarbon-based block copolymer, preferably a copolymer, optionally hydrogenated, with styrene blocks and with ethylene / C3-C4 alkylene blocks. , more preferably a diblock copolymer, preferably hydrogenated, such as a styrene-ethylene / propylene copolymer, a styrene-ethylene / butadiene copolymer. The hydrocarbon block copolymer (or the mixture of hydrocarbon block copolymers) may be present in a content ranging from 0.1% to 15% by weight, preferably ranging from 0.1% to 10% by weight, more preferably ranging from 0.5% to 5% by weight, more preferably from 0.5% to 3% by weight, relative to the total weight of the composition. HYDROPHILIC (S) / GELIFYING (S) LIPOPHILY (S) GELIFYING SYSTEM (S) According to an advantageous variant, a composition according to the invention comprises an additional lipophilic gelling agent chosen from particulate gelling agents, organopolysiloxane elastomers, semi-synthetic polymers and crystalline esters, dextrin esters, hydrogen bonded polymers, hydrocarbon block copolymers and mixtures thereof, and in particular at least one organopolysiloxane elastomer.

In particular, a composition according to the invention comprises an additional lipophilic gelling agent chosen from particulate gelling agents, semicrystalline polymers, dextrin esters, hydrogen-bonded polymers, hydrocarbon block copolymers and mixtures thereof.

LIPOPHILIC (S) HYDROPHILIC (S) / GELIFYING (S) SYSTEM (FR) As an illustrative and nonlimiting example of hydrophilic gelling / gelling agent (s) systems, lipophilic (s) particularly suitable for In particular, the following systems may be mentioned: copolymers of 2-acrylamido-2-methylpropanesulphonic acid, crosslinked and or neutralized / hydrophobic silica aerogels; copolymers of 2-acrylamido-2-methylpropanesulphonic acid, crosslinked and or neutralized / hydrophobic silica aerogels and modified clays; 2-acrylamido-2-methylpropane sulfonic acid copolymers, crosslinked and or neutralized / hydrophobic silica aerogels and silicone elastomers; copolymers of 2-acrylamido-2-methylpropane sulfonic acid, crosslinked and or hydrophobicized silica / hydrophobic aerogels, modified clays and silicone elastomers. According to a particularly preferred form, the composition according to the invention comprises: at least one non-starch hydrophilic gelling agent chosen from 2-acrylamido-2-methylpropanesulphonic acid (AMPS®) copolymers, crosslinked and or neutralized, and more particularly copolymers of AMPS® and hydroxyethyl acrylate and - at least one lipophilic gelling agent chosen from hydrophobic silica aerogels, - at least one UV filter, and optionally an additional gelling agent chosen from among the particulate gelling agents, organopolysiloxane elastomers, semicrystalline polymers, dextrin esters, hydrogen-bonded polymers, hydrocarbon block copolymers and mixtures thereof, and in particular modified clay and more particularly hectorites modified with di-stearyl di- methyl ammonium. In particular, the composition according to the invention comprises: at least one non-starch hydrophilic gelling agent chosen from 2-acrylamido-2-methylpropanesulphonic acid (AMPS®), cross-linked and or neutralized copolymers, and more particularly copolymers of AMPS® and hydroxyethyl acrylate and - at least one lipophilic gelling agent chosen from hydrophobic silica aerogels, at least one UV filter, and optionally an additional gelling agent chosen from among particulate gelling agents, semi-crystalline polymers, dextrin esters, hydrogen-bonded polymers, hydrocarbon block copolymers and mixtures thereof, and in particular modified clay and more particularly di-stearyl dimethyl ammonium chloride-modified hectorites. Even more particularly, said UV filter is chosen from water-soluble organic UV filters, liposoluble organic filters and their mixtures, and more particularly liposoluble organic UV filters.

UV FILTERS The compositions according to the invention contain at least one UV filter. Preferably, the UV filter that is suitable for the invention is chosen from water-soluble UV filters, liposoluble UV-screening agents, insoluble UV-screening agents, and mixtures thereof.

Among these UV filters, water-soluble organic filters, liposoluble organic filters, insoluble organic filters, inorganic filters can be distinguished. Preferably, the UV filter (s) are chosen from water-soluble organic UV filters, liposoluble organic filters and their mixtures and more particularly fat-soluble organic UV filters.

By "water-soluble UV filter" is meant any UV radiation filtering compound capable of being completely dissolved or miscibilized in the molecular state in an aqueous phase or capable of being solubilized in colloidal form (for example in micellar form) in an aqueous phase.

By "liposoluble filter" is meant any UV radiation filtering compound capable of being completely dissolved or miscibilized in the molecular state in a fatty phase or capable of being solubilized, in colloidal form (for example in micellar form) in a fatty phase.

By "insoluble UV filter" is meant any UV radiation filtering compound having a solubility in water of less than 0.5% by weight and a solubility of less than 0.5% by weight in most organic solvents such as paraffin oil, fatty alcohol benzoates and triglycerides of fatty acids, for example Miglyol 812® 25 marketed by the company DYNAMIT NOBEL. This solubility, performed at 70 ° C is defined as the amount of product in solution in the equilibrium solvent with an excess of suspended solid after return to room temperature. It can easily be evaluated in the laboratory.

3025094 I / WATER SOLUBLE ORGANIC UV FILTERS WITH WATER-SOLUBLE ORGANIC UVA FILTERS By "water-soluble organic UVA filter" is meant any organic compound filtering UVA radiation in the wavelength range 320 to 400 nm capable of being completely dissolved or miscible. in the molecular state in an aqueous phase or capable of being solubilized in colloidal form (for example in micellar form) in an aqueous phase.

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

These filters correspond to the following general formula (I): wherein F denotes a hydrogen atom, an alkali metal or an NH (R 1) 3+ radical in which the radicals R 1, which may be identical or different, denote a hydrogen atom, a C 1 -C 4 alkyl or hydroxyalkyl radical or a Mn + / n group, Mn + denoting a polyvalent metal cation in which n is equal to 2 or 3 or 4, Mn + denoting preferably a metal cation selected from Ca2 +, Zn2 +, Mg2 +, Ba2 +, A13 + and Zr4 +. It is understood that the compounds of formula (I) above may give rise to the "cis-trans" isomer around one or more double bonds and that all the isomers come into the of the present invention. Among the water-soluble organic UVA filters that may be used according to the present invention, mention may also be made of compounds comprising at least two benzoazolyl groups containing sulphonic groups, such as those described in patent application EP-A-0669323. They are described and prepared according to the syntheses indicated in US Pat. No. 2,463,264 and the patent application EP-A-0669323.

The compounds comprising at least two benzoazolyl groups according to the invention have the following general formula (II): embedded image in which: Z represents an organic radical of valence (1 + n) containing one or more double bonds arranged such that it completes the double bond system of at least two benzoazolyl groups as defined within the hooks to form a fully conjugated set; X 'denotes S, O or NR 6 - R 1 denotes hydrogen, C 1 -C 18 alkyl, C 1 -C 4 alkoxy, C 5 -C 15 aryl, C 2 -C 18 acyloxy, SO 3 Y or COOY; - The radicals R2, R3, R4 and R5, identical or different, denotes a nitro group or a radical R1; - R6 denotes hydrogen, a C1-C4 alkyl or a C1-C4 hydroxyalkyl; Y denotes hydrogen, Li, Na, K, NH4, 1 / 2Ca, 1 / 2Mg, 1 / 3A1 or a cation resulting from the neutralization of a free acid group by an organic nitrogen base; m is 0 or 1; n is a number from 2 to 6; - 1 is a number from 1 to 4; - provided that + n does not exceed the value 6.

Of these compounds, those for which the Z group is selected are preferably selected from the group consisting of: (a) a linear aliphatic C2-C6 hydrocarbon radical which may be interrupted by a C5-C12 aryl group or a heteroaryl C 4 -C 10 in particular chosen from the following groups: -CH = CH-, -CH = CH-CH = CH- or -CI-1 CH = CH (b) a C 5 -C 15 aryl group which can be interrupted by an olefin linear aliphatic C2-C6 hydrocarbon radical, in particular chosen from the following groups: ## STR2 ## (c) a C3-C10 heteroaryl residue, chosen in particular from the following groups: ## STR3 ## where R6 has the same meaning indicated above; said radicals Z as defined in paragraphs (a), (b) and (c) may be substituted with C1-C6 alkyl, C1-C6 alkoxy, phenoxy, hydroxy, methylenedioxy or amino optionally substituted with one or 2 C 1 -C 5 alkyl radicals.

Preferably, the compounds of formula (II) contain, per molecule of 1, 3 or 4 SO3Y groups. By way of examples of compounds of formula (II) which may be used, mention may be made of the compounds of formulas (a) to (j) and of the following structure and their salts: HO3S (a) HO3S SO3H (b) SO3H ( c) HO3S SO3H (d) 3025094 89 SO3H (e) HO3S (f) SO3H HO3S SO3H (g) HO3S SO3H (h) HO3S SO3H (j) HO3S SO3H (J) Of all these compounds, the most preferred is 1,4-bisbenzimidazolylphenylen-3,3 ', 5,5'-tetrasulfonic acid (INCI name: Disodium Phenyl 3025094 Dibenzimidazole Tetrasulfonate) (compound (d)) or one of its salts of the following structure sold in particular under the name of NEOHELIOPAN AP® by the company Symrise: 5 HO, S S031-1 Among the water-soluble organic UVA filters that can be used according to the present invention, mention may also be made of benzophenone compounds comprising at least one sulphonic acid function, such as, for example, following compounds: Benzophenone-4, sold in particular by BASF under the name Uvinul HO-S = 0 il 0 Benzophenone -5 structure Benzophenone-9, sold in particular by BASF under the name Uvinul DS49e: Na Na. N / A.

Among the water-soluble organic UVA filters, use will more particularly be made of benzene-1,4-di (3-methylidene-10-camphorsulfonic acid) and its various salts (INCI name: Terephthalylidene Dicamphor Sulfonic Acid), in particular manufactured by the company. CHIMEX under the trade name MEXORYL SX®. The water-soluble organic UVA filter (s) according to the invention are preferably present in the compositions according to the invention at a concentration of active material ranging from 0.01 to 30%, preferably from 0.1 to 15%, in weight relative to the total weight of the composition. B / WATER-SOLUBLE ORGANIC UVB FILTERS By "water-soluble organic UVB filter" is meant any organic compound filtering the UVB radiation in the wavelength range between 280 and 320 nm capable of being completely dissolved or miscibilized in the molecular state in an aqueous phase or capable of being solubilized in colloidal form (for example in micellar form) in an aqueous phase.

The water-soluble organic UVB filters are especially chosen from: water-soluble cinnamic derivatives such as ferulic acid or 3-methoxy-4-hydroxycinnamic acid; water-soluble benzylidene camphor compounds; Water-soluble phenylbenzimidazole compounds; water-soluble p-aminobenzoic compounds (PABA); water-soluble salicylic compounds and mixtures thereof.

Examples of water-soluble organic UVB filters are those referred to below under their INCI name: 3025094 92 Para-aminobenzoic compounds: PABA, PEG-25 PABA sold in particular under the name "UVINUL P 25®" by BASF.

5 Salicylate Compounds: Dipropylene Glycol Salicylate sold in particular under the name "DIPSAL®" by SCHER, TEA Salicylate, sold in particular under the name "NEO HELIOPAN Tse" by Symrise, 10 Compounds Benzylidene Camphor: Benzylidene Camphor Sulfonic Acid marketed in particular under the name "MEXORYL SL® "by CHIMEX, Camphor Benzalkonium Methosulfate marketed in particular under the name" MEXORYL soe "by CHIMEX. Phenylbenzimidazole compounds: Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name "Eusolex 232®" by Merck.

The Phenylbenzimidazole Sulfonic Acid filter sold in particular under the trade name "EUSOLEX 232®" by MERCK will be used more particularly. The water-soluble organic UVB filter (s) according to the invention are preferably present in the compositions according to the invention at a concentration of active material ranging from 0.01 to 30%, preferably from 0.1 to 15%, by weight relative to the total weight of the composition. II / LIPOSOLUBLE ORGANIC UV FILTERS By "liposoluble organic UVB filter" is meant any organic compound filtering the UVB radiation in the wavelength range between 280 and 320 nm, which may be completely dissolved or miscible in the state. molecular in a fatty phase or capable of being solubilized in colloidal form (for example in micellar form) in a fatty phase. Of the fat-soluble organic UV filters, some of them are liquid at room temperature.

The liposoluble organic UV filters are especially chosen from cinnamic derivatives; anthranilates; salicylic derivatives, dibenzoylmethane derivatives, camphor derivatives; benzophenone derivatives; 13, 13-diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives, especially those mentioned in US Pat. No. 5,624,663; imidazolines; p-aminobenzoic acid derivatives (PABA); benzoxazole derivatives as described in patent applications EP 0832642, EP 1027883, EP 1300137 and DE 10162844; filter polymers and silicone filters such as those described in particular in the application WO-93/04665; dimers derived from α-alkylstyrene such as those described in DE 19855649; 4,4-diarylbutadienes as described in applications EP 0967200, DE 19746654, DE 19755649, EP-A-1008586, EP 1133980 and EP 133981; merocyanine derivatives merocyanines as described in US Pat. No. 4,195,999, WO 2004/006878, WO 2008/090066, WO 2011113718, WO 2009027258, and IP COM 20 JOURNAL No. 000179675D published on February 23, 2009, IP COM JOURNAL No. 000182396D published on April 29, 2009, IP COM JOURNAL No. 000189542D published November 12, 2009, IP COM Journal N'IPCOM000011179D published on 04/03/2004 and their mixtures.

Examples of fat-soluble organic UV filters are those referred to below under their INCI name: Derivative of dibenzoylmethane Butyl Methoxy Dibenzoylmethane or avobenzone, sold for sale under the trade name "PARSOL 1789" by DSM, for example NUTRITIONAL PRODUCTS; Derivatives of para-aminobenzoic acid: Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the name "ESCALOL 5 507" by ISP; Salicylic derivatives: Homosalate sold in particular under the name "Eusolex HMS" by Rona / EM Industries, Ethylhexyl Salicylate sold in particular under the name "NEO HELIOPAN OS" by SYMRISE; Cinnamic derivatives: Ethylhexyl methoxycinnamate sold in particular under the trade name "PARSOL MCX" by DSM NUTRITIONAL PRODUCTS, Isopropyl Methoxy Cinnamate, Isoamyl Methoxy cinnamate sold in particular under the trade name "NEO HELIOPAN E 1000" by SYMRISE, Cinoxate, Diisopropyl Methylcinnamate; Derivatives of I3,13-diphenylacrylate: Octocrylene sold in particular under the trade name "Uvinul N539" by BASF, Etocrylene, sold in particular under the trade name "UVINUL N35" by BASF; Derivatives of benzophenone: Benzophenone-1 sold in particular under the trade name "UVINUL 400" by BASF, Benzophenone-2 sold in particular under the trade name "UVINUL D50" by BASF, 3025094 Benzophenone-3 or Oxybenzone, sold in particular under the name commercial "UVINUL M40" by BASF, Benzophenone-6 sold in particular under the trade name "Helisorb 11" by Norquay, 5 Benzophenone-8 sold in particular under the trade name "Spectra-Sorb UV-24" by American Cyanamid, Benzophenone-12, 2- (4-diethylamino-2-hydroxybenzoyl) benzoate of n-hexyl sold in particular under the trade name "UVINUL A +" such as "UVINUL A + GRANULAR" or in the form of a mixture with octylmethoxycinnamate, especially under the name commercial "UVINUL A + B" by BASF; Derivatives of benzylidene camphor: 3-Benzylidene camphor sold in particular under the name "Mexoryl 15 SD" by Chimex, 4-Methylbenzylidene camphor sold in particular under the name "Eusolex 6300" by Merck, Polyacrylamidomethyl Benzylidene Camphor marketed in particular under the name "Mexoryl SW" by CHIMEX; Derivatives of phenylbenzotriazole: Drometrizole Trisiloxane sold in particular under the name "Silatrizole" by Rhodia Chimie; Triazine derivatives: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold in particular under the trade name "Tinosorb S" by BASF, Ethylhexyl triazone sold in particular under the trade name "UVINUL T150" by BASF, Diethylhexyl Butamido Triazone sold especially under the trade name "UVASORB" HEB - by SIGMA 3V, 3025094 96 - the triazine silicones substituted with two aminobenzoate groups as described in EP 0841341, in particular 2,4-bis (n-butyl 4'-aminobenzalmalonate) -6 - [(3- {1,3,3,3-tetramethyl-1-trimethylsilyloxy] disiloxanyl} propyl) amino] s-triazine; Anthranilic Derivatives: Menthyl anthranilate sold in particular under the trade name "Neo Heliopan MA" by SYMRISE, Imidazoline derivatives: Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate; Derivatives of benzalmalonate: Di-neopentyl 4'-methoxybenzalmalonate, Polyorganosiloxane with benzalmalonate functions such as Polysilicone-15 sold in particular under the trade name "PARSOL SLX" by DSM; 4,4-Diarylbutadiene derivatives: 1,1-dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene, benzoxazole derivatives: 2,4-bis- [5-1 (dimethylpropyl) benzoxazole; 2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine sold in particular as Uvasorb K2A by Sigma 3V, and mixtures thereof; Lipophilic merocyanine derivatives - Octy1-5-N, N-diethylamino-2-phenysulfonyl-2,4-pentadienoate, and mixtures thereof; Preferred liposoluble organic screening agents are selected from: Butyl Methoxy Dibenzoylmethane 3025094 Ethylhexyl Methoxycinnamate Ethylhexyl Salicylate, Homosalate, Butyl Methoxydibenzoylmethane Octocrylene, Benzophenone-3, 2- (4-diethylamino-2-hydroxybenzoyl) benzoate n-hexyl. 4-Methylbenzylidene camphor, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Ethylhexyl triazone, Diethylhexyl Butamido Triazone, 2,4,6-tris (dineopentyl 4'-amino benzalmalonate) -s-triazine 2,4,6-tris- (4) Diisobutylamino benzalmalonate) -s-triazine dineopentyl 2,4-bis (4'-aminobenzalmalonate) -6- (n-butyl 4'-aminobenzoate) -s-triazine, Drometrizole Trisiloxane Polysilicone-15 1-dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine and mixtures thereof. The preferred liposoluble organic screening agents are chosen more particularly from butyl methoxydibenzoylmethane octocrylene, ethylhexyl salicylate and n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate. Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Ethylhexyl triazone, Diethylhexyl Butamido Triazone, Drometrizole Trisiloxane and mixtures thereof.

The liposoluble organic UV screening agent (s) are preferably present in the compositions according to the invention at a content ranging from 0.1% to 50% by weight and in particular from 0.5% to 30% by weight, relative to to the total weight of the composition.

INSOLUBLE ORGANIC UV AND INSOLUBLE UV FILTERS AND INSOLUBLE ORGANIC UV FILTERS The insoluble organic UV filters according to the invention preferably have an average particle size which varies from 0.01 to 51 μm and more preferably from 0.01 to 51 μm. to 2 μm and more particularly from 0.020 to 2 μm. The average particle diameter was measured by a particle size distribution analyzer of the Culter N4 PLUS type manufactured by Bechman Coulter INC. The insoluble organic filters according to the invention can be brought into the desired particulate form by any ad-hoc means such as in particular dry milling or in a solvent medium, sieving, atomization, micronisation, spraying.

The insoluble organic screening agents according to the invention in micronized form can in particular be obtained by a method of grinding an insoluble organic UV filter in the form of coarse particles in the presence of a suitable surfactant making it possible to improve the dispersion of the particles thus obtained in the cosmetic formulations. An example of a method for micronizing insoluble organic filters is described in GB-A-2 303 549 and EP-A-893119. The grinding apparatus used according to these documents may be a jet mill, ball mill, vibrator or hammer mill and preferably a high speed grinder or an impact mill and more particularly a rotary ball mill, a vibratory mill, tube mill or a rod mill.

According to this particular process, alkylpolyglucosides of structure C.E12 .pi.pub.pi (C6E11005) .sub.H wherein n is an integer of 8 to 16 and x is, as surfactants for the grinding of said filters. the average degree of polymerization of the unit (C6H1005) and varies from 1.4 to 1.6. They may be chosen from C1-C12 esters of a compound of structure C.E12.-p10 (C6E11005) 'H and more precisely an ester obtained by reaction of a C1-C12 carboxylic acid such as formic, acetic, propionic, butyric, sulphosuccinic, citric or tartaric acid with one or more free OH functions on the glucoside unit (C6E11005). As alkylpolyglucoside, mention may be made in particular of decylglucoside.

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

The insoluble organic UV filters in accordance with the invention may be chosen especially from organic UV filters of the oxalanilide type, of the triazine type, of the benzotriazole type; vinyl amide type; of the cinnamide type; of the type comprising one or more benzazole and / or benzofuran, benzothiophene or indole groups; aryl vinylene ketone type; of the phenylene bis-benzoxazinone derivative type, amide derivative, sulfonamide or acrylonitrile carbamate type or mixtures thereof. As used in the present invention, the term benzazole includes both benzothiazoles, benzoxazoles and benzimidazoles.

A / Oxalanides Among the UV filters of the oxalanilide type according to the invention, mention may be made of those having the structure: (I) 3025094 in which T1, T'1, T2 and T'2 denote, identical and different, a C 1 -C 8 alkyl radical or a C 1 -C 8 alkoxy radical. These compounds are described in the patent application WO 95/22959.

By way of examples, mention may be made of the commercial products TINUVIN 315® and TINUVIN 312® sold by the company BASF and respectively of structure: B / Triazines. Among the insoluble UV-screening agents of the triazine type according to the invention, it is possible to also mention those corresponding to the following formula (II): T3 NON T 5 T4 wherein T3, T4, T5, independently, are phenyl, phenoxy, pyrrolo, in which phenyl, phenoxy, pyrrolo unsubstituted or substituted by one, two or three substituents selected from OH, C1-C18alkyl or C1-C18alkoxy, C1-Ciscarboxyalkyl, C8-C8cycloalkyl, methylbenzylidenecamphor, - (CH = CH). (C0) - OT6, with T6 being C1-C18alkyl or cinnamyl. These compounds are described in WO 97/03642, GB 2286774, EP-743309, WO 98/22447, GB 2319523. C (CH 3) 3 OC, H 5 NH 2. the invention may also be mentioned insoluble s-triazine derivatives bearing benzalmalonate and / or phenylcyanoacrylate groups such as those described in application EP-A-0790243 (forming an integral part of the content of the description).

Among these insoluble triazine-type UV filters, mention will be made more particularly of the following compounds: 2,4,6-tris (diethyl 4'-aminobenzalmalonate) -s-triazine, 2,4,6-tris (4'-aminobenzalmalonate diisopropyl) -s-triazine, 2,4,6-tris (dimethyl 4'-aminobenzalmalonate) -s-triazine, 2,4,6-tris (a) ethyl cyano-4-aminocinnamate) -s-triazine. Among the UV triazine type filters according to the invention, mention may also be made of the insoluble s-triazine derivatives bearing benzotriazole and / or benzothiazole groups such as those described in the application WO98 / 25922 (forming an integral part of the content of the description). Among these compounds, mention may be made more particularly of: 2,4,6-tris [(3'-benzotriazol-2-yl-2'-hydroxy-5'-methyl) phenylamino] -s20 triazine, -2,4 6-tris [(3'-benzotriazol-2-yl-2'-hydroxy-5'-ter-octyl) phenylamino] -strapriazine. There may also be mentioned the symmetrical triazines substituted by naphthalenyl groups or polyphenyl groups described in US Pat. No. 6,225,467, WO2004 / 085412 (see compounds 6 and 9) or the "Symetrical Triazine Derivatives" IP.COM Journal document, IP.COM INC. WEST HENRIETTA, NY, US (September 20, 2004) including 2,4,6-tris (di-phenyl) -triazine and 2,4,6-tris (ter-phenyl) -triazine which is repeated in patent applications WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007, WO 2006/034992, WO 2006/034985.

C. Benzotriazoles Among the insoluble organic UV-screening agents of the benzotriazole type according to the invention, mention may be made of those of the following formula (III) as described in the application WO 95/22959 (forming an integral part of the content of the description) in which T7 denotes a hydrogen atom or a C1-C18 alkyl radical; Tg and T9, identical or different, denote a C 1 -C 18 alkyl radical optionally substituted with a phenyl. By way of example of compounds of formula (III), mention may be made of the commercial products TINUVIN 328, 320, 234 and 350 of the BASF Company with the following structure: ## STR2 ## ## STR2 ## C (CH 3) 3 C (CH 3) 3 C (CH 3) 2 C (CH 3) 2 C (CH 3) 3 3025094 Among the insoluble organic UV screening agents of the benzotriazole type according to the invention, mention may be made of compounds such as described in US Pat. No. 5,687,521, US Pat. No. 5,373,037, US Pat. No. 5,362,881 and in particular [2,4'-dihydroxy-3- (2H-benzotriazol-2-yl) -5- (1,1,3), 3-tetramethylbutyl) -2'-n-octoxy-5'-benzoyl] diphenylmethane sold in particular under the name MIXXIM PB30® by the company Fairmount Chemical with structure: OH 0 (nC, H17) OH tenC8I-117 0 CH2 Among the organic insoluble UV-filters of the benzotriazole type in accordance with the invention, mention may be made of methylene bis (hydroxyphenylbenzotriazole) derivatives having the following structure: CH 2 (IV) 10 11 in which the radicals T 10 and T 11, which are identical or different, sign C1-C18 alkyl radical may be substituted by one or more radicals selected from C1-C4 alkyl, C5-C12 cycloalkyl or aryl residue. These compounds are known per se and described in US Pat. No. 5,237,071, US 5,166,355, GB-A-2,303,549, DE 197,246 and EP-A-893,119 (integral to the description). In the formula (I) defined above: the C 1 -C 18 alkyl groups may be linear or branched and are for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-octyl, n-amyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, tetradecyl, hexydecyl, or octadecyl; C 5 -C 12 cycloalkyl groups are, for example, cyclopentyl, cyclohexyl, cyclooctyl; aryl groups are for example phenyl, benzyl.

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

Among the organic insoluble vinyl-amide type filters, there may be mentioned, for example, the compounds of the following formula which are described in the application WO 95/22959 (an integral part of the content of the description): T12- (Y) rC (= O) -C (T) = C (T-14) -N (T 5) (T-16) (V) N'N compound (c) Of the compounds of formula (IV), those of the following structure: OH compound (a) OH compound (b) 3025094 wherein T12 is a C1-C18 alkyl radical, preferably C1-C5 alkyl or a phenyl group optionally substituted with one, two or three radicals selected from OH, C 1 -C 18 alkyl, C 1 -C 8 alkoxy, or -C (= O) -OT 17 where T 17 is C 17 -C 18 alkyl; T13, T14, T15 and T16, which may be identical or different, denote a C1-C18 alkyl radical, preferably a C1-C5 alkyl radical, or a hydrogen atom; Y is N or O and r is 0 or 1. Among these compounds, mention will be made in particular of: 4-octylamino-3-penten-2-one; ethyl-3-octylamino-2-butenoate; 3-Octylamino-1-phenyl-2-buten-1-one - 3-dodecylamino-1-phenyl-2-buten-1-one. E / Cinnamamides Among the insoluble organic cinnamamide type filters in accordance with the invention, mention may also be made of the compounds as described in the application WO 95/22959 (forming an integral part of the content of the description) and corresponding to the following structure Wherein OT18 is a hydroxy or C1-C4 alkoxy radical, preferably methoxy or ethoxy; T19 is hydrogen, C1-C4 alkyl, preferably methyl or ethyl; T20 is - (CONH) s-phenyl or s is 0 or 1 and the phenyl group may be substituted with one, two or three groups selected from OH, C1-C18 alkyl, C17-C6 alkoxy, or a group -C (= O) -OT21 where T21 is a C1-C18 alkyl and more preferably T21 is a phenyl, 4-methoxyphenyl or phenylaminocarbonyl group.

Mention may also be made of cinnamamide dimers such as those described in US Pat. No. 5,888,481, for example the compound of structure: ## STR1 ## Among the insoluble organic benzazole type screening agents, mention may be made of those corresponding to one of the formulas following: wherein each of the symbols X independently represents an oxygen or sulfur atom or an NR 2 group, each of the symbols Z independently represents a nitrogen atom or a CH group, each of the symbols R 1 independently represents an OH group , a halogen atom, a linear or branched C 1-8 alkyl group, optionally containing a silicon atom, or a linear or branched C 1-8 alkoxy group, each of the numbers m is independently 0, 1 or 2 , n represents an integer from 1 to 4 inclusive, p is 0 or 1, each of the numbers q is independently 0 or 1, (VII) (A) pn (VIII) (Ri) 111 3025094 each of the symbols R2 independently represents a hydrogen atom, a linear or branched C 1 -C 8 alkyl or benzyl group, optionally containing a silicon atom, A represents a radical of valence n chosen from those of formulas: (b) (C) (0) wherein R 3 is each R 4 (j) (k) (1) R 3), wherein each of R 3 is independently a halogen atom or an alkyl group or C1-4 alkoxy, linear or branched, or hydroxy, R4 represents a hydrogen atom or a linear or branched C1-4 alkyl group, c = 0-4, d = 0-3, e = 0 or 1 , and f = 0 - 2.

These compounds are described in particular in DE 676 103 and CH 350 763, US Pat. No. 5,501,850, US Pat. No. 5,961,960, EP 0669323, US Pat. No. 5,518,713 and US Pat. 264, the article of J. Am. Chem. Soc., 79, 5706 5708, 1957, the article of J. Am. Chem. Soc., 82, 609-5611, 1960, the patent application EP 0921126, the patent application EP 712855. As examples of preferred compounds of formula (VII) of the family of 2-arylbenzazoles, it is possible to mention 2-benzoxazol-2-yl-4-methylphenol, 2- (1H-3025094 benzimidazol-2-yl) -4-methoxyphenol or 2-benzothiazol-2-ylphenol, these compounds may be prepared for example according to the processes described in patent CH 350 763. By way of examples of preferred compounds of formula (VII) of the family of benzimidazolylbenzazoles, mention will be made of 2,2'-bis-benzimidazole, 5,5 ', 6, 6'-tetramethyl-2,2'-bis-benzimidazole, 5,5'-dimethyl-2,2'-bis-benzimidazole, 6-methoxy-2,2'-bisbenzimidazole, 2- (1H-benzimidazole) -2-yl) -benzothiazole, 2- (1H-benzimidazol-2-yl) benzoxazole and N, N'-dimethyl-2,2'-bis-benzimidazole, these compounds can be prepared according to the procedures described in US Pat. Nos. 5,961,960 and 2,463,10,264. As an example preferred compounds of formula (VII) of the phenylene benzazole family are 1,4-phenylenebis (2-benzoxazolyl), 1,4-phenylenebis (2-benzimidazolyl), 1, 3-phenylene-bis- (2-benzoxazolyl), 1,2-phenylene-bis (2-benzoxazolyl), 1,2-phenylene-bis (benzimidazolyl), 1,4-phenylene-bis- (N-2-ethylhexyl-2-benzimidazolyl) and 1,4-phenylene-bis- (N-dimethylsilylmethyl-2-benzimidazolyl), these compounds can be prepared according to the procedures described in US Patent 2,463,264 and in the publications J. Am. Chem. Soc., 82, 609 (1960) and J. Am. Chem. Soc., 79, 5706-5708 (1957).

Examples of preferred compounds of formula (VII) of the benzofuranyl-benzoxazole family are 2- (2-benzofuranyl) -benzoxazole, 2- (benzofuranyl) -5-methylbenzoxazole and 2 These compounds may be prepared according to the procedures described in US Pat. diphenyl-1,7-dihydro-benzo [1,2-d; 4,5-d] -di-imidazole corresponding to the formula 3025094 109 or 2,6-distyryl-1,7-dihydro-benzo [1,2-d; 4,5-d '] - di-imidazole or 2,6-di (p-tert-butyl styryl) -1,7-dihydro-enzo [1,2-d; 4,5-d] -di-imi dazol e, which can be prepared according to the application EP 0 669 323.

As the preferred compound of formula (IX), there may be mentioned 5,5'-bis - [(phenyl-2) -benzimidazole] of the formula: the preparation of which is described in J. Chim. Phys., 64, 1602 (1967).

Of these insoluble organic compounds which filter UV radiation, 2- (1H-benzimidazol-2-yl) benzoxazole, 5ole, 6-methoxy-2,2'-bis-benzimidazole, 2- ( 1H-benzimidazol-2-yl) -benzothiazole, 1,4-phenylenebis (2-benzoxazolyl), 1,4-phenylenebis (2-benzimidazolyl), 1,3-phenylenebis (2-benzoxazolyl) ), 1,2-phenylene-bis (2-benzoxazolyl), 1,2-phenylenebis (2-benzimidazolyl) and 1,4-phenylenebis (N-trimethylsilylmethyl-2-benzimidazolyl). G / Aryl Vinylene Ketones Among the insoluble organic filters of the aryl vinylene ketone type, mention may be made of those corresponding to one of the following formulas (X) and (XI): R 6 (X) B (XI) in which: n '= 1 or 2, 3025094 B, in the formula (X) when n' = 1 or in the formula (XI), is an aryl radical selected from the following formulas (a ') to (d'), or in the formula (X) when n '= 2, is a radical selected from the following formulas (e') to (h '): (R8) p, (b') (d ') 5 (e') (h ') in which: each of the symbols R8 independently represents an OH group, a halogen atom, a linear or branched C1-6 alkyl group optionally containing a silicon atom, a linear or branched C1-6 alkoxy group and optionally containing a silicon atom, a linear or branched C1-5 alkoxycarbonyl group, or a linear or branched C1-6 alkylsulfonamide group optionally containing a silicon atom or an amino acid function , p 'represents an integer from 0 to 4 inclusive, q' represents 0 or 1, R5 represents hydrogen or an OH group, R6 represents hydrogen, a linear or branched C1-6 alkyl group and optionally containing a silicon atom, a cyano group, a C1-6 alkylsulfonyl group, a phenylsulfonyl group, R7 represents a linear or branched C1-6 alkyl group and optionally containing a silicon atom or a phenyl group capable of forming a bicycle and optionally substituted with one or two radicals R4, OR R6 and R7 together form a C2-10 hydrocarbon radical monocyclic, bicyclic or tricylic, optionally interrupted by one or more atoms of nitrogen, sulfur and oxygen and can to contain another carbonyl, and optionally substituted by a linear or branched C1-C8 alkylsulfonamide group, and optionally containing a silicon atom or an amino acid function; provided that when n '= 1, R6 and R7 do not form a camphor ring. By way of examples of compounds of formula (X) in which n '= 1, 5 insoluble, filtering UV radiation, having an average particle size of between 10 nm and 5 nm, the following families may be mentioned: compounds of the styryl ketone type as described in patent application JP 04 134 042 such as 1- (3,4-dimethoxy-phenyl) -4,4-dimethyl-pent-1-en-3-one: MeO OMe 10 - compounds of the benzylidene cineole type such as those described in the article by E. Mariani et al., 16th IFSCC Congress, New York (1990)) such as 1,3,3-trimethyl-5- (4-methoxy-benzylidene) 2-oxa-bicyclo [2.2.2] octan-6-one: OMe - compounds of the benzylidene chromanone type such as those described in application JP 04 134 043 such as 3- (4-methoxy-benzylidene) -2 , 3,4a, 8-tetrahydro-chromen-4-one: OMe - compounds of the benzylidene thiochromanone type such as those described in patent application JP 04 134 043 such as 3- (4-methoxy-benzylidene) -2,3,4a, 8a-tetrahydro-chromen-4-thione: SOMe - compounds of the benzylidene quinuclidinone type such as those described in application EP 0 576 974 such as 4-methoxybenzylidene-1-azabicyclo [2.2.2] octan-3-one: OMe-compounds of the type benzylidene cycloalkanone such as those described in patent application FR 2,395,023, such as 2- (4-methoxy-benzylidene) -cyclopentanone and 2- (4-methoxy-benzylidene) -cyclohexanone: o MeO 10 -benzylidene compounds hydantoin such as those described in application JP 01 158 090 such as 5- (3,4-dimethoxy-benzylidene) -imidazolidine-2,4-dione: MeO Met) MeO 15 - compounds of the benzylidene indanone type such as those described in the application JP 04 134 043 such as 2- (4-methoxy-benzylidene) -indan-1-one: OMe - compounds of the benzylidene tetralone type such as those described in patent application JP 04 134 043 such as 2- (4 methoxy-benzylidene) -3,4-dihydro-2H-naphthalen-1-one: OMe - benzylidene furanone compounds such as those described in patent application EP 0 390 683 such as 4- (4-methoxybenzylidene) -2,2,5,5-tetramethyldihydro-furan-3-one: compounds of the benzylidene benzofuranone type such as those described in US Pat. JP 04 134 041 such as 2-benzylidene-benzofuran-3-one: - compounds of the benzylidene indanedione type such as 2- (3,5-di-tert-butyl-4-hydroxy-benzylidene) -indan 1,3-dione: benzylidene benzothiofuranone compounds such as those described in JP 04,134,043) such as 2-benzylidene-benzo [b] thiophen-3-one: benzylidene barbituric compounds such as 5- (4-methoxybenzylidene) -1,3-dimethyl-pyrimidine-2,4,6-trione: 3025094 benzylidene pyrazolone compounds such as 4- (4-methoxybenzylidene) -5-methyl-2-phenyl-2,4-dihydro-pyrazol-3-one: Me 5 - benzylidene imidazolone compounds such as that 5- (4-methoxybenzylidene) -2-phenyl-3,5-dihydro-imidazol-4-one: raec - chalcone compounds such as 1- (2-hydroxy-4-methoxyphenyl) - 3-phenylpropenone: benzylidene one compounds as described in FR 2,506,156 such as 3-hydroxy-1- (2-hydroxy-4-methoxy-phenyl) -3-phenyl-propenone: Examples of compounds of formula (X) in which n '= 2 insoluble, filtering UV radiation, having an average particle size of between 10 nm and 5 μm, may be mentioned. the following families: 3025094 - phenylene bis methylidene-nor-camphor compounds as described in EP 0 693 471 such as 1,4-phenylene-bis- {3-methylidenebicyclo [2.2.1] heptan-2- one}: 5 - the compounds of the typ e phenylene bis methylidene camphor as described in document FR 2,528,420 such as 1,4-phenylenebis (3-methylidene-1,7,7-trimethylbicyclo [2.2.1] heptan-2-one} or 1,3-phenylene-bis- {3-methylidene-1,7,7-trimethyl-bicyclo [2.2.1] heptan-2-one} - phenylene bis-methylidene-camphorsulfonamide compounds such as those described in FR 529 887 such as 1,4-phenylene-bis-3,3'-methylidene camphor-10,10-sulfonamide ethyl or 2-ethylhexyl: And -1 -1 OR 3025094 116 And L1- and - phenylene bis methylidene cineole compounds as described in E. Mariani et al, 16th IFSCC Congress, New York (1990) as 1,4-phenylene-bis- {5-methylidene- 3,3-dimethyl-2-oxa-bicyclo [2.2.2] octan-6-one}: the compounds of the phenylene bis-methylidene ketotricyclodecane type as described in application EP 0 694 521 as 1.4 phenylenebis (octahydro-4,7-methano-6-inden-5-one): compounds of the phenylene bisalkylene ketone type such as those described in patent application JP 04 134 041, such as 1,4-phenylenebis (4,4-dimethyl-pent-1-en-3-one): compounds of the phenylene bis methylidene furanone type as described in application FR 2 638 354, such as 1,4-phenylenebis (4-methylidene-2,2,5,5-tetramethyl-dihydrofuran-3-one) Compounds of the phenylene bis-methylidene quinuclidinone type such as those described in patent application EP 0 714 880, such as 1,4-phenylenebis (2-methylidene) -aza-bicyclo [2.2.2] octan-3-one As compounds of formula (XI), the following families can be mentioned - bis benzylidene cycloalkanone compounds such as 2,5-dibenzylidene-cyclopentanone: gamma pyrone compounds as described in US Pat. JP 04 290 882 such as 2,6-bis (3,4-dimethoxy-phenyl) -pyran-4-one: Among these insoluble organic compounds filtering rayon UV light of the aryl vinylene ketone type, the compounds of formula (X) in which n '= 2 are particularly preferred.

5H / Phenylene bis-benzoxazinones Among the insoluble organic phenylene bis-benzoxazinone type screening agents, mention may be made of those corresponding to the following formula (XII): (XII) with R representing a divalent aromatic radical chosen from formulas (e) to (h) following: embedded image in which: each of the symbols R 9 independently represents an OH group, a halogen atom, a linear or branched C 1-6 alkyl group and optionally containing a silicon atom, an alkoxy group; at C 1-6, linear or branched and optionally containing a silicon atom, a C 1-5 alkoxycarbonyl group, linear or branched, or a C 1-6 alkylsulfonamide group, linear or branched and optionally containing a silicon atom or a amino acid function, p "represents an integer between 0 and 4 inclusive, q" represents 0 or 1, 20 As examples of compounds of formula (XII), insoluble, filtering UV radiation, having an average size of part between 10 nm and 5 iam, the following derivatives may be mentioned: - 2,2'-p-phenylene bis (3,1-benzoxazin-4-one), sold in particular under the trade name of CYASORB UV- 3638® by CYTEC, 2,2 '- (4,4'-biphenylene) bis (3,1-benzoxazin-4-one), 3025094 119 - 2,2' - (2,6-naphthylene) ) bis (3,1-benzoxazin-4-one). I / Derivatives amide, sulfonamide or acrylonitrile carbamate Among the insoluble organic filters of the amide, sulfonamide or acrylonitrile carbamate derivative type, mention may be made of those corresponding to the following formula (XIII): NH- (XIII) in which: R10 represents a linear or branched C1-C8 alkyl group, n "'is 0, 1 or 2, X2 represents a divalent radical of formula - (C = O) -Ri - (C = O) -, - SO2 -R11- SO2- or - (C = O) -O-R11-0- (C = O) -, Y represents a radical - (C = O) -Ri2 or -SO2R13, R11 represents a single bond or a radical divalent C1-C30 alkylene or C3-C30 alkenylene, linear or branched, may carry one or more hydroxyl substituents and may contain, in the carbon chain, one or more heteroatoms selected from oxygen, nitrogen and of silicon, R12 represents a radical -OR14 or -NEIR14, R13 represents a linear or branched C1-C30 alkyl radical, or an unsubstituted or radically substituted phenyl ring; C1-C4 alkyl or alkoxy radicals R14 represents a C1-C30 alkyl or C3-C30 alkenyl radical, linear or branched, which may carry one or more hydroxyl substituents and may contain, in the carbon chain, one or more heteroatoms selected from oxygen, nitrogen and silicon atoms.

Although in formula (XIII) above, only the isomers in which the cyano substituent is in the cis position relative to the para-amino-phenyl substituent are represented, this formula should be understood to include also the corresponding trans-isomers; for each of the two double bonds and independently, the cyano and para-amino-phenyl substituents may be in the cis or trans configuration with respect to each other. By way of example, mention may be made of 2-ethylhexyl 2-cyano-3- [4- (acetylamino) phenyl] -acrylate dimer of formula: .1 / polyvalent metals Another particular family of insoluble organic insoluble filters The invention relates to polyvalent metal salts (eg Ca 2+, Zn 2+, Ba 2 +, M 3 + or Zr 4+) of organic sulphonic or carboxylic filters such as the polyvalent metal salts of sulphonated benzylidene camphor derivatives such as those described in US Pat. FR-A 2,639,347; polyvalent metal salts of sulfonated benzimidazole derivatives such as those described in EP-A-893119; polyvalent metal salts of cinnamic acid derivatives such as those described in JP-87 166 517. Mention may also be made of metal or ammonium or substituted ammonium complexes of organic UV-A and or UV-B as described in patent applications WO 93/10753, WO 93/11095 and WO 95/05150. Among the insoluble organic UV filters, there may also be mentioned the compound 1, 1 '- (1,4-piperazinediyl) bis [1 [244- (diethylamino) -2-hydroxybenzoyl] phenyl] methanone (CAS 919803-06 8) of the following structure: ## STR3 ## as described in WO 2007/071584; this compound being advantageously used in micronized form (average size of 0.02 to 2 μm) obtainable, for example, according to the micronization process described in applications GB-A-2 303 549 and EP-A-893119 and in particular under aqueous dispersion form. According to a particularly preferred form of the invention, the insoluble organic UV screening agents chosen from (i) the symmetrical triazine filters substituted by naphthalenyl groups or polyphenyl groups described in US Pat. No. 6,225,467, the application WO 2004/085412 will be used. (see compounds 6 and 9) or the document "Symetrical Triazine Derivatives" IP.COM IPCOM000031257 Journal, INC WEST HENRIETTA, NY, US (September 20, 2004) including 2,4,6-tris (di-phenyl) -triazine and 2,4,6-tris (terphenyl) -triazine which is incorporated in patent applications WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007, WO2006 / 034992, WO2006 / 034985, these compounds being advantageously used in micronized form (average particle size of 0.02 to 3 μm) obtainable for example according to the micronization process described in applications GB-A-2 303 549 and EP-A-893119 and in particular in the form aqueous dispersion; (Ii) methylene bis- (hydroxyphenylbenzotriazole) compounds of the following formula (IV): wherein the radicals T10 and T11, which may be identical or different, denote a C1-C18 alkyl radical which may be be substituted with one or more radicals selected from C 1 -C 4 alkyl, C 5 -C 12 cycloalkyl or aryl radical; (iii) and mixtures thereof.

According to a particularly preferred embodiment of the invention, the methylene bis (hydroxyphenyl benzotriazole) compounds of formula (IV) are in the form of an aqueous dispersion of particles having an average particle size which varies from 0.01 to 51 μm and more. preferably from 0.01 to 2 μm and more particularly from 0.020 to 2 μm with at least one surfactant having the structure C0E120 + 1 0 (C61-11005), in which n is an integer of 8 to 16 and x is the average degree of polymerization of the unit (C6E11005) and varies from 1.4 to 1.6 as defined above. Said surfactant is preferably used at a concentration ranging from 1 to 50% by weight and more preferably from 5 to 40% by weight relative to the benzotriazole filter and the amount of benzotriazole filter of formula (I) in the aqueous dispersion. preferably varies from 10 to 50% by weight and more preferably from 30 to 50% by weight relative to the total weight of the dispersion. The average particle diameter was measured by a particle size distribution analyzer of the Culter N4 PLUS® type manufactured by Bechman Coulter INC. According to a particularly preferred form of the invention, the methylene bis (hydroxyphenyl benzotriazole) compounds of formula (IV) may be in the form of an aqueous dispersion of particles having an average particle size ranging from 0.02 to 21 μm. and more preferably from 0.01 to 1.5 μm and more particularly from 0.02 to 1 μm in the presence of at least one polyglyceryl mono- (C 8 -C 20) alkyl ester having a degree of polymerization of glycerol of at least 5 such as the aqueous dispersions described in the application WO 2009/063392.

As examples of polyglyceryl mono- (C 8 -C 20) alkyl polyglycol surfactants, mention may be made of decaglyceryl caprate, decaglyceryl laurate, decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate, 3025094 isostearate and the like. 123 decaglyceryl, hexaglyceryl caprate, hexaglyceryl laurate, hexaglyceryl myristate, hexaglyceryl oleate, hexaglyceryl stearate, hexaglyceryl isostearate, pentaglyceryl caprate, pentaglyceryl laurate pentaglyceryl myristate, pentaglycerol oleate, pentaglyceryl stearate, pentaglyceryl isostearate. More particularly, use will be made of decaglyceryl caprate such as the products sold under the following trade names Sunsoft Q10Ye, Sunsoft Qiose, Sunsoft Q12Y®, Sunsoft Q12S®, Sunsoft M12J® by the company Taiyo Kagaku Co. Ltd., Nikkol. Decaglyn 1-L by Nikko Chemicals Co. Ltd., RYOTO-Polyglyceryl LioDe and L-7D® by Mitsubishi-Kagaku Co. Ltd., - Decaglyceryl laurate such as the products sold under the following trade names SUNSOFT Q14Y®, SUNSOFT Q14S®, SUNSOFT Q12Y®, Sunsoft Q12S®, Sunson M12J® by Taiyo Kagaku Co. Ltd., NIKKOL Decaglyn 1-M® by Nikko Chemicals Co. Ltd., RYOTO-Polyglycerylester M-10D and M-7D by Mitsubishi-Kagaku Co. Ltd., - Decaglyceryl stearate such as the products sold under the following trade names SUNSOFT Q18Y®, SUNSOFT Q18S®, SUNSOFT Q12Y®, Sunsoft Q12S®, Sunsoft M12J® by Taiyo Kagaku Co. Ltd., NIKKOL Decaglyn 1 -SV by Nikko Chemicals Co. Ltd., RYOTO-Polyglycerylester S-15D® by Mitsubishi-Kagaku Co. Ltd., - hexaglieryl caprate such as the products sold under the following trade names NIKKOL Hexaglyn 1-L ® by Nikko Chemicals Co. Ltd., GLYSURF 6ML by Aoki Oil Industrial Co. Ltd., UNIGLY GL-106® by Nippon Oil & Fats Co. Ltd., - hexaglyceryl myristate such as products sold under the trade names NIKKOL Hexaglyn 1-M®, NIKKOL Hexaglyn 1-Ove by Nikko Chemicals Co. Ltd, GLYSURF 6m by Aoki Oil Industrial Co., Ltd., UNIGLY GL-106 by Nippon Oil & Fats Co. Ltd., - Hexaglyceryl stearate such as the products sold under the following trade names NIKKOL Hexaglyn 1-M®, NIKKOL Hexaglyn 1-SV® by the 3025094 124 company Nikko Chemicals Co. Ltd., EMALEXMSG- 6K® by Nihon-Emulsion Co. Ltd., UNIGLY GL-106 by Nippon Oil & Fats Co. Ltd., - hexaglyceryl isostearate such as the products sold under the following trade names MATSUMATE MI-610® by Matsumoto Fine Chemical Co. Ltd., - pentaglyceryl caprate such as products sold under the following trade names SUNSOFT A10Ee, by Taiyo Kagaku Co. Ltd., - pentaglyceryl laurate such as the products sold under the trade names SUNSOFT Al2Ee, SUNSOFT A121Ee, by Taiyo 10 Kagaku Co. Ltd., - pentaglyceryl myristate such as the products sold under the trade names Sunsoft A14Ee, Sunsoft A141Ee, by Taiyo Kagaku Co. Ltd., - pentaglyceryl oleate such as the products sold under the following trade names SUNSOFT A17Ee, SUNSOFT A171Ee, by Taiyo Kagaku Co. Ltd., - pentaglyceryl stearate, such as the products sold under the following trade names SUNSOFT A18Ee, SUNSOFT A181Ee, by Taiyo Kagaku Co. Among these surfactants, it is preferred to use those having an HLB greater than or equal to 14.5 and more preferably greater than or equal to 15. As examples of polyglyceryl mono- (C 8 -C 20) alkyl polyglyceryl surfactants having a degree of polymerization. having a glycerol polymerization degree of at least 5 having an HLB greater than or equal to 14.5, mention may be made of decaglyceryl caprate, decaglyceryl laurate, decaglyceryl myristate, decaglyceryl oleate, stearate decaglyceryl, decaglyceryl isostearate, hexaglyceryl laurate, pentaglyceryl caprate, pentaglyceryl laurate, pentaglyceryl myristate, pentaglyceryl oleate, pentaglyceryl stearate. Examples of polyglycerol mono- (C 8 -C 20) alkyl polyglyceryl surfactants having a degree of polymerization having a glycerol polymerization degree of at least 5 having an HLB greater than or equal to 15 include decaglyceryl caprate, decaglyceryl laurate.

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

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

In the case of these aqueous dispersions, the compound methylene bis (hydroxyphenylbenzotriazole) of the formula (IV), the compound 2,2'-methylene-bis-4- (2H-benzotriazol-2-yl) -4- (1) will be used more particularly. , 1,3,3-tetramethylbutyl) phenol] of structure: Compound (a) such as the commercial product sold under the name TINOSORB M® by BASF which is an aqueous dispersion comprising decylglucoside, xanthan gum and propylene glycol (INCI name: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (and) Aqua (and) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum).

The insoluble organic UV filter (s) of the invention are present at a concentration of active material preferably ranging from 0.1 to 30% by weight, and more particularly from 0.5 to 20% by weight relative to the weight. total of the composition. B / INSOLUBLE UV INORGANIC FILTERS The inorganic UV filters used in accordance with the present invention are metal oxide pigments. More preferably, the inorganic UV filters of the invention are metal oxide particles having an average particle size of less than or equal to 0.50 μm, more preferably between 0.005 and 0.50 μm and even more preferentially between 0.01 and 0.2 μm, more preferably between 0.01 and 0.1 μm, and more preferably between 0.015 and 0.05 μm.

By "elementary size" is meant the size of non-aggregated particles. They may be chosen in particular from oxides of titanium, zinc, iron, zirconium, cerium or their mixtures.

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

The metal oxide pigments may be coated or uncoated. The coated pigments are pigments which have undergone one or more surface treatments of a chemical, electronic, mechanochemical and / or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (of titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin ), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

The coated pigments are more particularly titanium oxides coated with: - silica such as the product "Sunveil" from the company IKEDA, - silica and iron oxide such as the product "SUNVEIL F" from the company IKEDA, Silica and alumina such as the products "MICROTITANIUM DIOXIDE MT 500 SA" and "MICROTITANIUM DIOXIDE MT 100 SA" from the company TAYCA, "TIOVEIL" from the company TIOXIDE, 3025094 127 - alumina such as the products "TIPAQUE TTO-55 (B)" and "TIPAQUE TTO-55 (A)" from ISHIHARA, and "UVT 14/4" from SACHTLEBEN PIGMENT S, - alumina and aluminum stearate such as the products "MICROTITANIUM DIOXIDE MT 100 T, MT 100 TX, MT 100 Z, MT-01" from the company TAYCA, the products "Solaveil CT-10 W" and "Solaveil CT 100" from the company UNIQEMA and the product " Eusolex T-AVO "from MERCK, - silica, alumina and alginic acid such as the product" MT-100 AQ "of the company TAYCA tee, 10 - aluminum alumina and laurate such as the product "MICROTITANIUM DIOXIDE MT 100 S" from TAYCA, - iron oxide and iron stearate such as the product "MICROTITANIUM DIOXIDE MT 100 F "of the company TAYCA, - zinc oxide and zinc stearate such as the product" BR 351 "from the company TAYCA, - silica and alumina and treated with a silicone such as the products" MICROTITANIUM DIOXIDE MT 600 SAS "," MICROTITANIUM DIOXIDE MT 500 SAS "or" MICROTITANIUM DIOXIDE MT 100 SAS "from TAYCA, - silica, alumina, aluminum stearate and treated with a silicone such as the product" STT-30-DS "from the company TITAN KOGYO, - silica and treated with a silicone such as the product" UV-TITAN X 195 "from the company SACHTLEBEN PIGMENTS, - alumina and treated with a silicone such as the products "TIPAQUE TTO55 (S)" from ISHIHARA, or "UV TITAN M 262" from SACHTLEBEN 2 5 PIGMENTS, - triethanolamine such as the product "STT-65-S" from the company TITAN KOGYO, - stearic acid such as the product "TIPAQUE TTO-55 (C)" from ISHIHARA, 30 hexametaphosphate sodium such as the product "MICROTITANIUM DIOXIDE MT 150 W" from the company TAYCA. - TiO 2 treated with octyl trimethyl silane sold in particular under the trade name "T 805" by the company Degussa Silices, - TiO 2 treated with a polydimethylsiloxane sold in particular under the trade name "70250 Cardre UF TiO2SI3" by the company CARDRE, 5 - the anatase / rutile TiO2 treated with a polydimethylhydrogensiloxane sold in particular under the trade name "MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBIC" by the company COLOR TECHNIQUES. It is also possible to mention TiO 2 pigments doped with at least one transition metal such as iron, zinc, manganese and more particularly manganese. Preferably, said doped pigments are in the form of an oily dispersion. The oil present in the oily dispersion is preferably chosen from triglycerides including those of capric / caprylic acids. The oily dispersion of titanium oxide particles may further comprise one or more dispersing agents such as, for example, a sorbitan ester such as sorbitan isostearate, a polyoxyalkylenated fatty acid and glycerol ester such as TRI-PPG3 MYRISTYLETHER CITRATE and POLYGLYCERYL-3 POLYRICINOLEATE. Preferably, the oily dispersion of titanium oxide particles comprises at least one dispersing agent chosen from fatty acid esters and polyoxyalkylenated glycerol. More particularly, mention may be made of the oily dispersion of manganese-doped TiO 2 particles in capric / caprylic acid triglyceride in the presence of TRI-PPG-3 MYRISTYLETHER CITRATE and POLYGLYCERYL-3-POLYRICINOLEATE and SORBITAN ISOSTERATE by INCI name: TITANIUM DIOXIDE (and) TRI-PPG-3 MYRISTYLETHER CITRATE (and) POLYGLYCERYL-3 RICINOLEATE (and) SORBITAN ISOSTEARATE as the product sold in particular under the trade name OPTISOL TD50 by the company CRODA. Uncoated titanium oxide pigments are for example sold by the company Tayca under the trade names "MICROTITANIUM DIOXIDE 30 MT 500 B" or "MICROTITANIUM DIOXIDE MT600 B", by the company DEGUSSA under the name "P 25", by the company WACKHER under the name "transparent titanium oxide PW", by the company MIYOSHI KASEI under the name 3025094 129 "UFTR", by the company TOMEN under the name "ITS" and by the company TIOXIDE under the name "TIOVEIL AQ" . The uncoated zinc oxide pigments are, for example: those marketed in particular under the name Z-cote by the company Sunsmart; those marketed in particular under the name "Nanox" by the company Elementis; those marketed in particular under the name "Nanogard WCD 10 2025" by Nanophase Technologies; The coated zinc oxide pigments are, for example: those marketed in particular under the name "Zinc Oxide CS-5" by the company Toshibi (ZnO coated with polymethylhydrogenosiloxane); Those marketed in particular under the name "Nanogard Zinc Oxide FN" by Nanophase Technologies (as a 40% dispersion in Finsolv TN, Cu-Cu alcohol benzoate); those marketed in particular under the name "DAITOPERSION Zn-30" and "DAITOPERSION Zn-50" by the company Daito (dispersions in cyclopolymethylsiloxane / polydimethylsiloxane oxyethylenated, containing 30% or 50% of zinc oxides coated with silica and the polymethylhydrogensiloxane); those marketed in particular under the name "NFD Ultrafine ZnO" by the company Daikin (ZnO coated with perfluoroalkyl phosphate and a copolymer based on perfluoroalkylethyl dispersed in cyclopentasiloxane); Those marketed in particular under the name "SPD-Z1" by the company Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); those marketed especially under the name "Escalol Z100" by the company ISP (ZnO treated alumina and dispersed in the mixture methoxycinnamate ethylhexyl / PVP-hexadecene copolymer / methicone); those marketed in particular under the name Fuji ZnO-SMS-10 by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); 3025094 - those marketed in particular under the name "Nanox Gel TN" by Elementis (ZnO dispersed at 55% in benzoate of C12-C15 alcohols with polycondensate of hydroxystearic acid).

Uncoated cerium oxide pigments may be, for example, those sold under the name "COLLOIDAL CERIUM OXIDE" by the company RHONE P OULENC. Uncoated iron oxide pigments are for example sold by ARNAUD under the names "NANOGARD WCD 2002 (FE 45B)", "NANOGARD IRON FE 45 BL AQ", "NANOGARD FE 45R AQ", "NANOGARD WCD". 2006 (FE 45R) ", or by MITSUBISHI under the name" TY-220 ". The coated iron oxide pigments are for example sold by ARNAUD under the names "NANOGARD WCD 2008 (FE 45B FN)", "NANOGARD WCD 2009 (FE 45B 556)", "NANOGARD FE 45 BL 345", 15 "NANOGARD FE 45 BL", or by BASF under the name "OXYDE DE FER TRANSPARENT". Mention may also be made of mixtures of metal oxides, in particular titanium dioxide and cerium dioxide, including the titanium dioxide and cerium-coated cerium dioxide equivalent mixture, sold by the company IKEDA under the name "SUNVEIL". A ", as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as the product" M 261 "sold by the company SACHTLEBEN PIGMENTS or coated with alumina, with silica and with glycerine such as the product "M 211" sold by SACHTLEBEN PIGMENTS. According to the invention, titanium oxide pigments, coated or uncoated, are particularly preferred. The insoluble inorganic UV filters of the invention are preferably present in the compositions according to the invention at a content ranging from 0.1% to 50% by weight, more particularly from 0.1% to 40% by weight, and in particular from 0.5 to 30% by weight relative to the total weight of the composition.

As stated above, according to a particularly preferred embodiment, the UV filter (s) are chosen from water-soluble organic UV filters, liposoluble organic UV filters, and mixtures thereof.

According to one particular form of the invention, the composition comprises: at least one aqueous phase gelled with at least one non-starch hydrophilic gelling agent chosen from 2-acrylamido-2-methylpropanesulphonic acid (AMPSO) copolymers, crosslinked and or neutralized and more particularly a copolymer of AMPS® and of hydroxyethyl acrylate - at least one oily phase gelled by at least one lipophilic gelling agent chosen from hectorites modified with a C 10 to C 22 ammonium chloride, and more particularly a hectorite modified with di-stearyl dimethyl ammonium chloride. said phases forming a macroscopically homogeneous mixture therein; said composition further comprising at least one UV filter selected from water soluble organic UV filters, liposoluble organic UV filters, and mixtures thereof and preferably liposoluble organic UV filters. Aqueous Phase The aqueous phase of a composition according to the invention comprises water and optionally a water-soluble solvent.

By "water-soluble solvent" is meant in the present invention a liquid compound at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25 ° C and atmospheric pressure). The water-soluble solvents that can be used in the composition of the invention may also be volatile.

Among the water-soluble solvents that can be used in the composition according to the invention, there may be mentioned lower monoalcohols having from 1 to 5 carbon atoms, such as ethanol and isopropanol, glycols having from 2 to 8 atoms. carbon such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C3 and C4 ketones and C2-C4 aldehydes.

The aqueous phase (water and optionally the water-miscible solvent) may be present in the composition in a content ranging from 5% to 95%, more preferably from 30% to 80% by weight, preferably 40% by weight. at 75% by weight, relative to the total weight of said composition. According to another variant embodiment, the aqueous phase of a composition according to the invention may comprise at least one C2-C32 polyol.

For the purposes of the present invention, the term "polyol" means any organic molecule comprising at least two free hydroxyl groups. Preferably, a polyol according to the present invention is present in liquid form at room temperature. A polyol suitable for the invention may be a linear, branched or cyclic alkyl compound, saturated or unsaturated, bearing on the alkyl chain at least two -OH functions, in particular at least three -OH functions, and more particularly at least four functions -OH. The polyols which are particularly suitable for the formulation of a composition according to the present invention are those having in particular 2 to 32 carbon atoms, preferably 3 to 16 carbon atoms. Advantageously, the polyol may be, for example, chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, 1,3 propanediol, butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol and glycerol. polyglycerols, such as glycerol oligomers such as diglycerol, polyethylene glycols, and mixtures thereof. According to a preferred embodiment of the invention, said polyol is chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, glycerol, polyglycerols, polyethylene glycols, and mixtures thereof. In a particular embodiment, the composition of the invention may comprise at least propylene glycol. According to another particular embodiment, the composition of the invention may comprise at least glycerol. Oily phase For the purposes of the invention, an oily phase comprises at least one oil. The term "oil" means any fatty substance in liquid form at ambient temperature at atmospheric pressure.

An oily phase suitable for the preparation of the cosmetic compositions according to the invention may comprise hydrocarbon oils, silicone oils, fluorinated or not, or mixtures thereof. The oils may be volatile or non-volatile.

They can be of animal, vegetable, mineral or synthetic origin. According to an alternative embodiment, the oils of silicone origin are preferred. For the purposes of the present invention, the term "non-volatile oil" means an oil having a vapor pressure of less than 0.13 Pa. For the purposes of the present invention, the term "silicone oil" means an oil comprising at least one at least one silicon atom, and in particular at least one Si-O group. The term "fluorinated oil" means an oil comprising at least one fluorine atom. The term "hydrocarbon oil" means an oil containing mainly hydrogen and carbon atoms.

The oils may optionally include oxygen, nitrogen, sulfur and / or phosphorus atoms, for example as hydroxyl or acid radicals. By "volatile oil" is meant, within the meaning of the invention, any oil capable of evaporating on contact with the skin in less than one hour, at ambient temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic compound which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (101 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg). of Hg). Volatile oils Volatile oils can be hydrocarbon or silicone. Among the volatile hydrocarbon oils having from 8 to 16 carbon atoms, mention may be made especially of branched C 8 -C 16 alkanes, such as iso-alkanes (also known as isoparaffins) with C 8 -C 16, isododecane, isodecane and the like. isohexadecane and for example the oils sold under the trade names Isopars or permetyls, C8-C16 branched esters 3025094 134 such as isohexyl neopentanoate, and mixtures thereof. Preferably, the volatile hydrocarbon oil is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof, in particular from isododecane, isodecane and isohexadecane, and is especially isohexadecane.

It is also possible to mention volatile linear alkanes comprising from 8 to 16 carbon atoms, in particular from 10 to 15 carbon atoms, and more particularly from 11 to 13 carbon atoms, for example such as n-dodecane (C12). and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97, as well as their mixtures, the undecane-tridecane mixture, the mixtures of n-undecane (C11) and n- tridecane (C13) obtained in Examples 1 and 2 of WO 2008/155059 from Cognis, and mixtures thereof. Silicone volatile oils that may be mentioned include linear silicone volatile oils such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane and dodecamethylpentasiloxane. Cyclic silicone volatile oils that may be mentioned include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.

Nonvolatile oils Nonvolatile oils may, in particular, be chosen from hydrocarbon oils, fluorinated and / or nonvolatile silicone oils. As non-volatile hydrocarbon-based oils, mention may be made in particular of: hydrocarbon-based oils of animal origin, hydrocarbon-based oils of vegetable origin, synthetic ethers having from 10 to 40 carbon atoms, such as dicapryl ether, synthetic esters, such as the oils of formula R 1 COROR 2, in which R 1 represents a residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R 2 represents a hydrocarbon chain, in particular, a branched chain containing from 1 to 40 atoms of carbon provided R1 + R2 is 10. The esters may be, in particular, selected from alcohol and fatty acid esters, such as, for example, cetostearyl octanoate, esters of isopropyl alcohol, such as 3025094 isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, octyl stearate, hydroxylated esters, such as lactate. isostearyl, the hydroxyst octyl ester, ricinoleates of alcohols or polyhydric alcohols, hexyl laurate, esters of neopentanoic acid, such as isodecyl neopentanoate, isotridecyl neopentanoate, esters of isononanoic acid, such as isononyl isononanoate, sotridecyl isononanoate, polyol esters and pentaerythritol esters, such as dipentaerythritol tetrahydroxystearate / tetraisostearate, branched-chain carbon-containing liquid fatty alcohols and / or or unsaturated having from 12 to 26 carbon atoms, such as 2-octyldodecanol, isostearyl alcohol, oleic alcohol, - higher C12-C22 fatty acids, such as oleic acid, linoleic acid, linolenic acid, and mixtures thereof, non-phenyl silicone oils, for example caprylyl methycone, and phenyl silicone oils, for example phenyl trimethicones, phenyl dimethicones, phenyls, trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, and 2-phenylethyl trimethylsiloxysilicates, dimethicones or phenyltrimethicone of viscosity less than or equal to 100 cSt, trimethylpentaphenyltrisiloxane, and mixtures thereof; as well as the mixtures of these different oils. Preferably, a composition according to the invention comprises volatile and / or nonvolatile silicone oils. Such silicone oils are particularly preferred when the lipophilic gelling agent is an organopolysiloxane elastomer.

A composition according to the invention may comprise from 1% to 95% by weight, more preferably from 5% to 40% by weight, by weight of oil (s) relative to the total weight of said composition. As specified above, the gelled oily phase according to the invention may have a threshold stress greater than 1.5 Pa and preferably greater than 10 Pa. This threshold stress value reflects a gel-like texture of this oily phase.

Dyestuffs A composition according to the invention may further comprise at least one particulate or non-particulate matter, water-soluble or non-water-soluble, and preferably at least 0.01% by weight relative to the total weight of the composition. .

For obvious reasons, this amount is likely to vary significantly with regard to the intensity of the desired color effect and the color intensity provided by the dyestuffs in question and its adjustment is clearly within the competence of the man of the art. 'art. A composition according to the invention may comprise from 0.01% to 25% by weight, in particular from 0.1% to 25% by weight, in particular from 1% to 20% by weight and preferably from 5% to 18% by weight. % by weight of dyestuffs, relative to the total weight of said composition. As specified above, the dyestuffs that are suitable for the invention can be water-soluble but also fat-soluble.

For the purposes of the invention, the term "water-soluble dyestuff" means any generally organic compound, natural or synthetic, soluble in an aqueous phase or water-miscible and colorable solvents. As water-soluble dyes that are suitable for the invention, synthetic or natural water-soluble dyes may be mentioned, such as, for example, FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanin (beet), carmine, copper chlorophylline, methylene blue, anthocyanins (enocianin, black carrot, hibiscus, elderberry), caramel, riboflavin.

Water-soluble dyes are, for example, beet juice and caramel. For the purposes of the invention, the term "liposoluble coloring matter" means any generally organic compound, natural or synthetic, soluble in an oily phase, or solvents miscible with a fatty substance and capable of coloring.

As liposoluble dyes that are suitable for the invention, mention may in particular be made of fat-soluble, synthetic or natural dyes such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6 and DC Yellow. 11, DC Violet 2, 3025094 137 DC Orange 5, Sudan red, carotenes (13-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, yellow quinoline, annatto, curcumin. The particulate coloring materials may be present in a proportion of from 0.01% to 25% by weight, in particular from 0.1% to 25% by weight, in particular from 1% to 20% by weight and preferably from 5% to 18% by weight of particulate materials, based on the total weight of the composition containing them. It may especially be pigments, pearlescent agents and / or particles with metallic reflections.

The term "pigments" should be understood to mean white or colored, mineral or organic particles, insoluble in an aqueous solution, intended to color and / or opacify the composition containing them. A composition according to the invention may comprise from 0.01% to 25% by weight, in particular from 0.1% to 25% by weight, in particular from 1% to 25% by weight and preferably from 5% to 18% by weight. % by weight of pigments, relative to the total weight of said composition. Preferably, when the composition according to the invention is a makeup composition, it may comprise at least 5%, and preferably at least 3% by weight of pigments, relative to the total weight of said composition.

The pigments may be white or colored, mineral and / or organic. As inorganic pigments that may be used in the invention, mention may be made of oxides or dioxides of titanium, zirconium or cerium, as well as oxides of zinc, iron or chromium, ferric blue, manganese violet, ultramarine blue and chromium hydrate, and mixtures thereof.

It may also be a pigment having a structure which may for example be sericite / brown iron oxide / titanium dioxide / silica. Such a pigment is marketed for example under the reference Coverleaf NS or JS by the company Chemicals And Catalysts and has a contrast ratio close to 30. It can also be pigments having a structure which can be, for example, of type microspheres of silica containing iron oxide. An example of a pigment having this structure is that marketed by the company Miyoshi under the reference PC Ball PC-LL-100 P, this pigment consisting of silica microspheres containing yellow iron oxide. Advantageously, the pigments according to the invention are iron oxides and / or titanium dioxides.

By "nacres", it is necessary to include colored particles of any shape, iridescent or otherwise, in particular produced by certain shellfish in their shell or else synthesized, and which exhibit a color effect by optical interference. A composition according to the invention may comprise from 0% to 15% by weight of nacres, relative to the total weight of said composition. The nacres can be chosen from pearlescent pigments, such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with with an organic dye, as well as pearlescent pigments based on bismuth oxychloride. It can also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic dyestuffs. Mention may also be made, by way of example of nacres, of natural mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride.

Among the nacres available on the market, mention may be made of the nacres Timica, Flamenco and Duochrome (based on mica) marketed by ENGELHARD, the nacres Timiron marketed by Merck, nacres based on mica Prestige marketed by the Eckart company and the nacres based on Sunshine synthetic mica sold by the company Sun Chemical.

The nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or reflection. Advantageously, the nacres according to the invention are micas coated with titanium dioxide or iron oxide and bismuth oxychloride.

For the purposes of the present invention, the term "metal-reflecting particles" is intended to mean any compound the nature, size, structure and surface condition of which makes it possible for it to reflect the incident light, in particular in a non-iridescent manner.

The particles with a metallic sheen that can be used in the invention are in particular chosen from: particles of at least one metal and / or at least one metal derivative; particles comprising a substrate, organic or inorganic, monomaterial or multimaterial, at least partially covered by at least one metal-reflecting layer comprising at least one metal and / or at least one metal derivative; and - mixtures of said particles. Among the metals that may be present in said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te. Se and their mixtures or alloys. Ag, Au, Cu, Al, Zn, Ni, Mo, Cr, and mixtures or alloys thereof (eg, bronzes and brasses) are preferred metals. The term "metal derivatives" denotes compounds derived from metals, in particular oxides, fluorides, chlorides and sulphides. As an illustration of these particles, mention may be made of aluminum particles, such as those sold under the names Starbrite 1200 EAC® by Siberline and Metalure® by Eckart, and glass particles coated with a metal layer. especially those described in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

Hydrophobic treatment of dyestuffs The pulverulent dyestuffs as described above may be surface-treated, totally or partially, with a hydrophobic agent, to make them more compatible with the oily phase of the composition of the invention, in particular so that they have good wettability with oils. Thus, these treated pigments are well dispersed in the oily phase. Hydrophobic-treated pigments are described in particular in document EP-A-1086683. The hydrophobic treatment agent may be chosen from silicones such as methicones, dimethicones and perfluoroalkylsilanes; fatty acids such as stearic acid; metallic soaps such as aluminum dimyristate, aluminum salt of hydrogenated tallow glutamate; perfluoroalkyl phosphates; hexafluoropropylene polyoxides; perfluoropolyethers; amino acids; amino acids N-3025094 acyl or their salts; lecithin, isopropyl trisostearyl titanate, isostearyl sebacate, and mixtures thereof. The term alkyl mentioned in the compounds mentioned above denotes in particular an alkyl group having from 1 to 30 carbon atoms, preferably having from 5 to 16 carbon atoms. Advantageously, a composition according to the invention may further comprise one or more filler (s) conventionally used in skincare and / or makeup compositions. These fillers are colorless or white, solid particles of all shapes, which are in an insoluble form and dispersed in the medium of the composition. Of mineral or organic nature, natural or synthetic, they make it possible to confer on the composition containing them softness, dullness and uniformity in makeup. In addition, these fillers advantageously make it possible to fight against various attacks such as sebum or sweat. As an illustration of these fillers, mention may be made of talc, mica, silica, kaolin, poly-13-alanine and polyethylene powders, tetrafluoroethylene polymer powders (Teflon®), lauroyl-lysine, starch, boron nitride, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industry), acrylic acid copolymers, silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite, barium sulfate, aluminum oxides, polyurethane powders, composite fillers, hollow silica microspheres, and glass or ceramic microcapsules. It is also possible to use particles, which are in the form of portions of hollow spheres, as described in patent applications JP-2003 128 788 and JP-2000 191 789. In particular, such fillers may be present in a composition according to the invention in a content of between 0.01% and 30% by weight, in particular between 0.1% and 25% by weight, in particular between 1% and 20% by weight, relative to the total weight of the composition.

According to one embodiment of the invention, a composition may comprise at least solid particles such as pigments and / or dispersant agents. Advantageously, a composition according to the invention may further comprise a dispersing agent. Such a dispersing agent may be a surfactant, an oligomer, a polymer or a mixture of several of them. According to a particular embodiment, a dispersing agent according to the invention is a surfactant. According to one particular variant, a composition according to the invention comprises at least 1% by weight of surfactant relative to the total weight of the composition, or even is devoid of surfactant. Active For a particular care application, a composition according to the invention can include at least one moisturizing agent (also called humectant). Preferably, the moisturizing agent is glycerin. The moisturizing agent (s) may be present in the composition in a content ranging from 0.1% to 30% by weight, especially from 0.5% to 15% by weight, or even from 1% to 10% by weight, relative to the total weight of said composition. Other active agents which can be used in the composition of the invention include, for example, vitamins. Preferably, a composition according to the invention comprises at least one active ingredient. It falls within the routine operations of those skilled in the art to adjust the nature and the quantity of the additives present in the compositions according to the invention, so that the desired cosmetic properties of these are not affected. According to one embodiment, a composition of the invention may advantageously be in the form of a photoprotective composition for the care of the skin and / or keratinous fibers, in particular the hair, in particular the body and the face.

According to another embodiment, a composition of the invention may advantageously be in the form of a make-up makeup base composition. According to another embodiment, a composition of the invention may advantageously be in the form of a foundation. According to one embodiment, a composition of the invention may advantageously be in the form of a make-up composition for the skin and in particular the face. It can be an eyeshadow or a blush. According to another embodiment, a composition of the invention may advantageously be in the form of a lip product, in particular a lipstick. Such compositions are especially prepared according to the general knowledge of those skilled in the art. Throughout the description, including the claims, the phrase "having one" should be understood as being synonymous with "having at least one", unless the opposite is specified. Expressions "between ... and ..." and "from ... to ..." must be understood as inclusive terms unless otherwise specified. The invention is illustrated in more detail by the examples presented hereinafter.

Unless otherwise indicated, the amounts indicated are expressed as a percentage by weight. Methodology for dynamic rheology measurements in oscillation These are harmonic rheological measurements that measure the elastic modulus.

The measurements are carried out using a Haake RS600 rheometer on a product at rest, at 25 ° C. with a plane plane 60 mm and a 2 mm gap. The measurements in harmonic regime make it possible to characterize the viscoelastic properties of the products. The technique involves subjecting a material to a sinusoidally varying stress over time and measuring the response of the material to that stress. In a field where the behavior is linear viscoelastic (zone where the deformation is proportional to the stress), the constraint (T) and the deformation (y) are two sinusoidal functions of the time which are written in the following way: (t) = ro sin (wt) y (t) = yo sin (wt + δ) where: ro represents the maximum amplitude of the stress (Pa); yo represents the maximum amplitude of the deformation (-); = 2IN represents the pulsation (rad.s-1) with N representing the frequency (Hz); and S represents the phase shift of the stress with respect to the deformation (rad). Thus, the two functions have the same angular frequency but they are out of phase by an angle δ. According to the phase shift S between r (t) and y (t), the behavior of the system can be apprehended: - If S = 0, the material is purely elastic; If S = II / 2, the material is purely viscous (Newtonian fluid); and - If 0 <S <II / 2, the material is viscoelastic. In general, the stress and the deformation are written in complex form: T * (t) = To eiwi y * (t) = yo e (word + Ô) A complex modulus of rigidity, representing the overall resistance of the material the deformation whether of elastic or viscous origin, is then defined by: G * = r * / y * = G '+ iG "Where: G' is the modulus of conservation or elastic modulus which characterizes the stored energy and totally restored during a cycle, G '= (ro / yo) cos S, and G "is the loss modulus or viscous modulus which characterizes the energy dissipated by internal friction during a cycle, G "= (ro / yo) sin δ The parameter adopted is the modulus of average stiffness G * measured at the plateau 30 measured at a frequency of 1 Hz.

EXAMPLES In the following tables, the amount of each compound is given in% by weight / total weight of the composition. The following formulas are prepared so that the mass percentage of the oily phase, the mass percentage of the aqueous phase, the mass percentage of oily gelling agent, the mass percentage of aqueous gelling agent, are constant. mass percentage of UV filters. All other constituents of the formulas are present in the same mass percentage. Compounds Compositions Example 1 Example 2 Comparative Completion (Composition gel / gel) (direct emulsion) PHASE B Homosalate 4 4 LIPOPHILE sold under the name Neo Heliopan HMS PBF by Symrise Ethylhexyl salicylate 2 2 sold under the name Neo Heliopan OS by Symrise Octocrylene marketed under The name Uvinul N53 9 T by BASF Butyl methoxydibenzoylmethane 4 4 sold under the name Avobenzone by MFCI Bis-ethylhexyloxyphenol 2 2 methoxyphenyl triazine sold under the name Tinosorb S by BASF Ethylhexyl triazone 11 marketed under the name Uvinul T150 by BASF Disteardimonium Hectorite 2,69 2,69 marketed under the name Bentone 38 VCG by Element s Silylated silica sold under 1 1 the name DC V% -2270 Aerogel fine particles by Dow Corning Dimethicone sold under 71 7.1 the name DC Toray SH200 C Fluid 5cs by Dow Corning Dimethicone and Dimethicone 15.4 15.4 crosspolymer sold under the name DC 9041 Silicon Elastomer Blend by Dow Corning Stearic Acid marketed - 1.5 under the name Radiacid 0461 by Oleon 3025094 Compounds Example 1 Example 2 Comparative Conformity (Gel / Gel Composition) (Direct Emulsion) Glyceryl Stearate and PEG-100 - 15 Stearate marketed under the name Simulsol 165 by Seppic Denat alcohol marketed under 5.31 5.31 the name Ethanol SDA 40B 200 Proof by Sasol PHASE A Water-deionized water 38.35 38.35- HYDROPHILE Disodium EDTA marketed 0.2 0.2 under the name EDETA BD by BASF Caprylyl glycol marketed under the name marketed under the name Dermasoft Octiol by Dr. Straetmans 07 07 Phenoxyethanol marketed under the name Sepicide LD by Seppic 02 02 Glycerine marketed under the 6.6 6.6 name Glycerine USP by VVF Triethanolamine marketed - 0.45 under the name Triethanolamine 99% Dow Chemical Potassium cetyl phosphate - 1 sold under the name Amphisol K by DSM Nutritional Products Hydroxyethyl acrylate / sodium 445 - acryloylmethyl taurate copolymer marketed under the name Sepinin EMT 10 by Seppic Preparation of compositions Preparation of lipophilic phases L The fatty phase is gelled by at least airgel, an oily gelling agent with or without organic or particulate filters. In Example 1, the fatty phase is gelled by airgel associated with bentone. The example outside the invention 2 is also gelled by the same gelling agents. In a first step, all the lipophilic and hot-soluble raw materials are weighed in a beaker and solubilized with mechanical stirring at 80 ° C. As soon as the filter solution is macroscopically clear, the oily gelling agents are added with mechanical stirring using a "deflocculator". In obtaining a homogeneous gelled phase, the solvents are added under the same mechanical stirring. The gel obtained is homogeneous. Preparation of hydrophilic phases H The components of the aqueous phase are weighed in a beaker and placed under stirring. The aqueous phase is gelled with at least one aqueous gelling agent with or without organic or particulate filters. In Example 1, the aqueous phase is gelled with Sepinov EMT 10.

The aqueous gelling agent is introduced into the aqueous solvents with stirring using a "deflocculator" at room temperature. The gel obtained is homogeneous The aqueous phase of the example outside the invention 2 is not gelled by Sepinov EMT 10, but contains an equivalent mass percentage of surfactants and associated neutralizer.

Procedure of Gel / Gel-Example In Accordance With the lipophilic and hydrophilic phases being macroscopically homogeneous, the gel / gel is prepared by mixing the two phases in a mixer of the "Petri" type equipped with a tank and an axial blade. with moderate stirring for 4 minutes.

The final gel is characterized by a macroscopically homogeneous, bicontinuous dispersion. Method of Preparation of the Emulsion - Comparative Example 2 Since the lipophilic and hydrophilic phases are macroscopically homogeneous, the emulsion is prepared by introducing the L phase into the H phase with stirring using a rotor homogenizer. -stator under a stirring speed of 4500 RPM for 20 minutes. The emulsion is cooled to room temperature. The final emulsion is characterized by drops of size between 1 lm and 20um.

Measurements The SPF, PPD and sensory analysis of these compositions 1 and 2 were measured.

In vitro Evaluation Protocol for Filtering Efficiency (SPF) The sun protection factor is determined according to the "in vitro" method described by B. L. Diffey in J. Soc. Cosmet. Chem. 40, 127-133, (1989). The measurements were carried out using a UV-1000S spectrophotometer from the company Labsphere. Each composition is applied to a rough PMMA plate, in the form of a homogeneous and regular deposition at a rate of 1 mg / cm 2. Protocol for In Vitro PPD Measurement The in vitro PPD index measurements were carried out under the same conditions using a UV-1000S spectrophotometer from Labsphere. Each composition is applied to a rough PMMA plate, in the form of a homogeneous and regular deposition at a rate of 1 mg / cm 2. The value "UV-A Index ppd: Action Spectrum" Persistent Pigment Darkening "is extracted. The UVA PPD sun protection factor (FP UVAppd) is expressed mathematically by the ratio of the UV-A radiation dose required to reach the UV filter pigmentation threshold (MPPDp) on the UV-A radiation dose required. to reach the threshold of pigmentation without UV filter (MPPDnp). MPPDp FP UVA ppD - 25 Evaluation protocol of the sensory properties of formulas on the skin The sensory properties of the formulas on the skin are evaluated by applying the formula on a forearm at a rate of 2 mg / cm 2 and observation of a time drying time equal to 2 minutes. The freshness is assessed during the application while the greasy and soft appearance is appreciated after application between the fingers and the forearm surface. MPPDnp 3025094 148 Results Results Test property Example 1 Comparative Example 2 SPF in vitro 43.9 +/- 4.8 21.3 +/- 3.9 PPD in vitro 21.8 +/- 2.1 10.4 +/- 1,1 Sensory analysis Fresh on application, softer Toucher plus gras These results show that the composition 1 of the invention makes it possible to obtain a level of filtering efficiency greater than the composition 2, direct emulsion with 5 airgel, while showing improved sensoriality.

Claims (19)

REVENDICATIONS1. Composition, in particular cosmetic makeup and / or care of keratin materials, comprising: at least one aqueous phase gelled with at least one non-starch hydrophilic gelling agent; at least one oily phase gelled with at least one selected lipophilic gelling agent; among hydrophobic silica aerogels; said phases forming a macroscopically homogeneous mixture therein; said composition further comprising at least one UV filter. 2. Composition according to the preceding claim, wherein the or UV filters are present in whole or in part, and preferably only in the gelled aqueous phase or are present in whole or in part, and preferably only in the phase oily gelled. 3. Composition according to one of the preceding claims wherein the hydrophilic gelling agent is selected from synthetic polymeric gelling agents, natural or non-starch polymeric gelling agents, mixed silicates and pyrogenic silicas, and mixtures thereof. 4. Composition according to the preceding claim, wherein the hydrophilic gelling agent is chosen from crosslinked polymers of ammonium acrylamido-2-methyl propane sulfonate, copolymers of AMPS® and of hydroxyethyl acrylate, copolymers acrylate / Cio- C30-alkylacrylate and crosslinked (meth) acrylic acid homopolymers, preferably copolymers of AMPS® and hydroxyethyl acrylate. 5. Composition according to the preceding claim, wherein the lipophilic gelling agent chosen from silylated silicas. 6. Composition according to one of the preceding claims comprising an additional lipophilic gelling agent chosen from additional particulate gelling agents, semi-crystalline polymers, dextrin esters, hydrogen bonded polymers, hydrocarbon block copolymers and mixtures thereof. A composition according to any one of the preceding claims, comprising: at least one non-starch hydrophilic gelling agent selected from 2-acrylamido-2-methylpropanesulphonic acid (AMPS®) copolymers, cross-linked and or neutralized, and more particularly the copolymers of AMPS® and of hydroxyethyl acrylate and at least one lipophilic gelling agent chosen from hydrophobic silica aerogels, at least one UV filter and, optionally, an additional gelling agent chosen from particulate gelling agents and semi-crystalline polymers. crystalline esters, dextrin esters, hydrogen bonded polymers, hydrocarbon block copolymers and mixtures thereof, and in particular modified clays and more particularly hectorites modified with di-stearyl dimethyl ammonium chloride. 8. Composition according to any one of the preceding claims, in which the UV-screening agent (s) is (are) chosen from water-soluble organic UV-screening agents, liposoluble organic UV-screening agents, and mixtures thereof, preferably liposoluble organic UV-screening agents. 9. Composition according to any one of the preceding claims, containing the aqueous and oily phases in an aqueous phase / oily phase weight ratio of 95/5 to 5/95, preferably 30/70 to 80/20. 10. Composition according to any one of the preceding claims, further comprising at least solid particles such as pigments and / or fillers. 11. Composition according to any one of the preceding claims, further comprising volatile and / or nonvolatile silicone oils. 12. A composition according to any one of the preceding claims, further comprising at least one moisturizing agent, preferably glycerine. 13. A process for preparing a composition, in particular a cosmetic makeup and / or skincare keratin comprising at least a step of mixing: an aqueous phase gelled with at least one non-starch hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent, said lipophilic gelling agent being chosen from hydrophobic silica aerogels; said phases forming a macroscopically homogeneous mixture therein; Said composition further comprising at least one UV filter. 14. Method according to the preceding claim, comprising a step of mixing at least two gelled phases. 15. A process according to any one of claims 13 or 14, wherein the mixing is carried out at ambient temperature. 16. A cosmetic process for making up and / or caring for keratinous substances, in particular the skin of the body and / or face, and / or keratinous fibers, in particular the hair, comprising at least one step of applying to said material keratin composition as defined in any one of claims 1 to 12. 17. A cosmetic process for making up and / or caring for keratinous substances, in particular the skin of the body and / or face, and / or keratinous fibers, in particular the hair, comprising at least the application on said keratinous substances of a macroscopically homogeneous composition obtained by extemporaneous mixing, before application or at the time of application to said keratinous material, of at least one aqueous phase gelled with at least one non-starch hydrophilic gelling agent, and at least one gelled oily phase; by at least one lipophilic gelling agent chosen from hydrophobic silica aerogels; said composition further comprising at least one UV filter. 18. Cosmetic process for limiting the darkening of the skin, and / or for improving the color and / or homogeneity of the complexion, comprising the application on the surface of the keratinous material of a composition as defined according to US Pat. any of claims 1 to 12. 19. Cosmetic process for preventing and / or treating the signs of aging of a keratinous material, comprising the application on the surface of the keratinous material of a composition as defined according to any one of Claims 1 to 12.