FR2798663A1 - Gel used in cosmetic compositions comprises water soluble film forming sulfonated oligomeric terephthalic copolyester and suspension of elastomeric organopolysiloxane in aqueous phase - Google Patents

Abstract

Gel comprises a water soluble film forming sulfonated polymer as a gelling agent and particles of an at least partially crosslinked solid elastomeric organopolysiloxane in suspension in an aqueous phase.

Description

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The present invention relates to an aqueous gel comprising a particular hydrophilic sulfonated polymer-type hydrophilic gelling agent and an aqueous dispersion of organopolysiloxane and a composition comprising the same. The present invention relates to an aqueous gel comprising a water-soluble sulfonated film-forming polymer and an aqueous dispersion of organopolysiloxane. comprising in particular intended for the cosmetic and / or dermatological fields. The invention also relates to the use of this gel and / or this composition for the makeup of the skin and / or keratin materials and / or mucous membranes of humans. This gel may be in the form of a paste or a solid product, in particular a stick.

Cosmetic compositions, in particular make-up compositions such as lipsticks, foundations, body make-up products, concealer, eye shadow or powders, generally comprise fatty substances such as oils and / or waxes, and a particulate phase generally composed of fillers and pigments. They may thus be in the form of a gel, in the form of a stick or stick or in the form of a soft paste, such as for example certain foundations, eyeshadows or lipsticks.

These compositions, when they are applied to the skin, the mucous membranes or the semi-mucous membranes, have the disadvantage of transferring. By this is meant that the composition is capable of being deposited, at least in part, on certain supports with which it is brought into contact, such as, for example, a glass, a garment or the skin.

By being deposited, said composition leaves a mark on said support. It follows therefore a poor persistence of the composition on the skin or mucous membranes, hence the need to regularly renew its application.

Moreover, the appearance of unacceptable traces on certain clothes and in particular on blouse collars may exclude some women from the use of this type of makeup.

Another disadvantage of these compositions lies in the migration problem. It has indeed been found that certain compositions have a tendency to propagate inside fine lines and / or wrinkles of the skin, in the case of foundations; in the fine lines around the lips, in the case of lipsticks; in the folds of the eyelid, in the case of eyeshadow. In the case of eye shadows, the appearance of streaks in the makeup, generated by the movements of the eyelids, has also been observed.

All these phenomena generate an unsightly effect that we obviously want to avoid.

For several years, many cosmeticians have been interested in cosmetic compositions, including lipsticks, foundations or

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 core of 'no transfer' body make-up products. Thus, today's so-called 'no transfer' make-up products are often obtained by forming a polymer film by evaporation of a solvent.

It is also known that the presence of volatile oils within these make-up products improves their 'no transfer' properties. It is possible to associate with these volatile oils silicone compounds.

However, if it is now known that the combination of volatile oils with certain silicone compounds makes it possible to obtain a satisfactory 'transfer-free' result, it nevertheless has the disadvantage of driving, after evaporation of the volatiles, to a film whose comfort is not optimal.

 As a result, current make-up products known as 'no-transfer' are often uncomfortable after drying and often have a dry, non-moisturizing film.

 Moreover, it is particularly advantageous to have in cosmetics products in the form of sticks insofar as such products are very practical to use, they are easily transportable, the product is not likely to flow.

 However, conventional sticks are often formulated based waxes and have some disadvantages in addition to those already described above: they have a bold character that is not appreciated by users and they lack freshness on application.

 In addition, it is difficult to introduce hydrophilic active agents.

 To provide hydration, comfort and freshness, we therefore seek more and more makeup sticks including an aqueous phase. It is of course known to make non-greasy sticks such as deodorant sticks but these are often formulated with soaps such as sodium stearate or triethanolamine as a gelling agent and they thus have a basic pH that is aggressive for the skin and poor compatibility with makeup pigments.

 French application No. 9811361 discloses aqueous solid gels having good properties without transfer. However, these gels are particularly uncomfortable. They are rough. After drying, the film may crack with friction and you may feel tears and dryness of the skin.

 There is therefore still a need for products, in particular make-up products, which transfer little or nothing (that is to say products without transfer) while having good cosmetic properties, in particular properties of slipperiness. application, as well as qualities of softness, hydration and comfort after makeup (no tugging and no drying).

 Now, the Applicant has surprisingly found that by combining a particular hydrophilic gelling agent of sulfonated polyester type with a suspension

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 In a particular silicone rubber powder, it was possible to produce a gel, particularly solid gel, of 'no transfer' makeup having excellent qualities of comfort, softness, coverage and non-friability of the film and of which the freshness effect persists over time.

Makeup products are thus produced which are not only 'non-transferable' but which also have good cosmetic properties, in particular comfort and hydration.

The invention therefore relates to a gel characterized in that it comprises in an aqueous phase: - i) at least one hydrophilic gelling agent of sulfonated water-soluble film-forming polymer type, - ii) at least partially solid elastomeric organopolysiloxane particles crosslinked in suspension in said aqueous phase.

The gels according to the invention have excellent qualities of non-transfer and non-migration after evaporation of the aqueous phase. In addition, they are comfortable, do not pull the skin and do not leave feeling of dryness after application. They leave a pleasant feeling of freshness on the skin. They leave the body soft and dull.

When the gels according to the invention are solid, they are easily transportable, do not flow, are very homogeneous and easy to apply. Taking the product is easy, it can be done directly on the body or with the finger or with the brush or with the sponge, by taking a sufficient quantity of product, easy to apply then on the skin of homogeneous way, without require prior mooring. The makeup obtained is uniform and homogeneous. The film does not crack, does not crumble and resists rubbing.

These gels are stable in time and temperature. Thus, after being kept for two months at room temperature or at 45 ° C., they show no phenomenon of syneresis (exudation) or phase shift: their appearance and their hardness is stable fifteen days after the formulation of the product.

The gels according to the invention do not exude, even at low levels of gelling agent, and they do not necessarily require the intervention of a particular preparation technique. They provide the application a feeling of great freshness while maintaining good cosmetic properties, especially softness.

The particular hydrophilic gelling agents used according to the invention are water-soluble film-forming sulfonated polymers.

For the purposes of the present application, the term "gelling agent" means a compound which, in the presence of a solvent such as water, creates more or less strong intermacromolecular bonds, thus inducing a three-dimensional network which freezes said solvent. In the present application, the term "film-forming polymer" means a polymer capable of forming on its own or in the presence of an auxiliary filamentary agent.

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 cation, an isolatable film after application of the composition comprising it on the skin. In the present application, the term "water-soluble polymer" is understood to mean a polymer which is solubilized in the aqueous phase. This polymer is not in the form of an aqueous dispersion within the gel according to the invention.

Preferably, the hydrophilic gelling agents according to the invention are sulphonated polyesters. More preferably, they are terephthalic copolyester oligomers comprising essentially repeating dicarboxylate units of formula (I): [-CO-A-CO-O- (CH 2 -CH 2 O) n-] (I) in which - A represents a grouping 1,4-phenylene, sulfo-1,3-phenylene and optionally 1,3-phenylene, n is from 1 to 4, at least 35 mol% of said units of formula (I) being units of formula (I); ) for which A represents a 1,4-phenylene group and n is equal to 1; at least 7 mol% of said units of formula (I) being units of formula (I) for which A represents a sulfo-1 group; , 3-phenylene, the weight-average molecular weight of said copolyester oligomers being less than 20,000, preferably less than 15,000.

Preferably, at least 40 mol%, and more preferably between 40 and 90 mol% of the units of formula (1) are units of formula (I) for which A represents a 1,4-phenylene group and n is equal to 1.

Preferably, at least 10 mol%, more preferably between 10 and 25 mol% of the units of formula (I) are units of formula (I) for which A represents a sulpho-1,3-phenylene group.

The ends of the chains of said oligomers copolyesters may be similar or different and represented essentially by the groups of formula (I '): -CO-A-CO-O- (CH 2 -CH 2 -O) nH (I') in which A and n are defined above.

Said oligomers may also have, at the chain ends, and in a minor amount, groups of formulas -A-CO-OH -A-CO-OR formulas in which A is defined above and R represents a C 1 -C 4 alkyl group. .

When A represents a sulfo-1,3-phenylene group, it is more particularly

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 alkali metal sulphonate, especially sodium or potassium sulphonate, or mono-, di-, tri- or tetra-lower alkylammonium sulphonate. Lower alkylammonium is preferably an ammonium whose alkyl radical (s) are lower alkyl, preferably C 1 -C 6 alkyl. Preferably, it is a sodium sulfonate.

The oligomer copolyester may optionally comprise up to 20 mol%, preferably from 0.5 to 5 mol% of units of formula (I) for which A represents a 1,3-phenylene group.

According to a preferred embodiment of the invention, the oligomer copolyester above has a molecular weight in weight ranging from 5,000 to 14,000, and more preferably from 8,000 to 10,000.

The weight-average molecular masses are measured by gel permeation chromatography in dimethylacetamide containing 10-2N LiBr at 100 C. The results are expressed in polystyrene equivalents.

Said oligomers copolyesters can be obtained by the usual processes for the preparation of polyesters by molten route, solvent route or interfacial route, processes involving reactions: esterification of diacids and diols and polycondensation. transesterification of diesters and diols and polycondensation. of self-condensation of hydroxy acids. Schotten-Baumann using diols and acid chlorides and polycondensation. for the polymerization of lactones by controlling the minimum content of units of formula (I) for which A represents a 1,4-phenylene group and n is equal to 1, similar to the initial stoichiometric ratios of the different monomers and the control of the side reactions .

A particularly advantageous method of preparation is that by transesterification / polycondensation and / or esterification / polycondensation by melt using a transesterification and / or esterification catalyst.

The control of the structure is obtained by controlling the minimum content of units of formula (I) for which A represents a 1,4-phenylene group and n is equal to 1, similar by the initial stoichiometric ratios of the various diacid monomers and / or diesters and diol and by use of an etherifying limiting agent, limiting agent which can be a basic compound such as aliphatic or aromatic amines or an alkali or alkaline earth metal hydroxide or acetate.

The control of the molecular weight is obtained in a manner known to those skilled in the art, by appropriate compromise between pressure, temperature and time.

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The terephthalic copolyester oligomers used according to the invention may be prepared by esterification and / or transesterification / polycondensation of a monomeric composition based on: - acid, anhydride or diester terephthalic (Tp) - acid, anhydride or sulfoisophthalic diester ( Slp) - optionally acid, anhydride or isophthalic diester (Ip) - and ethylene glycol (EG) in relative amounts corresponding to: * a molar ratio (Slp) / [(Tp) + (Slp) + (lp) )] of at least 7/100, preferably at least 10/100, most preferably 10/100 to 25/100 * a molar ratio (Ip) / [(Tp) + (Slp) + (lp)) ] of not more than 20/100, preferably not more than 5/100 * a molar ratio (EG) / [(Tp) + (Slp) + (Ip)] of 2/1 to 3/1. in the presence of an esterification and / or transesterification catalyst and an etherification limiter.

The terephthalic monomer (Tp) is preferably used in the form of lower diester (C1-C4 dialkyl diester), dimethyl preferably.

The sulfoisophthalic monomer (Slp) is preferably used in the form of an alkali metal sulphonate (in particular sodium) of lower diester (of C1-C4 alkyl), preferably of methyl. Dimethyl 5-sodiooxysulfonyl isophthalate may be particularly mentioned.

The optional isophthalic monomer (Ip) is preferably used in the form of isophthalic acid.

When all the "diacid" monomers are used in the form of diesters, the transesterification (interchange) operation between these "diacid" monomers and the ethylene glycol is carried out at a temperature greater than or equal to 130 ° C., preferably of the order 140 to 220 ° C and most particularly of the order of 180 to 220 ° C; at this temperature the methanol (preferential case of the methyl diesters) formed is removed from the reaction medium, preferably by distillation.

This interchange operation is carried out in the presence of a metal transesterification catalyst and an etherification limiter. Said catalyst is preferably a metal carboxylate, such as manganese acetate, zinc acetate, cobalt acetate or calcium acetate, or an organic or inorganic titanate, such as butyl titanate , nitrilo-2,2 ', 2 "-triethyl titanate (or titanium aminotriethanolate also acting as an etherification limiter) or calcium titanate, the preferred catalysts are organic titanates; in amounts of the order of at least 0.001% by weight expressed as titanium, preferably of the order of 0.002% to 0.02% by weight of titanium relative to the weight of reactants present.

The etherifying limiting agent may be a basic compound such as amines

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 aliphatic or aromatic (triethanolamine, guanidine carbonate, dimethylaniline, naphthylamine ...) or a hydroxide or acetate of alkali or alkaline earth metals (sodium acetate, potassium, sodium benzoate ...). It is generally used in an amount of the order of 0.001% to 0.05% relative to the weight of reagents present.

The duration of the interchange operation is 1 to 4 hours; it is generally of the order of 2 to 3 hours.

When more than 90% of the theoretical amount of methanol has been distilled, the excess polyol is removed by raising the temperature of the reaction medium to 230 C.

The polycondensation operation is preferably carried out at a temperature of the order of 230 to 280 ° C., preferably of the order of 240 to 260 ° C., in another reactor previously heated to this temperature and progressively evacuated to at a pressure of up to 10 Pa; Pressure reduction up to about 10 millibar lasts about 40 minutes.

The polycondensation operation takes place with elimination of polyol molecules, this operation is stopped when the driving torque of the stirring shaft indicates a value equivalent to approximately 0.5 to 5 meters.newton for a temperature of 250 ° C. the reaction mass and an agitation speed of 80 rpm of an anchor-shaped mobile in a 7.5 liter reactor. The vacuum is then broken with nitrogen, and the polymer is poured into an ingot mold; after cooling, the polymer is ground.

 When one of the "diacid" monomers is present in diacid or anhydride form and the other (s) in the form of diester (s), said oligomers copolyesters are obtained by first carrying out a transesterification operation of the monomers diesters with ethylene glycol under the conditions described above, followed by an esterification operation in the middle of the diacid or anhydride monomer with ethylene glycol, and then polycondensation under the conditions described above, the total amount of ethylene glycol being distributed between the two operations (transesterification and esterification).

 If necessary, the esterification operation is carried out by adding to the reaction medium resulting from the transesterification operation, the monomer in diacid or anhydride form and ethylene glycol previously suspended, at a temperature corresponding to that of the end of the interchange temperature; the introductory period is of the order of 1 hour.

This esterification operation is carried out at a temperature of the order of 230 to 280 ° C., preferably of the order of 250 to 260 ° C., in the presence of a catalyst of the same type as that of transesterification and an agent etherification limiter.

The operation is carried out in the presence of the same types of catalyst and etherification limiter that those implemented during the transesterification operation, and in the same proportions.

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The reaction is carried out with removal of water which is withdrawn from the reactor at the same time as the excess polyol.

This type of preparation process is described in particular in the patent application WO 95/32997.

As the terephthalic copolyester oligomer suitable for the present invention, mention may be made of the product sold under the trade name Skybon EW-110 by the company SK Chemicals.

The water-soluble film-forming sulphonated polymer gelling agent according to the invention may be present in the gel according to the invention in a content ranging from 0.5 to 30% by weight, relative to the total weight of the gel. According to the form sought; pasty or solid, different amounts of gelling agent according to the invention will be used. For a solid gel, use will preferably be from 5 to 20% by weight of gelling agent according to the invention, more preferably from 7 to 15% by weight, relative to the total weight of the gel. For a pasty gel, it is preferable to use from 1 to 5% by weight of gelling agent according to the invention, more preferably from 1 to 3% by weight, relative to the total weight of the gel.

Preferably, the gel according to the invention is solid. For the purposes of the present invention, the term "solid gel" means a gel having a defined hardness, in compression mode, by the maximum recorded force, for a displacement set at 1 mm, ranging from 10 g to 500 grams, at ambient temperature ( 20-25 C), after penetration by a 10 mm diameter ebonite wheel into the matrix of the 40 mm diameter gel, at a penetration speed of 1 mm / s and removal of said mobile from the gel matrix at a speed of of 2 mm / s, the maximum force recorded for a given displacement being measured with a texture analyzer of the "TAXT2" type marketed by the company RHEO.

More preferably, the maximum force before rupture is from 30 to 350 g.

The gel according to the invention also comprises particles of solid organopolysiloxane elastomer at least partially crosslinked in suspension in an aqueous phase.

 By elastomeric means a flexible, deformable material having viscoelastic properties and in particular the consistency of a sponge or a flexible sphere. Its elasticity model is such that this material resists deformation and has limited capacity for extension and contraction. This material is able to recover its original shape after stretching. This elastomer is formed of high molecular weight polymer chains whose mobility is limited by a uniform network of crosslinking points.

The elastomeric organopolysiloxanes according to the invention are partially or fully crosslinked and of three-dimensional structure, and are in the form of powder dispersed in water.

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The elastomeric organopolysiloxanes according to the invention may be chosen from the crosslinked polymers described in application JP-A-10/175816. According to this application, they are obtained by addition reaction and crosslinking, in the presence of a catalyst, especially of the platinum type, of at least: - (a) an organopolysiloxane (i) having at least two vinyl groups in position [ alpha] - # of the silicone chain per molecule; and - (b) an organosiloxane (ii) having at least one hydrogen atom bonded to one silicon atom per molecule.

In particular, the organopolysiloxane (i) is chosen from polydimethylsiloxanes and is more specifically an α-co-dimethylvinyl polydimethylsiloxane.

The elastomeric organopolysiloxanes of the composition according to the invention are advantageously in the form of an aqueous suspension. This suspension may in particular be obtained as follows: (a) mixture of organopolysiloxane (i) and organosiloxane (ii); (b) adding the aqueous phase containing an emulsifier to the mixture of step (a); (c) emulsifying the aqueous phase and said mixture; (d) adding hot water to the emulsion of phase (c); and (e) polymerizing organopolysiloxane (i) and organosiloxane (ii) in emulsion in the presence of a platinum catalyst.

The water is advantageously added at a temperature of 40-60 C. After step (e), it is possible to dry the particles obtained, to evaporate all or part of the trapped water.

The organopolysiloxanes of the composition of the invention are, for example, those sold under the names BY 29-122 and BY 29-119 by the company Dow-Corning Toray. A mixture of these commercial products can also be used.

Preferably, the elastomeric organopolysiloxane powder is present in the composition in a solids content ranging from 0.5 to 50% by weight, relative to the total weight of the gel, preferably from 1 to 30% by weight. and preferably from 15 to 25% by weight.

In particular, the elastomeric organopolysiloxane particles (active material) may have a size ranging from 0.1 to 500 m and better from 3 to 200 m. These particles may be spherical, flat or amorphous with, preferably, a spherical shape.

According to the invention, the organopolysiloxane particles are present in the composition in the form of an aqueous suspension; they are therefore directly suspended in water.

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These particles of organopolysiloxane, to disperse stably in water, can be combined with one or more nonionic, cationic or anionic surfactants of HLB>: 8. Preferably, step c) is carried out in the presence of a nonionic surfactant.

The proportion of surfactants is preferably from 0.1 to 20 parts by weight per 100 parts by weight of the elastomeric organopolysiloxane composition, and more preferably from 0.5 to 10 parts by weight (see JP-A description). - 10/175816).

The gels of the invention also contain a cosmetically or physiologically acceptable medium, that is to say a medium that is compatible with all keratin materials such as the skin, the nails, the hair, the eyelashes and eyebrows, the mucous membranes and the semi-mucous membranes, and any other cutaneous zone of the body and the face.

The gels according to the invention may also comprise a floral water such as blueberry water and / or mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water and / or thermal water.

Preferably, the gels according to the invention comprise up to 85% by weight, preferably from 10 to 60% by weight, relative to the total weight of the gel, of water.

The gels according to the invention may also comprise solvents other than water, for example primary alcohols such as ethanol and isopropanol, glycols such as propylene glycol, butylene glycol, dipropylene glycol and diethylene. glycol, glycol ethers such as mono-, di- or tripropylene glycol (C1-C4) alkyl ethers, mono, di- or triethylene glycol, and mixtures thereof.

It is possible to modify the rigidity of the gels according to the invention by adding one or more salts which will increase this rigidity. These salts may be chosen from the salts of mono-, di- or trivalent metals, and more particularly the alkali metal and alkaline earth metal salts and in particular the sodium, calcium or magnesium salts.

The gel according to the invention may also comprise a film-forming polymer in the form of particles in aqueous dispersion, generally known under the name of latex or pseudolatex.

Among the latices or pseudolatexes that can be used in the gel of the present invention, mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin, and their mixtures. As commercial products that can be used according to the present invention, mention may be made of the acrylate copolymer sold under the trade name Neocryl BT-24 by the company Zeneca, the polyvinylpyrrolidone / polyurethane (1/1) mixture in water at 15% sold under the trademark Aquamere H-1511 by the company HYDROMER INC., the acrylic copolymer in aqueous dispersion at 60%

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 sold under the trade name Neocryl A-523 by ZENECA RESINS.

The gels according to the invention may also comprise water-soluble or fat-soluble dyes chosen from the usual dyes of the field in question such as the disodium salt of a culvert, the disodium salt of alizarin green, the yellow of quinoline, the trisodium salt of amaranth. , the disodium salt of tartrazine, the monosodium salt of rhodamine, the disodium salt of fuchsin, the xanthophyll, the Red Sudan III (CTFA name D & C red 17), lutein, quinizarin green (CTFA name DC green 6), the Alizurol SS purple (CTFA name DC Violet N 2), carotenoid derivatives such as lycopene, beta-carotene, bixin, capsanthine, and / or mixtures thereof.

The gel according to the invention may also comprise a pulverulent phase which may comprise at least one pigment and / or a nacre and / or a filler and / or their mixtures.

By pigments, one must understand white or colored particles, mineral or organic, insoluble in the medium, intended to color and / or opacify the composition.

The pigments may be present in a proportion of 0-40% by weight, relative to the total weight of the gel, preferably in the proportion of 0.1 to 30% and more preferably in the proportion of 1-20%. They may be white or colored, inorganic and / or organic, of usual or nanometric size. Nanoscale means pigments whose average particle size ranges from 5 to 100 nm.

Among the pigments and mineral nanopigments, mention may be made of titanium, zirconium or cerium dioxides, as well as oxides of zinc, iron or chromium, nanotitans and ferric blue. Among the organic pigments, mention may be made of carbon black, and lacquers commonly used to impart to the lips and to the skin a makeup effect, which are salts of calcium, barium, aluminum or zirconium, acidic dyes such as halogenoacid, azo or anthraquinone dyes and / or mixtures thereof.

 The pigments may in particular be coated with silicone compounds such as PDMSs and / or with polymers, in particular polyethylenes or with fluorinated compounds. The SA pigments from Maprecos or the PI pigments from Myoshi can be mentioned.

By nacres, we must understand iridescent particles that reflect light.

 The pearlescent agents may be present in the gel in a proportion of 0-40% by weight, preferably in a proportion of 0.1 to 30% and more preferably in a proportion of 1 to 20% by weight.

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Among the nacres that can be envisaged, mention may be made of natural mother-of-pearl, mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride, and with colored titanium mica.

By fillers, it is necessary to include colorless or white particles, mineral or synthetic, lamellar or non-lamellar, intended to give the body or rigidity to the composition, and / or softness, dullness and uniformity make-up.

The fillers, which may be present in the gel in a proportion of 0-60% by weight, relative to the total weight of the gel, preferably in a proportion of 0.1 to 40%, more preferably 1-20%, may be mineral or synthetic, lamellar or non-lamellar.

composés SiO2/TiO2/ Si02, TiO2lCe02/Si02, ou encore Ti02/ZnO/Talc, les polymè- res de polyéthylène terephtalate/polyméthacrylate en forme de paillettes et/ou leurs mélanges. Mention may be made of talc, mica, silica, kaolin, nylon, poly-ssalanine and polyethylene powders, Teflon, lauroyl-lysine, starch, boron nitride and bismuth oxychloride. , tetrafluoroethylene polymer powders, polymethyl methacrylate powders, polyurethane powders, polystyrene powders, polyester powders, synthetic hollow microspheres, micro sponges, silicone resin microbeads, zinc and titanium oxides , oxides of zirconium or cerium, precipitated calcium carbonate, magnesium carbonate and hydrocarbonate, hydroxyapatite, hollow silica microspheres, glass or ceramic microcapsules, metal soaps derived from organic acids carboxylic compounds having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, such as zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate,

SiO 2 / TiO 2 / SiO 2, TiO 2 1 CeO 2 / SiO 2 or TiO 2 / ZnO / Talc compounds, flake-like polyethylene terephthalate / polymethacrylate polymers and / or mixtures thereof.

The gels according to the invention may also comprise a fatty phase comprising at least one oil.

Among the oils that can be used, mention may be made of oils of animal, vegetable or mineral origin, such as paraffin oil, petroleum jelly, perhydrosqualene, apricot oil, wheat germ oil, sweet almond, calophyllum, sesame, macadamia, grape seed, rapeseed, copra, peanut, palm, castor oil, avocado, jojoba, olive or grain sprouts; esters of fatty acids and polyol, in particular liquid triglycerides; alcohols; acetylglycerides; octanoates, decanoates or ricinoleates of alcohols or polyalcohols; triglycerides of fatty acids; desglycerides, fluorinated and perfluorinated oils; synthetic oils such as fatty esters; silicone oils such as volatile silicone oils, polymethylsiloxanes, polymethylphenylsiloxanes, polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, fluorinated silicones and perfluorinated oils.

The fatty phase of the gels according to the invention may furthermore comprise other fatty substances, which may be chosen by those skilled in the art on the basis of their

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 general births, so as to give the final gel the desired properties, for example in consistency, texture and / or transfer. These additional fatty substances may be waxes, gums and / or pasty fatty substances of animal, vegetable, mineral or synthetic origin, and mixtures thereof.

There may be mentioned in particular: silicone gums, waxes of animal, vegetable, mineral or synthetic origin, such as microcrystalline waxes, paraffin wax, petrolatum, petroleum jelly, ozokerite, montan wax; beeswax, lanolin and its derivatives; Candelilla, Ouricury, Carnauba, Japan waxes, cocoa butter, cork fiber waxes or sugar cane waxes; 25 C solid hydrogenated oils, ozokerites, fatty esters and glycerides at 25 ° C; polyethylene waxes and waxes obtained by Fischer-Tropsch synthesis; hydrogenated oils that are solid at 25 ° C .; lanolins; concrete fatty esters at 25 ° C .; silicone waxes; fluorinated waxes; their mixtures.

The fatty phase may be present in proportions of, for example, up to 30% by weight, preferably from 0.5 to 10% by weight and better still from 1 to 5% by weight, relative to the total weight of the gel. , these proportions varying according to the chosen application.

 The gel according to the invention may furthermore comprise any complementary compound conventionally used in the cosmetics field, such as antioxidants, essential oils, preservatives, lipophilic or hydrophilic cosmetic or pharmaceutical active ingredients, moisturizers, vitamins, fatty acids essential, sphingolipids, self-tanning compounds such as DHA, sunscreens.

 Of course, those skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the gel according to the invention are not, or not substantially, impaired by the addition envisaged. .

 The gels of the invention can be incorporated into cosmetic compositions and constitute for example the continuous phase.

 The present invention also relates to a makeup product for the skin and / or mucous membranes and / or keratinous fibers comprising a gel and / or a composition as defined above.

The gels and the compositions according to the invention may thus constitute make-up or skincare products, in particular the body, the face and / or the scalp, or the keratinous fibers, in particular the hair, the nails, eyelashes and / or eyebrows, or mucous membranes, in particular lips. They can thus constitute makeup products of the body, foundations,

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 eye shadows, blushes, concealer, lipsticks, lip pencils, mascaras, eye pencils, sticks for dyeing or makeup hair strands.

Gels and aqueous continuous phase compositions according to the invention can be prepared according to preparation methods well known to those skilled in the art.

The present invention also relates to a non-therapeutic method for making up the skin and / or mucous membranes and / or keratinous fibers, characterized in that a gel is applied to the keratin materials and / or mucous membranes and / or or a composition as defined above.

The subject of the present invention is also the use of at least one hydrophilic gelling agent of the water-soluble film-forming sulphonated polymer type and of at least partially crosslinked solid organopolysiloxane elastomer particles suspended in an aqueous phase in a cosmetic gel, in particular a solid gel. , or for the preparation of a gel, for the purpose of improving the resistance on the skin of said gel.

The subject of the present invention is also the use of at least one hydrophilic gelling agent of the water-soluble film-forming sulphonated polymer type and of at least partially crosslinked solid organopolysiloxane elastomer particles suspended in an aqueous phase in a cosmetic gel, in particular a solid gel. , or for the preparation of a gel, for the purpose of limiting and / or reducing and / or eliminating the transfer and / or migration of said gel.

The invention is further illustrated in the following examples.

In the following examples, the amounts are given as a percentage by weight relative to the total weight of the composition.

 EXAMPLE 1: A Terephthalic Copolyester Oligomer In a 7.5 liter stainless steel reactor equipped with an anchor stirrer rotating at 80 rpm connected to a KYOWA torque meter, a double jacket for the circulation of a heat transfer liquid and a distillation column regulated by a solenoid valve are introduced: - 11.47 moles of dimethyl terephthalate - 2.53 moles of sodium 5-dimethylisophthalate sulfonate - 39.16 moles of ethylene glycol - 54 ppm by weight of titanium, in the form of titanium aminotriethanolate as catalyst and etherification limiting agent.

The mixture is preheated to 180 ° C. It is then heated to a temperature of 220 ° C. in about 130 minutes to distill more than 90% of the theoretical amount of methanol.

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The reaction mixture is then brought to 230 ° C. in 30 minutes. When the reaction mass has reached this temperature, a suspension is introduced in 60 minutes, still at 230 ° C., the composition of which is as follows: 0.5 mole of isophthalic acid 2.36 moles of terephthalic acid 8 moles ethylene glycol.

The reaction mass is then brought to the temperature of 250 ° C. in 60 minutes.

During the period of introduction of the mixture and during the heating period up to 250 C, a mixture of water and ethylene glycol is distilled without retrogradation.

The reaction mixture is then transferred to an autoclave preheated to 250 ° C. and then pressurized to 100 millibar in 22 minutes. After 2 minutes under these conditions of temperature and pressure, the reaction mass is poured and cooled.

The copolyester obtained has the structural characteristics described in Table 1 below, in which: "mol% of the diacid units" corresponds to the content, in%, of each diacid or diester used relative to all the diacids or diesters used, "Tp" means: terephthalic unit "Ip" means: isophthalic unit "Slp" means: sulfoisophthalic unit.

 The characteristics of the "glycol" part of the copolyesters are obtained by methanolysis of the products at 190 ° C. for 16 hours followed by analysis by the technique of vapor phase chromatography and assay by internal calibration.

- "mol% of the diol units" corresponds to the content, in%, of the oxyethylene "G" units, di (oxyethylene) "2G" units, tri (oxyethylene) "3G" units and tetra (oxyethylene) units " 4G ", with respect to all the diol units.

 "% GT / # units" corresponds to the mol% of the units of formula (I) [-CO-A-CO-O- (CH 2 -CH 2 -O) n-] (I) where A is 1,4 phenylene and n = 1 with respect to all of the units of formula (1) in which A is 1,4-phenylene, 1,3-sulpho-phenylene and optionally 1,3-phenylene and n is from 1 to 4;

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"% GTIE motives" is calculated by the following formula:% GT / # units = (mol% of Tp units) x (% molar of G units) / 100 * The molar mass of polyesters (Mw) is determined by permeation chromatography gel (GPC) in 100% DMAc / LiBr, the results are given in polystyrene equivalents.

<Tb>
<Tb>

% <SEP> molar <SEP> of <SEP> motifs <SEP> diacids
<tb> Tp <SEP> 82
<tb> Ip <SEP> 3
<tb> Slp <SEP> 15
<tb>% GT / # <SEP> patterns <SEP> 46.5
<tb>% <SEP> molar <SEP> of <SEP> motifs <SEP> diols
<tb> G <SEP> 56.8
<tb> 2G <SEP> 30.7
<tb> 3G <SEP> 10
<tb> 4G <SEP> 2.5
<tb> Mw <SEP> 8 <SEP> 000 <SEP>
<Tb>
EXAMPLE 2 The Applicant has carried out the following solid gel: terephthalic copolyester oligomer of Example 1 8% Organopolysiloxane in aqueous suspension at 63% solids (BY29-119 from Dow Corning) 47.62% -polymer of acrylate (Neocryl BT-24 from Zeneca) 11.1% - phenyl trimethicone 2.5% - preservative 0.9% - pigments 15.55% - water 14.33%

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 This gel is prepared in the following manner: the terephthalic copolyester oligomer is swollen in water with stirring for 2 hours at room temperature. Then the organopolysiloxane in aqueous suspension, the acrylate polymer, the oil and the pigments are successively added. The preservative previously dissolved in water is added in the end.

Stirring is maintained for 10 minutes to ensure the homogeneity of the preparation. The whole is then cast in stick.

The hardness of this gel, measured as described above is: 165 g.

This gel is transfer free and extremely comfortable, soft to the touch, resistant to friction.

EXAMPLE 3 The Applicant has made the following solid gel: terephthalic copolyester oligomer of Example 1 11% Organopolysiloxane in aqueous suspension at 63% solids (BY29-119 from Dow Corning) 31.75% -polymer of acrylate (Neocryl BT-24 from Zeneca) 11.1% - phenyl trimethicone 2.5% - preservative 0.9% - pigments 15.55% - water 27.2% This gel is prepared in the same way as in Example 2

 The hardness of this gel, measured as described above, is: g.

This gel is transfer free and extremely comfortable, soft to the touch, resistant to friction. It gives the application a freshness effect that persists over time.

Claims (40)

 1. Gel characterized in that it comprises in an aqueous phase: - i) at least one hydrophilic gelling agent of sulfonated water-soluble film-forming polymer type, - ii) particles of solid organopolysiloxane elastomeric at least partially crosslinked suspended in said aqueous phase. 2. Gel according to claim 1, characterized in that said sulfonated polymer is a sulfonated polyester. 3. Gel according to claim 1 or 2, characterized in that said sulfonated polymer is a terephthalic copolyester oligomer comprising essentially repeating dicarboxylate units of formula (I): [-CO-A-CO-O- (CH 2 -CH 2 O) n -] (I) in which - A represents a 1,4-phenylene, sulfo-1,3-phenylene and optionally 1,3-phenylene group, lnvade 1 to 4, - at least 35 mol% of said units of formula ( I) being units of formula (I) for which A represents a 1,4-phenylene group and n is equal to 1, - at least 7 mol% of said units of formula (I) being units of formula (1) wherein A represents a sulfo-1,3-phenylene group, the weight-average molecular weight of said copolyester oligomers being less than 20,000. 4. Gel according to claim 3, characterized in that the oligomer copolyester has a molecular weight less than 15,000. 5. Gel according to claim 3 or 4, characterized in that the terephthalic copolyester oligomer has a molecular weight in weight ranging from 5,000 to 14,000, and more preferably from 8,000 to 10,000. 6. Gel according to any one of the preceding claims, characterized in that the terephthalic copolyester oligomer comprises at least 40 mol% of said units of formula (I) for which A represents a 1,4-phenylene group and n is equal to 1. 7. Gel according to any one of the preceding claims, characterized in that the terephthalic copolyester oligomer comprises from 40 to 90 mol% of said units of formula (I) for which A represents a 1,4-phenylene group and n is equal to to 1. 8. Gel according to any one of the preceding claims, characterized by the <Desc / Clms Page number 19>  the terephthalic copolyester oligomer comprises at least 10 mol% of the units of formula (1) for which A represents a 1,3-sulpho-phenylene group. 9. Gel according to any one of the preceding claims, characterized in that the terephthalic copolyester oligomer comprises 10% and 25% by mole of said units of formula (I) for which A represents a 1,3-sulfo-phenylene group. 10. Gel according to any one of the preceding claims, characterized in that the terephthalic copolyester oligomer comprises up to 20% by mole, and preferably from 0.5% to 5% by mole, of units of formula ( I) for which A represents a 1,3-phenylene group. 11. Gel according to any one of the preceding claims, characterized in that the hydrophilic gelling agent of the sulfonated water-soluble film-forming polymer type is present in a content ranging from 0.5% to 30% by weight, relative to the total weight of the gel. .  12. Gel according to claim 11, characterized in that said content ranges from 5% to 20% by weight, preferably from 7 to 15% by weight, relative to the total weight of the gel.  13. Gel according to any one of the preceding claims, characterized in that it is solid.  14. Gel according to any one of the preceding claims, characterized in that it has a hardness defined by a maximum force before rupture ranging from 10 to 500 g.  15. Gel according to the preceding claim, characterized in that said maximum force before rupture ranges from 30 to 350 g.  16. Gel according to any one of the preceding claims, characterized in that the organopolysiloxane elastomeric is obtained by addition reaction and crosslinking, in the presence of a catalyst, at least: - an organopolysiloxane (i) having two vinyl groups in the [alpha] - # position of the silicone chain per molecule; and an organosiloxane (ii) having at least one hydrogen atom bonded to one silicon atom per molecule.  17. Gel according to any one of the preceding claims, characterized in that the organopolysiloxane (i) is chosen from polydimethylsiloxanes.  18. Gel according to any one of the preceding claims, characterized in that the organopolysiloxane is an [alpha] - # - dimethylvinyl polydimethylsiloxane. <Desc / Clms Page number 20> 19. Gel according to claim 1, wherein the suspension of organopolysiloxane particles is obtained according to the following steps: ); (b) adding the aqueous phase containing an emulsifier to the mixture of step (a); (c) emulsifying the aqueous phase and said mixture; (d) adding hot water to the emulsion of phase (c); and (e) polymerizing organopolysiloxane (i) and organosiloxane (ii) in emulsion in the presence of a platinum catalyst. 20. Gel according to claim 19, characterized in that step (c) is obtained in the presence of a nonionic surfactant. 21. Gel according to any one of the preceding claims, characterized in that the organopolysiloxane particles have a size ranging from 0.1 to 500 m and preferably from 3 to 200 m. 22. Gel according to any one of the preceding claims, characterized in that the organopolysiloxane is present in a solids content ranging from 0.5% to 50% by weight, relative to the total weight of the gel. 23. Gel according to claim 22, characterized in that said content is 1% to 30% by weight, preferably 15 to 25% by weight, relative to the total weight of the gel. 24. Gel according to any one of the preceding claims, characterized in that it further comprises a cosmetically or physiologically acceptable medium. 25. Gel according to any one of the preceding claims, characterized in that it further comprises a film-forming polymer in the form of particles in aqueous dispersion. 26. Gel according to any one of the preceding claims, characterized in that it further comprises a pulverulent phase comprising at least one pigment and / or a nacre and / or a filler and / or their mixtures. 27. Gel according to claim 26, characterized in that the pigment is chosen from titanium, zirconium or cerium dioxides, zinc oxides, iron or chromium, nanotitans, ferric blue, carbon black. lacquers such as calcium, barium, aluminum or zirconium salts, acid dyes such as haloacid, azo or anthraquinone dyes, pigments coated with silicone compounds and / or with polyethylenes and / or by fluorinated compounds. <Desc / Clms Page number 21> 28. Gel according to claim 27, characterized in that the pigments are present at a content ranging from 0 to 40% by weight, preferably from 0.1 to 30% by weight, relative to the total weight of the gel. 29. Gel according to any one of claims 26 to 28, characterized in that the filler is selected from talc, mica, silica, kaolin, powders of nylon, poly-p-alanine and polyethylene, Teflon, lauroyl-lysine, starch, boron nitride, bismuth oxychloride, tetrafluoroethylene polymer powders, polymethyl methacrylate powders, polyurethane powders, polystyrene powders, polyester powders, synthetic hollow microspheres, micro sponges, silicone resin microbeads, zinc and titanium oxides, zirconium or cerium oxides, precipitated calcium carbonate, magnesium carbonate and hydrocarbonate, hydroxyapatite, hollow silica microspheres, microcapsules of glass or ceramic, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, such as zinc laurate, magnesium or lithium tetra, zinc laurate, magnesium myristate, SiO 2 / TiO 2 / SiO 2, TiO 2 / CeO 2 / SiO 2, or TiO 2 / ZnO / Talc, polymers of polyethylene terephthalate / polymethacrylate flake form and / or mixtures thereof. 30. Gel according to claim 29, characterized in that the fillers are present at a content ranging from 0 to 60% by weight, preferably ranging from 0.1 to 40% by weight, relative to the total weight of the gel. 31. Gel according to any one of the preceding claims, characterized in that it further comprises a fatty phase which comprises at least one oil. 32. Gel according to claim 31, characterized in that the oil is chosen from liquid paraffin, petrolatum, perhydrosqualene, apricot oil, wheat germ oil, sweet almond, calophyllum, sesame, macadamia, grape seed, rapeseed, copra, peanut, palm, castor oil, avocado, jojoba, olive or cereal sprouts; esters of fatty acids and polyol, in particular liquid triglycerides; desalcools; acetylglycerides; octanoates, decanoates or ricinoleates of alcohols or polyalcohols; triglycerides of fatty acids; desglycerides, fluorinated and perfluorinated oils; synthetic oils such as fatty esters; silicone oils such as volatile silicone oils, polymethylsiloxanes, polymethylphenylsiloxanes, polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, fluorinated silicones and perfluorinated oils. 33. Cosmetic composition characterized in that it comprises a gel as defined in any one of claims 1 to 32. 34. Makeup product for the skin and / or mucous membranes and / or keratinous fibers, characterized in that it comprises a gel as defined in any one of Claims 1 to 32 and / or a composition as defined in claim 33. <Desc / Clms Page number 22> 35. A product according to claim 34, characterized in that it constitutes a body make-up product, a foundation, an eye shadow, a blush, a concealer, a lipstick, a pencil of the body. lip contour, a mascara, a pencil around the eyes, a stick for dyeing or makeup strands of hair. 36. Non-therapeutic method for making up the skin and / or the mucous membranes and / or keratinous fibers, characterized in that a gel as defined is applied to the skin and / or the mucous membranes and / or the keratinous fibers. to any one of claims 1 to 32 and / or a composition as defined in claim 33 and / or a product as defined in any one of claims 34 or 35. 37. Use of at least one hydrophilic, water-soluble, film-forming, sulfonated polymeric gelling agent and particles of at least partially crosslinked elastomeric solid organopolysiloxane suspended in an aqueous phase for the preparation of a gel, for the purpose of improving the held on the skin of said gel. 38. Use of at least one hydrophilic, water-soluble, film-forming, sulfonated polymeric gelling agent and particles of at least partially crosslinked elastomeric solid organopolysiloxane suspended in an aqueous phase in a cosmetic gel, in particular a solid gel, with the aim of improving holding on the skin of said gel. 39. Use of at least one water-soluble film-forming sulfonated polymeric hydrophilic gelling agent and particles of at least partially crosslinked elastomeric solid organopolysiloxane suspended in an aqueous phase for the preparation of a gel, for the purpose of limiting and / or or to reduce and / or suppress the transfer and / or migration of said gel. 40. Use of at least one water-soluble film-forming sulfonated polymer hydrophilic gelling agent and of at least partially crosslinked elastomeric solid organopolysiloxane particles suspended in an aqueous phase in a cosmetic gel, in particular a solid gel, for the purpose of limiting and / or to reduce and / or to suppress the transfer and / or migration of said gel