WO2013160350A2

WO2013160350A2 - Cosmetic composition comprising a phosphorylated oligosaccharide and a sulfonic copolymer

Info

Publication number: WO2013160350A2
Application number: PCT/EP2013/058495
Authority: WO
Inventors: Céline DERRIPS; Cécile Fiandino
Original assignee: L'oreal
Priority date: 2012-04-26
Filing date: 2013-04-24
Publication date: 2013-10-31
Also published as: FR2989893B1; WO2013160350A3; FR2989893A1

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 copolymer of a (meth)acrylamido(C₁-C₂₂)alkylsulfonic acid, in particular crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid, of dimethylacrylamide, of lauryl methacrylate and of laureth-4 methacrylate. Use for caring for and making up keratin materials.

Description

Cosmetic composition comprising a phosphorylated oligosaccharide and a sulfonic copolymer

The present invention relates to compositions, in particular cosmetic compositions, comprising a phosphorylated oligosaccharide and a copolymer of 2-acrylamido-2-methylpropanesulfonic acid, and also to the use of these compositions in a process for treating human keratin materials.

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 denote, for example, the skin, mucous membranes, the lips, the scalp, the eyelashes, the eyebrows and the hair. Oligosaccharides of low molecular weight which have properties as regards lightening the complexion, for exfoliating the skin (WO 2003/013448) or for promoting the cell proliferation of keratinocytes or fibroblasts and for inhibiting the synthesis of certain proteases of elastase type are known (Andres E. et al., Pathol. Biol. (Paris), 2006 Sep; 54(7):420-5; WO 2002/020622). Phosphooligosaccha des such as POs-Ca would also make it possible to improve the elasticity of skin tissue and to combat the signs of aging of the skin (JP2009227632).

However, the introduction of phosphorylated oligosaccharides into an aqueous cosmetic formulation may be reflected by an appreciable decrease in the viscosity and/or destabilization of the composition. In particular, phosphorylated oligosaccharides must be fully dissolved and/or dispersed in the composition.

A composition which is too fluid is difficult to apply to keratin materials. Such a composition runs on keratin materials, in particular on the skin, onto which it is applied. Its application to the keratin materials that it is desired to treat lacks precision and therefore makes it relatively unattractive to use.

Furthermore, thickeners are sought which are not fluidized by the introduction of phosphorylated oligosaccharides.

Thus, there is a need for cosmetic compositions comprising a phosphorylated oligosaccharide and having good stability over time, especially after storage for 2 months at room temperature (25°C) or at a higher temperature, without substantial fluidization and/or destabilization.

The object of the present invention is, precisely, to satisfy 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 copolymer of 2-acrylamido-2- methylpropanesulfonic acid 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 copolymer of 2-acrylamido-2-methylpropanesulfonic acid to a composition comprising a phosphorylated oligosaccharide makes it possible to thicken the composition and to obtain a composition that is stable over time, with a satisfactory viscosity. Moreover, this makes it possible to adjust the phosphorylated oligosaccharide during the various preparation phases without modifying the viscosity.

Moreover, phosphorylated oligosaccharides are fully dissolved and/or dispersed in compositions comprising a particular copolymer of 2-acrylamido-2- methylpropanesulfonic acid. The compositions are homogeneous.

What is more, this specific combination of phosphorylated oligosaccharide- copolymer of 2-acrylamido-2-methylpropanesulfonic acid also makes it possible to confer, on a composition of the invention, a pleasant appearance and, during the application thereof, comfortable feel properties (in particular a less tacky skin).

The present invention also relates to a nontherapeutic treatment process for caring for or making up keratin materials, comprising the application to said keratin materials of a composition in accordance with the invention. Advantageously, such a process is intended for caring for and/or making up the skin. The term "phosphorylated oligosaccharide" means a linear or branched polysaccharide compound consisting of or containing:

a) from 2 to 10 monosaccharide units; and

b) one, two or more than two phosphate groups.

The 2 to 10 monosaccharide units may in particular be pentoses or hexoses. Preferentially, the monosaccharide units are hexoses, and may be selected, independently of each other, 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, pneumose and quinovose.

In particular, the monosaccharide units may all be glucoses.

In the context of the present patent application, the term "phosphorylated oligosaccharides" denotes, without preference, 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 via a-1 -4 glycoside bonds. In particular, the phosphorylated oligosaccharides may comprise or consist of a mixture of maltotriose phosphate, maltotetraose phosphate and maltopentaose phosphate.

The phosphorylated maltooligosaccharides preferably bear 1 or 2 phosphate groups and are optionally combined with calcium.

The phosphorylated oligosaccharides may in particular be those sold 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 phosphooligosaccharides (POs) may be obtained by enzymatic hydrolysis of potato starch using a mixture of bacterial liquefying a-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 fraction that is not hydrolyzable by the enzymes.

These POs comprise or consist of two fractions that may be separated by anion-exchange chromatography:

- a major fraction known as 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 known as PO-2, which is a mixture consisting in major amount of phosphorylated maltopentaose and maltohexaose, and in minor amount 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 fraction PO-1 consists of six monophosphorylated compounds (Kamasaka et al., Biosci. Biotech. Biochem., 1997, 61 (2), 238-244):

3-phosphoryl oligosaccharides [3³-phosphoryl maltotetraose (maltotetraose bearing a phosphate group on the carbon at C3 of the third glucosyl residue) and 3⁴-phosphoryl maltopentaose (maltopentaose bearing a phosphate group on the carbon at C3 of the fourth glucosyl residue)]; and

- 6-phosphoryl oligosaccharides [6³-phosphoryl maltotriose (maltotriose bearing a phosphate group on the carbon at C6 of the third glucosyl residue), 6²-phosphoryl maltotriose (maltotriose bearing a phosphate group on the carbon at C2 of the second glucosyl residue), 6³-phosphoryl maltotetraose (maltotetraose bearing a phosphate group on the carbon at C6 of the third glucosyl residue) and 6⁴-phosphoryl maltopentaose (maltopentaose bearing a phosphate group on the carbon at C6 of the fourth glucosyl residue)].

The mean degree of polymerization of the two dephosphorylated fractions PO-1 and PO-2 is 4.02 and 5.82, respectively.

The two fractions PO-1 and PO-2 may form a complex with calcium ions (calcium phosphooligosaccharides or POs-Ca). This complex contains about 5% calcium, by weight of calcium relative to the total weight of the POs-Ca.

In particular, the POs may 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 process, 1 g of potato starch is suspended in 100 ml of a solution containing 6 mM NaCI, 2 mM CaC^ and 3.0 U/ml of BLA (bacterial liquefying a-amylase). After having gradually heated the suspension to 100°C to liquefy it, the solution is cooled and incubated at 50°C for 1 hour. 1 ml of glucoamylase at 600 U/ml, 1 ml of pullulanase at 200 U/ml and 1 ml of BLA at 300 U/ml are then added, and the reaction mixture is incubated at 40°C for 2 hours

The amylolytic reaction progress may be monitored by the starch-iodine complex method and/or by the glucose oxidase method (see Barham and Trinder, Analyst, 1972, 97, 142-146). Since the action of the amylolytic enzymes is blocked by the phosphate groups linked to the glucose residues, the phosphorylated oligosaccharides are present in the indigestible fraction of this enzymatic treatment.

Once the enzymatic reaction is complete (which may be determined by a negative starch-iodine staining reaction), the solution is heated in a boiling water bath for 10 minutes and then applied onto a column of anion-exchange resin (for example Chitopearl BCW-2501 ; 1 φ x 2 cm or an equivalent column) which has been equilibrated with a 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) also containing 0.5 M NaCI.

The eluted phosphorylated oligosaccharides may be desalted, for example by precipitation with ethanol (at a concentration of 70% v/v) followed by washing with 70% ethanol before dissolution in deionized water, or by passing through a cation-exchange column (for example Dowex 50WX4, 20-50 mesh or an equivalent column).

The phosphorylated oligosaccharides complexed with calcium (POs-Ca) may 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 and preferably from 0.1 % to 5% by weight relative to the total weight of the composition. The composition according to the invention comprises a copolymer of (meth)acrylamido(Ci-C22)alkylsulfonic acids. The term "copolymer of (meth)acrylamido(Ci-C22)alkylsulfonic acids" means copolymers comprising at least one (meth)acrylamido(Ci-C22)alkylsulfonic acid monomer and at least one monomer other than (meth)acrylamido(d- C22)alkylsulfonic acids.

The copolymers of (meth)acrylamido(Ci-C22)alkylsulfonic acids according to the invention may or may not be crosslinked.

Crossl inked copolymers are preferably chosen. When they are crosslinked, the crosslinking agents may be selected from polyolefinically unsaturated compounds commonly used for the crosslinking of polymers obtained by free-radical polymerization.

Mention may be made, for example, of divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol di(meth)acrylate or tetraethylene glycol di(meth)acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth)acrylate, allyl ethers of alcohols of the sugar series, or other allyl or vinyl ethers of polyfunctional alcohols, and also allyl esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.

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

The (meth)acrylamido(Ci-C22)alkylsulfonic acids are chosen, for example, from acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2- methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3- heptanesulfonic acid, and also partially or totally neutralized forms thereof.

2-Acrylamido-2-methylpropanesulfonic acid (AMPS®), and also partially or totally neutralized forms thereof, will more particularly be used. 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 amino alcohol, such as, for example, the monoethanolamine salt, or in the form of an amino acid salt, such as, for example, the lysine or arginine salt.

Advantageously, the copolymer is salified in sodium or ammonium salt form.

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 containing from 6 to 50 carbon atoms such as (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or monoalkylene 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.

Used may especially be made of copolymers of 2-acrylamido-2- methylpropanesulfonic acid and of an optionally salified, hydroxylated C2-C₄ alkyl (meth)acrylate.

The hydroxylated C2-C₄ alkyl (meth)acrylate monomer may be chosen from 2- hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2,3-dihydroxypropyl acrylate and 2,3-dihydroxypropyl methacrylate.

Said copolymer may be salified, in particular in the form of an alkali metal salt, for instance the sodium or potassium salt, or in the form of an ammonium salt, or in the form of a salt of an amino alcohol, for instance the monoethanolamine salt, or in the form of an amino acid salt, for instance the lysine salt. Advantageously, the copolymer is salified in sodium salt form.

Preferably, the composition comprises the copolymer of 2-acrylamido-2- methylpropanesulfonic acid and of 2-hydroxyethyl acrylate, especially in sodium salt form, for instance the products sold under the trade name 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(Ci-C22)alkylsulfonic acids and of at least one ethylenically unsaturated monomer comprising at least one hydrophobic portion containing from 6 to 50 carbon atoms, more preferentially from 6 to 22 carbon atoms, even more preferentially 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 other than ethylenically unsaturated monomers comprising at least one hydrophobic part containing from 6 to 50 carbon atoms, chosen from (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or monoalkylene 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.

These copolymers are described especially in patent applications EP-A-750 899 and WO 2008/087 326 and patent US 5 089 578 and in the following publications from Yotaro Morishima:

- "Self-assembling amphiphilic polyelectrolytes and their nanostructures - Chinese Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336";

- "Micelle formation of random copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules 2000, Vol. 33, No. 10 - 3694-3704";

- "Solution properties of micelle networks formed by nonionic moieties covalently bound to a polyelectrolyte: salt 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 selected from the (meth)acrylates or (meth)acrylamides of formula (I) below: CH₂ C

(I)

O= C

-CH₂-CH(R₃)-O -FL

in which Ri and R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y denotes O or NH; R₂ denotes a hydrophobic hydrocarbon-based radical containing at least from 6 to 50 carbon atoms, more preferably from 6 to 22 carbon atoms, more preferably still from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from O to 100. The radical R2 is preferably selected from linear C6-C18 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl or n-dodecyl radicals); branched or cyclic C6-C18 alkyl radicals (for example cyclododecane (C12) or adamantane (C10) radicals); C6-C18 alkylperfluoro radicals (for example the group of formula -(CH₂)2-(CF₂)9-CF₃); the cholesteryl (C27) radical or a cholesterol ester residue, such as the cholesteryl oxyhexanoate group; or polycyclic aromatic groups, such as naphthalene or pyrene. Among these radicals, the ones that are more particularly preferred are linear alkyl radicals and more particularly the n- dodecyl radical. 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 constituted of ethylene oxide units and/or of propylene oxide units and even more particularly constituted of ethylene oxide units. The number of oxyalkylene units generally ranges from 1 to 50, more preferably from 2 to 25 and more preferably still from 3 to 10.

Among these polymers, mention may be made of:

- copolymers, which may or may not be crosslinked and which may or may not be neutralized, comprising from 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C8-Ci6)alkyl(meth)acrylamide units or of (Cs-Ci6)alkyl (meth)acrylate units, relative to the polymer, such as those described in patent application EP-A-750 899;

- terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C₆- Ci8)alkylacrylamide units, such as those described in patent US-5 089 578. Mention may also be made of copolymers of AMPS and of dodecyl methacrylate, and also crosslinked and noncrossl inked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.

The distribution of the monomers in the polymers of the invention may be, for example, alternate, block (including multiblock) or random.

Preferably, the composition comprises a crosslinked copolymer of 2-acrylamido- 2-methylpropanesulfonic acid, of dimethylacrylamide, of lauryl methacrylate and of laureth-4 methacrylate, for instance the products sold under the trade name Sepimax^® Zen by the company SEPPIC (INCI name: Polyacrylate Crosspolymer-6). Such polymers are described especially in patent application WO 2008/087 326.

The copolymer of 2-acrylamido-2-methylpropanesulfonic acid may be present in the composition according to the invention in an amount 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 calcium phosphorylated oligosaccharide (named A) and the copolymer of 2-acrylamido-2-methylpropanesulfonic acid (named B) described previously may be present in the composition according to the invention in an A B weight ratio ranging from 0.5 to 5.

Preferably, this A B weight ratio may range from 0.7 to 4. Preferentially, this A/B weight ratio may range from 1 to 2.5.

The viscosity of a composition of the invention may be measured via any process known to those skilled in the art, and especially according to the following conventional process. Thus, the measurement can be carried out at 25°C using a Rheomat 180 viscometer equipped with a spindle rotating at 200 rpm. Those skilled in the art may select the spindle for measuring the viscosity from the spindles M1 , M2, M3 and M4 on the basis of their general knowledge, so as to be able to perform the measurement.

The composition according to the invention comprises a physiologically acceptable aqueous medium. The term "physiologically acceptable medium" is intended to denote a medium that is compatible with human keratin materials and/or fibers, for instance, in a nonlimiting manner, the skin, mucous membranes, the nails, the scalp and/or the hair.

This physiologically acceptable aqueous medium comprises an aqueous phase, optionally as a mixture, or not, with one or more organic solvents, such as a Ci- Cs alcohol, in particular ethanol, isopropanol, tert-butanol, n-butanol, polyols such as glycerol, propylene glycol, butylene glycol, and polyol ethers.

A composition according to the invention may also comprise a fatty phase, which may comprise oils, gums and waxes normally used in the field of application under consideration.

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

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

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

As oils that can be used in the invention, mention may be made of mineral oils (liquid petroleum jelly), plant oils (liquid fraction of shea butter, sunflower oil), synthetic oils (Purcellin oil), silicone-based oils or waxes (cyclomethicone) and fluorinated oils (perfluoropolyethers). Fatty alcohols and fatty acids (stearic acid) may be added to these oils. When a composition is an emulsion, the proportion of the fatty phase may 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, waxes, emulsifiers and co- emulsifiers 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 that are common in the field under consideration, such as emulsifiers, hydrophilic or lipophilic gelling agents, waxes, hydrophilic or lipophilic additives, preserving agents, antioxidants, solvents, fragrances, fillers, UVA and/or UVB screening agents (organic or mineral, 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 range, for example, from 0.01 % to 30% of the total weight of the composition. In general, the amounts are adjusted as a function of the formulation prepared. Depending on their nature, these adjuvants may be introduced into the fatty phase, into the aqueous phase and/or into lipid spherules.

Advantageously, the composition according to the invention may comprise, in addition to the copolymer of 2-acrylamido-2-methylpropanesulfonic acid according to the invention, a 2-acrylamido-2-methylpropanesulfonic acid homopolymer, in particular in partially or totally neutralized form. Such a polymer makes it possible especially to reduce the tack of the composition when it is applied to the skin.

Preferentially, said homopolymer may be partially or totally neutralized with a mineral base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base such as monoethanolamine, diethanolamine or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds. They are generally neutralized. In the present invention, the term "neutralized" refers to polymers that are totally or virtually totally neutralized, i.e. at least 90% neutralized.

The homopolymer may have a number-average molecular weight ranging from 1000 to 20 000 000 g/mol, preferably ranging from 20 000 to 5 000 000 and even more preferentially from 100 000 to 1 500 000 g/mol.

The homopolymer may be crosslinked, especially with crosslinking agents that may be chosen from the polyolefinically unsaturated compounds commonly used for crosslinking 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, ethylene glycol or tetraethylene glycol di(meth)acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth)acrylate, allylic ethers of alcohols of the sugar series, or other allyl or vinyl ethers of polyfunctional alcohols, and also the allylic esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.

According to one preferred embodiment of the invention, the crosslinking agent is chosen from methylenebisacrylamide, allyl methacrylate and trimethylolpropane triacrylate (TMPTA). The degree of crosslinking generally ranges from 0.01 mol% to 10 mol% and more particularly from 0.2 mol% to 2 mol% relative to the polymer.

A polymer of this type that may especially be mentioned is the crosslinked and neutralized 2-acrylamido-2-methylpropanesulfonic acid homopolymer sold by the company Clariant under the trade name Hostacerin® AMPS (CTFA name: ammonium polyacryldimethyltauramide). A composition of the invention may be provided in any galenical form that may be envisioned.

In particular, a composition according to the invention may have the form of an aqueous or aqueous/alcoholic 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; or an aerosol composition also comprising a pressurized propellant. Preferentially, the composition according to the invention may be an oil-in-water or water-in-oil emulsion. More preferentially, 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 patent application WO-A-2009/080 958.

A composition according to the invention may also be in the form of a care product, an antisun or after-sun product, a daily photoprotective care product, a body product, a foundation to be applied to the face or the neck, a concealer product, a complexion corrector, a tinted cream or a makeup base for making up the face, or a body makeup composition.

A composition according to the invention may be used for the purposes of improving the general condition of the epidermis, in particular of the skin, and especially for maintaining or restoring its physiological functions and/or its esthetic appearance.

Other characteristics and advantages of the invention will emerge more clearly from the examples that follow, which are given as nonlimiting illustrations. In the text hereinbelow or hereinabove, the proportions are given as weight percentages, unless otherwise indicated.

Example 1 :

Two compositions (facial care cream) described in the table below were prepared: a composition according to the invention (A) containing a calcium phosphorylated oligosaccharide and a copolymer of sodium acrylamido-2- methylpropanesulfonate according to the invention and a composition B containing a sodium acrylamido-2-methylpropanesulfonate homopolymer.

Composition A according to the invention is stable and is thickened, whereas composition B is liquid.

The formulation not containing the AMPS® copolymer Sepimax Zen according to the invention is unstable.

Example 2:

A composition (facial care cream) having the composition described in the table below was prepared:

Example 2

Calcium phosphorylated 2% AM

oligosaccharide (POs-Ca from Ezaki

Glico)

Sodium acrylamido-2- methylpropanesulfonate/ 1 .5

lauryl methacrylate/lauryl methacrylate

oxyethylenated with 4 mol of ethylene

oxide/dimethylacrylamide copolymer

(Sepimax Zen from SEPPIC)

Ammonium acrylamido-2- methylpropanesulfonate crosslinked

homopolymer (Hostacerin AMPS®

from Clariant)

Mixture of glyceryl stearate and PEG- 0.75

100 stearate (Arlacel® 165 FL from

Uniqema)

Mixture of cetylstearyl glucoside and of 2

cetyl and stearyl alcohols (12/46/42)

(Montanov 68 from SEPPIC)

Dimethicone 10 cSt 2.5

Polyethylene glycol (20 OE) 2

(Carbowax Sentry Polyethylene Glycol

1000 NF, FCC Grade from Dow

Chemical)

Lactic acid 0.25

Stearyl alcohol 0.5

Cetyl alcohol 0.5

Apricot kernel oil 2

Preserving agent qs

Water qs 100%

The composition of Example 2 according to the invention is stable and thickened.

When applied to the skin, this composition combats the signs of aging of the skin.

Example 3:

Two compositions (facial care cream) described in the table below were prepared: a composition according to the invention (A) containing a calcium phosphorylated oligosaccharide and a copolymer of sodium acrylamido-2- methylpropanesulfonate according to the invention and a composition B containing an alkyl carboxyvinyl polymer.

Composition A according to the invention is stable and thickened, whereas, in compositions B and C, the phosphorylated oligosaccharide is poorly dispersed and forms lumps. Furthermore, composition C is liquid.

Claims

1 . A composition comprising, in a physiologically acceptable aqueous medium:

i) at least one phosphorylated oligosaccharide, and

ii) at least one copolymer of a (meth)acrylamido(Ci-C22)alkylsulfonic acid.

2. The composition as claimed in claim 1 , in which the phosphorylated oligosaccharides consist of 2 to 10 monosaccharide units and of one, two or more than two phosphate groups.

3. The composition as claimed in either of claims 1 and 2, in which the phosphorylated oligosaccharides, independently of each other, comprise monosaccharide units selected from fructose, psicose, sorbose, tagatose, glucose, galactose, mannose, allose, altrose, gulose, idose, talose, rhamnose, fucose fubulose, pneumose and quinovose.

4. The composition as claimed in any one of claims 1 to 3, in which the phosphorylated oligosaccharides are phosphorylated maltooligosaccharides bearing 1 or 2 phosphate groups.

5. The composition as claimed in any one of claims 1 to 4, in which the phosphorylated oligosaccharides may be obtained by enzymatic hydrolysis of potato starch using a mixture of bacterial liquefying a-amylase, glucoamylase and pullulanase.

6. The composition as claimed in any one of claims 1 to 5, in which the phosphorylated oligosaccharides comprise monophosphorylated maltotrioses, maltotetraoses and maltopentaoses, and maltotrioses, maltotetraoses, maltopentaoses, maltohexaoses, maltoheptaoses and maltooctaoses each containing at least two phosphate groups.

7. The composition as claimed in any one of claims 1 to 6, in which the phosphorylated oligosaccharides are in the form of complexes with calcium ions.

8. The composition as claimed in any one of the preceding claims, characterized in that the phosphorylated oligosaccharide(s) are present in a content ranging from 0.01 % to 10% by weight and preferably from 0.1 % to 5% by weight relative to the total weight of the composition.

9. The composition as claimed in any one of the preceding claims, characterized in that the copolymer(s) of (meth)acrylamido(Ci-C22)alkylsulfonic acids also comprise one or more ethylenically unsaturated monomers chosen from ethylenically unsaturated monomers comprising at least one hydrophobic part containing from 6 to 50 carbon atoms such as (meth)acrylic acids, β- substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or monoalkylene 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.

10. The composition as claimed in any one of the preceding claims, characterized in that the copolymer(s) of (meth)acrylamido(Ci-C22)alkylsulfonic acids are chosen from copolymers of (meth)acrylamido(Ci-C22)alkylsulfonic acids and of at least one ethylenically unsaturated monomer comprising at least one hydrophobic portion containing from 6 to 50 carbon atoms, more preferentially from 6 to 22 carbon atoms, even more preferentially from 6 to 18 carbon atoms and more particularly 10 to 14 carbon atoms.

1 1 . The composition as claimed in any one of the preceding claims, characterized in that the copolymer of (meth)acrylamido(Ci-C22)alkylsulfonic acids is a crosslinked copolymer of 2-acrylamido-2-methylpropanesulfonic acid, of dimethylacrylamide, of lauryl methacrylate and of laureth-4 methacrylate.

12. The composition as claimed in any one of the preceding claims, characterized in that the copolymer of (meth)acrylamido(Ci-C22)alkylsulfonic acids is a copolymer of 2-acrylamido-2-methylpropanesulfonic acid and of a hydroxylated C2-C₄ alkyl (meth)acrylate in the form of a salt chosen from alkali metal salts, ammonium salts, amino alcohol salts and amino acid salts.

13. The composition as claimed in any one of the preceding claims, characterized in that the copolymer of (meth)acrylamido(Ci-C22)alkylsulfonic acids is present in a content ranging from 0.1 % to 10% by weight and preferably ranging from 0.5% to 5% by weight relative to the total weight of the composition.

14. The composition as claimed in any one of the preceding claims, characterized in that it is in the form of an oil-in-water emulsion.

15. A nontherapeutic process for treating keratin materials, comprising the application to said keratin materials of a cosmetic composition as defined according to any one of the preceding claims.