FR2989893A1 - COSMETIC COMPOSITION COMPRISING A PHOSPHORYLATED OLIGOSACCHARIDE AND A SULFONIC COPOLYMER - Google Patents

Abstract

The invention relates to a composition comprising, in a physiologically acceptable aqueous medium, i) at least one phosphorylated oligosaccharide and ii) at least one (meth) acrylamido (C -C) alkylsulfonic acid copolymer, in particular crosslinked acid copolymers. 2-acrylamido-2-methylpropanesulfonic acid, dimethylacrylamide, lauryl methacrylate, and laureth-4 methacrylate, Application to the care and makeup of keratin materials.

Description

The present invention relates to cosmetic compositions comprising a phosphorylated oligosaccharide and a 2-acrylamido-2-methylpropanesulphonic acid copolymer, and the use of these compositions in a process. treatment of keratinous substances of human beings. More particularly, the compositions of the invention are intended for caring for and / or making up keratin materials. For the purposes of the invention, the term "keratin materials" is intended to mean, for example, the skin, the mucous membranes, the lips, the scalp, the eyelashes, the eyebrows and the hair.

Small molecular weight oligosaccharides having properties in the radiance of the complexion, for exfoliating the skin (WO 2003013448) or for promoting cell proliferation of keratinocytes or fibroblasts and for inhibiting the synthesis of certain proteases of the elastase type (Andres E) are known et al., Pathol Biol, Paris, 2006 Sep; 54 (7): 420-5; WO 2002020622). Phospho-oligosaccharides such as POs-Ca would also improve the elasticity of the cutaneous tissue and fight against the signs of skin aging (JP2009227632).

However, the introduction of phosphorylated oligosaccharides in an aqueous cosmetic formulation can result in a significant decrease in viscosity and / or destabilization of the composition. A too fluid composition is difficult to apply to keratin materials. Such a composition flows from the keratin materials, especially the skin, on which it is applied. Its application on the keratin materials that one wishes to treat lacks precision and thus makes its use unattractive.

Thus, there is a need for cosmetic compositions comprising a phosphorylated oligosaccharide having a good stability over time, especially after storage for 2 months at room temperature (25 ° C.) or at a higher temperature, without significant fluidification and / or destabilization. The present invention specifically aims to meet these needs. More specifically, the present invention relates to a composition comprising, in a physiologically acceptable medium containing an aqueous medium, at least one phosphorylated oligosaccharide and at least one 2-acrylamido-2-methylpropanesulfonic acid copolymer as described below. . The composition according to the invention is in particular a cosmetic and / or pharmaceutical composition, especially a dermatological and more particularly a cosmetic composition. Surprisingly, the inventors have observed that the addition of a particular 2-acrylamido-2-methylpropanesulfonic acid copolymer in a composition comprising a phosphorylated oligosaccharide makes it possible to thicken the composition and to obtain a stable composition. in time, with satisfactory viscosity. Moreover, this makes it possible to add the phosphorylated oligosaccharide during the various preparation phases without modifying the viscosity. Moreover, this specific phosphorylated oligosaccharide-2-acrylamido-2-methylpropanesulphonic acid copolymer combination also makes it possible to impart to a composition of the invention a pleasant appearance, and during its application, properties of comfortable feeling. The present invention also relates to a method of non-therapeutic treatment for the care or makeup of keratin materials, comprising the application to said keratin materials of a composition according to the invention. Advantageously, such a method is intended for care and / or make-up of the skin. By "phosphorylated oligosaccharide" is meant a polysaccharide compound, linear or branched, consisting of or containing: a) from 2 to 10 monosaccharide units; and b) one, two or more phosphate groups.

The 2-10 monosaccharide units may in particular be pentoses or hexoses. Preferably, the monosaccharide units are hexoses, and may, independently of one another, be selected from the group consisting of: aldohexoses, namely fructose, psicose, sorbose, and tagatose; - ketohexoses, namely glucose, galactose, mannose, allose, altrose, gulose, idose and talose; and deoxymonosaccharides, namely rhamnose, fucose fubulose, pneumosis, and quinovose. In particular, the monosaccharide units may all be glucose. In the context of the present application, "phosphorylated oligosaccharides" denotes indifferently several molecules of the same phosphorylated oligosaccharide or a mixture of several phosphorylated oligosaccharides.

The phosphorylated oligosaccharides may be in the form of a complex with cations, in particular calcium. The phosphorylated oligosaccharides may more specifically be phosphorylated maltooligosaccharides, i.e., phosphorylated oligosaccharides consisting of 2 (maltose), 3 (maltotriose), 4 (maltotetraose), 5 (maltopentaose), 6 (maltohexaose), 7 ( maltoheptaose), 8 (maltooctaose), 9 (maltononaose) or 10 (maltodecaose) glucose units linked together by glycosidic linkages a-1-4. In particular, the phosphorylated oligosaccharides may comprise or consist of a mixture of maltotriose phosphate, maltotetraose phosphate and maltopentaose phosphate.

The phosphorylated maltooligosaccharides preferably carry 1 or 2 phosphate groups and are optionally combined with calcium. The phosphorylated oligosaccharides may in particular be those marketed by the company Ezaki Glico, such as calcium phosphooligosaccharides POs-Ca (INCI name: Calcium Phosphoryl Oligosaccharides) which are a mixture of maltooligosaccharides to which are attached at least 1 or 2 phosphorus groups and calcium ions.

These phospho-oligosaccharides ("POs") can be obtained by enzymatic hydrolysis of potato starch using a mixture of liquefying bacterial α-amylase (EC 3.2.1.1), glucoamylase ( EC 3.2.1.3) and pullulanase (EC 3.2.1.41), the POs being present in the non-hydrolyzable fraction by the enzymes. These POs comprise or consist of two fractions that can be separated by anion exchange chromatography: a major fraction called "PO-1" which is a mixture consisting of monophosphorylated maltotriose, maltotetraose and maltopentaose (Kamasaka et al., Biosci. Biotech, Biochem, 1997, 61 (2), 238-244); and a minor fraction called "P0-2" which is a mixture consisting mainly of phosphorylated maltopentaose and maltohexaose, and in a minor proportion of phosphorylated maltotriose, maltotetraose, maltoheptaose and maltooctaose, the phosphorylated maltooligosaccharides each having at least two phosphate groups (Kamasaka et al. Biosci Biotech, Biochem, 1995, 59 (8), 1412-1416). In particular the P0-1 fraction consists of six monophosphorylated compounds Kamasaka et al., Biosci. Biotech. Biochem, 1997, 61 (2), 238-244): - 3-phosphoryl oligosaccharides [33-phosphoryl maltotetraose (maltotetraose carrying a phosphate group on the C3 carbon of the third glucosyl residue) and 34-phosphoryl maltopentaose (maltopentaose carrying a Phosphate group on the C3 carbon of the fourth glucosyl residue)]; and 6-phosphoryl oligosaccharides [63-phosphoryl maltotriose (maltotiosis bearing a phosphate group on the C6 carbon of the third glucosyl residue), 62-phosphoryl maltotriose (maltotriose bearing a phosphate group on the C2 carbon of the second glucosyl residue), Phosphorylated maltotetraose (maltotetraose bearing a phosphate group on the C6 carbon of the third glucosyl residue) and 64-phosphoryl maltopentaose (maltopentaose bearing a phosphate group on the C6 carbon of the fourth glucosyl residue)]. The average degree of polymerization of the two dephosphorylated P0-1 and P0-2 fractions is 4.02 and 5.82, respectively. Both P0-1 and P0-2 fractions can form a complex with calcium ions (calcium phospho-oligosaccharides or POs-Ca). This complex contains about 5% calcium by weight of calcium based on the total weight of POs-Ca. In particular, the POs can be obtained by hydrolysis of potato starch, according to the process described by Kamasaka et al., Biosci. Biotech.

Biochem, 1995, 59 (8), 1412-1416. According to this method, 1 g of potato starch is suspended in 100 ml of a solution containing 6 mM NaCl, 2 mM CaCl 2 and BLA (liquefied bacterial α-amylase) 3.0 U / ml. After gradually heating the suspension to 100 ° C for liquefying, the solution is cooled and incubated at 50 ° C for one hour. 1 ml of 600 U / ml glucoamylase, 1 ml of 200 U / ml pullulanase and 1 ml of 300 U / ml BLA are then added, and the reaction mixture is incubated at 40 ° C for two hours. Advancement of the amylolitic reaction can be followed by the starch-iodine complex method and / or glucose oxidase method (see Barham and Trinder, Analyst, 1972, 97, 142-146). As the action of the amylolitic enzymes is inhibited by phosphate groups bound to glucose residues, the phosphorylated oligosaccharides are present in the indigestible fraction of this enzymatic treatment. After the enzymatic reaction is complete (which can be determined by a negative starch-iodine staining reaction), the solution is heated in a boiling water bath for 10 minutes and then applied to a resin exchange column. anions (e.g., Chitopearl BCW-2501, x 2 cm or equivalent column) which has been equilibrated with 20 mM acetate buffer (pH 4.5). The neutral saccharides are washed from the column with the buffer and the phosphorylated oligosaccharides are then eluted with the same 20 mM acetate buffer (pH 4.5) additionally containing 0.5 M NaCl. The phosphorylated oligosaccharides eluted can be desalted, for example by ethanol precipitation (at a concentration of 70% v / v) followed by washes with 70% ethanol before dissolution in deionized water, or by passage through a cation exchange column (eg Dowex 30). 50WX4, 20-50 Mesh or equivalent column). Phosphorylated oligosaccharides complexed with calcium (P0s-Ca) can be prepared by neutralizing the desalted solution of phosphooligosaccharides with Ca (OH) 2 to pH 6.5. The calcium content is then 5 g of calcium per 100 g of total weight. The phosphorylated oligosaccharide (s) may be present in the composition according to the invention in a content ranging from 0.01% to 10% by weight, relative to the total weight of the composition, preferably from 0.1% to 5% by weight. weight. The composition according to the invention comprises a copolymer of (meth) acrylamido (C 1 -C 22) alkylsulphonic acids. By copolymer of (meth) acrylamido (C 1 -C 22) alkylsulphonic acids is meant copolymers comprising at least one (meth) acrylamido (C 1 -C 22) alkylsulphonic acid monomer and at least one monomer other than (meth) acrylamido acids. (C i -C 22) alkylsulfonic. The copolymers of (meth) acrylamido (C 1 -C 22) alkylsulphonic acids according to the invention may be crosslinked or non-crosslinked. Preferably, crosslinked copolymers are chosen.

When they are crosslinked, the crosslinking agents may be chosen from the olefinic polyunsaturated compounds commonly used for crosslinking the polymers obtained by radical polymerization. Examples that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol or tetraethylene glycol di (meth) acrylate. , trimethylol propane triacrylate, methylenebisacrylamide, methylenebis-methacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetra-allyloxyethane, trimethylolpropane diallylether, (meth) allyl acrylate, the allyl ethers of alcohols of the series of sugars, or other allyl- or vinyl-ethers of polyfunctional alcohols, and the allyl esters of the derivatives of phosphoric and / or vinylphosphonic acid, or mixtures of these compounds.

Methylenebisacrylamide, allyl methacrylate, or trimethylol propane triacrylate (TMPTA) will be used more particularly. The degree of crosslinking will generally vary from 0.01 to 10 mol% and more particularly from 0.2 to 2 mol% relative to the polymer.

The (meth) acrylamido (C1-C22) alkylsulphonic acids are, for example, chosen from acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid and 2-acrylamido acid. 2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and their partially or completely neutralized forms. More particularly, use will be made of 2-acrylamido-2-methylpropanesulfonic acid (AMPSC) and its partially or totally neutralized forms. Said copolymer may be salified, in particular in the form of an alkali metal salt such as, for example, the sodium or potassium salt, or in the form of an ammonium salt, or in the form of a salt of an aminoalcohol, such as, for example, monoethanolamine salt, or in the form of an amino acid salt such as for example the lysine salt, arginine. Advantageously, the copolymer is salified in the form of sodium salt or ammonium salt. The copolymers according to the invention also comprise one or more ethylenically unsaturated monomers chosen from ethylenically unsaturated monomers comprising at least one hydrophobic part having from 6 to 50 carbon atoms, such as (meth) acrylic acids, and their substituted alkyl derivatives. 13 or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth) acrylamides optionally substituted with one or more C1-C4 alkyl groups, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds. In particular, the copolymers of 2-acrylamido-2-methylpropanesulphonic acid and optionally hydroxylated (C 2 -C 4) alkyl (meth) acrylate may be used. The C2-C4 alkyl (meth) acrylate hydroxyl monomer may be selected from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2,3-dihydroxypropyl acrylate, methacrylate of 2, 3-dihydroxypropyl.

Said copolymer may be salified, in particular in the form of an alkali metal salt such as, for example, the sodium or potassium salt, or in the form of an ammonium salt, or in the form of a salt of an aminoalcohol such as, for example, salt monoethanolamine, or in the form of an amino acid salt such as, for example, the lysine salt. Advantageously, the copolymer is salified in the form of sodium salt. Preferably, the composition comprises the copolymer of 2-acrylamido-2-methylpropanesulphonic acid and of 2-hydroxyethyl acrylate, especially in the form of sodium salt, for example those sold under the trade names "SEPINOV® EMT 10" or "SIMULGEL® NS" by the company SEPPIC (INCI name: Hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer). Such polymers are described in application FR-A-2856691.

The preferred copolymers of the invention are chosen from copolymers of (meth) acrylamido (C1-C22) alkylsulphonic acids and of at least one ethylenically unsaturated monomer comprising at least one hydrophobic part having from 6 to 50 carbon atoms and more preferably from 6 to 22 carbon atoms and even more preferably from 6 to 18 carbon atoms and more particularly 10 to 14 carbon atoms. These copolymers according to the invention also comprise one or more ethylenically unsaturated monomers different from the ethylenically unsaturated monomers comprising at least one hydrophobic part having from 6 to 50 carbon atoms chosen from (meth) acrylic acids, and their 13-substituted alkyl derivatives. or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth) acrylamides optionally substituted by one or more C1-C4 alkyl groups, vinylpyrrolidone, maleic anhydride, itaconic acid or acid maleic or mixtures of these compounds.

These copolymers are described in particular in Patent Applications EP-A-750899, WO 2008/087326, US Patent 5089578 and in the following Yotaro Morishima publications: - "Self-assembling amphiphilic polyelectrolytes and their nanostructures - Chinese Journal of Polymer Science Flight. 18, No. 40, (2000), 323-336. "- Miscellanous formation of random copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules 2000, Vol. 33, No. 10 - 3694-3704 "; - "Solution properties of miscelle networks formed by non-ionic moieties covalently bound to a polyelectrolyte: known effects on rheological behavior - Langmuir, 2000, Vol.16, No. 12, 5324-5332"; Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and associative macromonomers - Polym. Preprint, Div. Polym. Chem. 1999, 40 (2), 220-221.

The ethylenically unsaturated monomers of these particular copolymers are preferably chosen from (meth) acrylates or (meth) acrylamides of the following formula (I): ## STR1 ## in which which R1 and R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y is 0 or NH; R2 denotes a hydrophobic hydrocarbon radical containing at least 6 to 50 carbon atoms and more preferably 6 to 22 carbon atoms and even more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100. The radical R2 is preferably chosen from linear C6-C18 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (for example cyclododecane (C12) or adamantane (C10)); perfluorinated C5-C18 alkyl radicals (for example the group of formula - (CH2) 2- (CF2) 9-CF3); the cholesteryl radical (C27) or a cholesteryl ester residue such as the cholesteryl oxyhexanoate group; polycyclic aromatic groups such as naphthalene or pyrene. Among these radicals, linear alkyl radicals, and more particularly the n-dodecyl radical, are more particularly preferred.

According to a particularly preferred form of the invention, the monomer of formula (I) comprises at least one alkylene oxide unit (x 1) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain is preferably composed of ethylene oxide units and / or propylene oxide units and even more particularly ethylene oxide units. The number of oxyalkylenated units generally varies from 1 to 50 and more preferably from 2 to 25 and even more preferably from 3 to 10.

Among these polymers, mention may be made of: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C 8 -C 16) alkyl (meth) units acrylamide or (C 8 -C 16) alkyl (meth) acrylate units with respect to the polymer, such as those described in application EP-A-750 899; terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and from 5 to 80 mol% of n- (C5-C18) alkylacrylamide units, such as those described in US Patent 5089578. Mention may also be made of copolymers of AMPS and of dodecyl methacrylate as well as copolymers of AMPS and n-dodecylmethacrylamide which are non-crosslinked and crosslinked, such as those described in the Morishima articles cited above. The distribution of the monomers in the polymers of the invention may be, for example, alternating, block (including multiblock) or any (statistical) block. Preferably, the composition comprises a crosslinked copolymer of 2-acrylamido-2-methylpropanesulfonic acid, dimethylacrylamide, lauryl methacrylate and laureth-4-methacrylate, for example those sold under the trade name " SEPIMAX® ZEN "by the company SEPPIC (INCI name: Polyacrylate Crosspolymer-6). Such polymers are described in application WO 2008/087326. The 2-acrylamido-2-methylpropanesulfonic acid copolymer may be present in the composition according to the invention in a content ranging from 0.1% to 10% by weight, relative to the total weight of the composition. Preferably, the content of said copolymer may range from 0.5% to 5% by weight, relative to the total weight of the composition. Advantageously, the phophorylated oligosaccharide of Ca (said A) and the copolymer of 2-acrylamido-2-methylpropanesulfonic acid (called B) described above may be present in the composition according to the invention in a weight ratio A / B ranging from 0.5 to 5 Preferably, this weight ratio A / B can range from 0.7 to 4. Preferably, this weight ratio A / B can range from 1 to 2.5.

The viscosity of a composition of the invention may be measured by any method known to those skilled in the art, and in particular according to the following conventional method. Thus, the measurement can be carried out at 25 ° C. using a Rhéomat 180, equipped with a mobile rotating at 200 rpm. The person skilled in the art can choose the mobile device for measuring the viscosity, among the mobiles, M1 or M2 or M3 or M4 on the basis of his general knowledge, so as to be able to carry out the measurement. The composition according to the invention comprises a physiologically acceptable aqueous medium. By "acceptable physiological medium" is meant a medium that is compatible with the materials and / or the keratin fibers of human beings, such as, for example, without limitation, the skin, the mucous membranes, the nails, the scalp and / or or the hair. This physiologically acceptable aqueous medium comprises an aqueous phase, optionally mixed or not with one or more organic solvents such as a C1-C8 alcohol, in particular ethanol, isopropanol, tert-butanol, n-butanol, polyols such as glycerine, propylene glycol, butylene glycol, and polyol ethers. A composition according to the invention may also comprise a fatty phase, which may comprise oils, gums, waxes usually used in the field of application in question.

Thus, according to one embodiment, a composition according to the invention may further comprise at least one fatty phase chosen from a solid fatty phase at room temperature (20-25 ° C.) and atmospheric pressure and / or a liquid fatty phase at room temperature. (20-25 ° C) and atmospheric pressure.

A liquid fatty phase suitable for the implementation of the invention may comprise a volatile oil, a non-volatile oil, and a mixture thereof. A volatile or non-volatile oil may be a hydrocarbon oil, in particular of animal or vegetable origin, a synthetic oil, a silicone oil, a fluorinated oil or a mixture thereof.

A solid fatty phase that is suitable for carrying out the invention may be, for example, chosen from pasty fatty substances, gums, and mixtures thereof.

As oils that can be used in the invention, mention may be made of mineral oils (vaseline oil), vegetable oils (liquid fraction of shea butter, sunflower oil), synthetic oils (Purcellin oil), oils or waxes silicone (cyclomethicone) and fluorinated oils (perfluoropolyethers). To these oils can be added fatty alcohols and fatty acids (stearic acid). When a composition is an emulsion, the proportion of the fatty phase can range from 5% to 80% by weight, and preferably from 5% to 50% by weight relative to the total weight of the composition. The oils, the waxes, the emulsifiers and the coemulsifiers used in the composition in emulsion form are chosen from those conventionally used in the cosmetics field. One or more emulsifiers may be present in a composition of the invention in a proportion ranging from 0.3% to 30% by weight, and in particular from 0.5% to 20% by weight relative to the total weight of the composition. The composition according to the invention may also contain adjuvants which are customary in the field in question, such as emulsifiers, hydrophilic or lipophilic gelling agents, waxes, hydrophilic or lipophilic additives, preservatives, antioxidants, solvents, perfumes, fillers, UVA and / or UVB filters (organic or inorganic, soluble or insoluble), pigments, fibers, chelating agents, odor absorbers, dyestuffs, and other cosmetic active agents. The amounts of these various adjuvants are those conventionally used in the cosmetics field, and may for example vary from 0.01% to 30% of the total weight of the composition. In general, the quantities are adjusted according to the formulation produced. These adjuvants, depending on their nature, can be introduced into the fatty phase, into the aqueous phase and / or into the lipid spherules.

Advantageously, the composition according to the invention may comprise, in addition to the 2-acrylamido-2-methylpropanesulfonic acid copolymer according to the invention, a homopolymer of 2-acrylamido-2-methylpropanesulfonic acid, in particular in the form partially or totally neutralized.

Such a polymer makes it possible in particular to reduce the tackiness of the composition when it is applied to the skin. Preferably, said homopolymer may be partially or completely neutralized with a mineral base (sodium hydroxide, potassium hydroxide, ammonia) or an organic base such as mono-, di- or tri-ethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids such as arginine and lysine, and mixtures of these compounds. They are usually neutralized. The term "neutralized" in the present invention means polymers that are totally or substantially completely neutralized, that is to say neutralized to at least 90%. The homopolymer may have a number average molecular weight of from 1000 to 20,000,000 g / mol, preferably from 20,000 to 5,000,000 and more preferably from 100,000 to 1,500,000 g / mol. The homopolymer may be crosslinked, in particular using crosslinking agents which may be chosen from the olefinic polyunsaturated compounds commonly used for the crosslinking of the polymers obtained by radical polymerization. Examples of crosslinking agents which may be mentioned are 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, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallylether allyl (meth) acrylate, the allyl ethers of alcohols of the series of sugars, or other allyl- or vinylethers of polyfunctional alcohols, and the allylic esters of the phosphoric acid derivatives and / or vinylphosphonic acid, 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 mol% and more particularly from 0.2 to 2 mol% relative to the polymer. Such polymers include, in particular, the cross-linked and neutralized homopolymer of 2-acrylamido-2-methylpropanesulphonic acid, sold by the company Clariant under the trade name "Hostacerin® AMPS" (CTFA name: ammonium polyacryldimethyltauramide). A composition of the invention may be in any conceivable galenic form. In particular, a composition according to the invention may have the form of an aqueous, hydroalcoholic solution; a dispersion; a water-in-oil, oil-in-water or multiple emulsion; a suspension; microcapsules or microparticles; vesicular dispersions of ionic and / or nonionic type; aerosol composition composition also comprising a propellant under pressure. Preferably, the composition according to the invention may be an oil-in-water or water-in-oil emulsion. More preferably, the composition according to the invention is an oil-in-water emulsion. When the composition comprises an oily phase, the latter may comprise a silicone elastomer. Examples of silicone elastomers are described in WO-A-2009/080958.

A composition according to the invention may also be in the form of a care product, a solar product or after sun, a daily photoprotective care product, a product for the body, d a foundation to be applied to the face or neck, a concealer, a concealer, a tinted cream or makeup base for face makeup or a makeup composition for the body. A composition according to the invention may be used for the purpose of improving the general condition of an epidermis, in particular the skin, and in particular for maintaining or restoring its physiological functions and / or its aesthetic appearance. Other characteristics and advantages of the invention will emerge more clearly from the examples which follow, given by way of illustration and not limitation. In what follows or the foregoing, the proportions are given in percent by weight unless otherwise indicated. Example 1: Two compositions (facial care cream) described in the following table were prepared: a composition according to the invention (A) containing a phosphorylated oligosaccharide of Ca and a copolymer acrylamido 2-methyl propane sulfonate of sodium according to the invention and a composition B containing a homopolymer of sodium acrylamido 2-methyl propane sulfonate.

Example AB Ca-phosphorylated oligosaccharide (EZAKI GLICO P0s-Ca) 2% MA 2% MA Water Qsp 100 Qsp 100 Copolymer acrylamido 2-methyl propane sulfonate sodium / lauryl methacrylate / lauryl methacrylate oxyethylenated with 4 moles of oxide ethylene / dimethylacrylamide (SEPIMAX ZEN from SEPPIC) 1,5 Polyacrylamidomethyl propanesulfonic acid partially neutralized with ammonia (HOSTACERIN AMPS® from Clariant) 1 Phenoxyethanol 1% 1% The composition A according to the invention is stable and is thickened while the composition B is liquid The formula does not contain the copolymer AMPS® SEPIMAX ZEN according to the invention is not stable. EXAMPLE 2 A composition (facial care cream) described in the following table was prepared: EXAMPLE 2 Phosphorylated Oligosaccharide of Ca (PO.sub.S-Ca of EZAKI GLICO) 2% MA Water Qsp 100 Copolymer acrylamido 2-methyl propane sulfonate of sodium / lauryl methacrylate / lauryl methacrylate oxyethylenated with 4 moles of ethylene oxide / dimethylacrylamide (SEPIMAX ZEN from SEPPIC) 1.5 Cross-linked homopolymer of ammonium acrylamido 2-methyl propane sulfonate (HOSTACERIN AMPS® from CLARIANT) Mixture of glyceryl stearate and 0.75 PEG-100 stearate (ARLACEL® 165 FL from Uniqema) Mixture of cetylstearyl glucoside and cetyl alcohol, stearyl (12/46/42) (MONTANOV 68 from Seppic) 2 Dimethicone 10 cst 2.5 Polyethylene glycol (20 0E) (CARBOWAX SENTRY POLYETHYLENE GLYCOL 1000 NF, FCC GRADE from Dow Chemical) 2 Lactic acid 0.25 Stearyl alcohol 0.5 Cetyl alcohol 0.5 Almond oil apricot 2 Preservative qs The composition of example 5 salt the invention is stable and thickened.

Claims (15)

REVENDICATIONS1. A composition comprising, in a physiologically acceptable aqueous medium, i) at least one phosphorylated oligosaccharide, and ii) at least one (meth) acrylamido (C1-C22) alkylsulfonic acid copolymer. The composition of claim 1, wherein the phosphorylated oligosaccharides consist of 2 to 10 monosaccharide units and one, two or more phosphate groups. 3. A composition according to any one of claims 1 or 2, wherein the phosphorylated oligosaccharides are, independently of one another, selected from the group consisting of fructose, psicose, sorbose, tagatose, glucose, galactose, mannose, allose, altrose, gulosis, idosis, talose, rhamnose, fucose fubulosis, pneumosis, and quinovose. 4. The composition of any one of claims 1 to 3, wherein the phosphorylated oligosaccharides are phosphorylated maltooligosaccharides bearing 1 or 2 phosphate groups. A composition according to any one of claims 1 to 4, wherein the phosphorylated oligosaccharides are obtainable by enzymatic hydrolysis of potato starch using a mixture of bacterial α-amylase. liquefying, glucoamylase and pullulanase. 6. A composition according to any one of claims 1 to 5, wherein the phosphorylated oligosaccharides comprise maltotrioses, maltotetraoses and maltopentaoses monophosphorylés, and maltotrioses, maltotetraoses, maltopentaoses, maltohexaoses, maltoheptaoses and maltooctaoses each having at least two phosphate groups. The composition according to any one of claims 1 to 6, wherein the phosphorylated oligosaccharides are in the form of complexes with calcium ions. 8. Composition according to any one of the preceding claims, characterized in that the phosphorylated oligosaccharide or oligosaccharides is present in a content ranging from 0.01 to 10% by weight, relative to the total weight of the composition, preferably from 0 to 10% by weight, relative to the total weight of the composition. , 1% to 5% by weight. 9. Composition according to any one of the preceding claims, characterized in that the copolymer (s) of (meth) acrylamido (C1C22) alkylsulphonic acids further comprises one or more ethylenically unsaturated monomers chosen from ethylenically unsaturated monomers comprising at least a hydrophobic part having from 6 to 50 carbon atoms, such as (meth) acrylic acids, their [3-substituted alkyl derivatives or their esters obtained with monoalcohols or mono or polyalkylene glycols, the optionally substituted (meth) acrylamides by one or more C 1 -C 4 alkyl groups, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures thereof. 10. Composition according to any one of the preceding claims, characterized in that the copolymer or copolymers of (meth) acrylamido (C1C22) alkylsulphonic acids are chosen from (meth) acrylamido (C1-C22) alkylsulfonic acid copolymers. and at least one ethylenically unsaturated monomer comprising at least one hydrophobic part having from 6 to 50 carbon atoms and more preferably from 6 to 22 carbon atoms and even more preferably from 6 to 18 carbon atoms and more particularly 10 to 14 carbon atoms. 30 11. Composition according to any one of the preceding claims, characterized in that the copolymer of (meth) acrylamido (C1C22) alkylsulphonic acids is a crosslinked copolymer of 2-acrylamido-2-methylpropanesulfonic acid, dimethylacrylamide , lauryl methacrylate, and laureth-4 methacrylate. - 2 9 89 893 20 12. Composition according to any one of the preceding claims, characterized in that the copolymer of (meth) acrylamido (C1C22) alkylsulphonic acids is a copolymer of 2-acrylamido-2-methylpropanesulfonic acid and (meth) C2-C4 alkyl acrylate hydroxyl salt form selected alkali metal salts, ammonium salts, salts of an amino alcohol, amino acid salts. 13. Composition according to any one of the preceding claims, characterized in that the copolymer of (meth) acrylamido (C1-C22) alkylsulphonic acids is present in a content ranging from 0.1% to 10% by weight, relative to the total weight of the composition, preferably from 0.5% to 5% by weight. 14. Composition according to any one of the preceding claims, characterized in that it is in the form of an oil-water emulsion. 15. A method of non-therapeutic treatment of keratin materials comprising applying to said keratin materials a cosmetic composition as defined in any one of the preceding claims.