WO2013087927A1 - Composition comprising silica aerogel particles and a hydrophilic acrylic homopolymer or copolymer - Google Patents

Composition comprising silica aerogel particles and a hydrophilic acrylic homopolymer or copolymer Download PDF

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Publication number
WO2013087927A1
WO2013087927A1 PCT/EP2012/075776 EP2012075776W WO2013087927A1 WO 2013087927 A1 WO2013087927 A1 WO 2013087927A1 EP 2012075776 W EP2012075776 W EP 2012075776W WO 2013087927 A1 WO2013087927 A1 WO 2013087927A1
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composition
μηη
mol
weight
ethylene oxide
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PCT/EP2012/075776
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French (fr)
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Mathilde LEMAL
Laure Fageon
Raluca Lorant
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L'oreal
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Publication of WO2013087927A1 publication Critical patent/WO2013087927A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/062—Oil-in-water emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/008—Preparations for oily skin

Definitions

  • composition comprising silica aerogel particles and a hydrophilic acrylic
  • the present patent application relates to a composition for topical application comprising at least 5% by weight, relative to the total weight of the composition, of a fatty phase dispersed in an aqueous phase, hydrophobic silica aerogel particles and at least one hydrophilic acrylic homopolymer or copolymer, and to the use of the said composition in cosmetics and dermatology, in particular for caring for or treating keratin materials.
  • galenical forms of cream-gel type i.e. oil- in-water compositions in the form of a dispersion of a fatty phase in an aqueous gel, containing little or no emulsifier.
  • These galenical forms are appreciated for their harmlessness, but also for their sensory effects. Specifically, they afford an opalescent appearance, and a fresh, aqueous feel on application.
  • Galenical forms of this type may be obtained with hydrophilic acrylic homopolymers or copolymers such as non-superabsorbent and at least partially neutralized acrylic acid homopolymers or copolymers and amphiphilic homopolymers or copolymers comprising at least one monomer bearing a sulfonic group.
  • compositions obtained are not very stable. To stabilize them, it is necessary to use emulsifying systems combined with large contents of surfactants and/or thickeners, which have the drawback of making the textures sensorily lank and of giving a tacky, sticky feel and a certain irritant potential, in particular for people with sensitive or reactive skin. Moreover, the compositions lose their opalescent appearance.
  • Patent application FR 2 925 360 proposes to combine an inulin modified with hydrophobic chains with a hydrophilic acrylic polymer in order to obtain stable emulsions that are sensorily pleasant, when the compositions contain more than 5% by weight of fatty substance relative to the total weight of the composition, even without added surfactant.
  • the opalescent appearance and the fresh, aqueous sensation obtained on applying these compositions is not entirely satisfactory, in particular when the fatty phase content is large.
  • compositions comprising hydrophobic silica aerogel particles and at least one hydrophilic acrylic homopolymer or copolymer make it possible to produce cream-gels with an opalescent appearance that afford a fresh, aqueous sensation on application, in the presence of a fatty phase, even in an amount of greater than or equal to 5%.
  • one subject of the present invention is a composition for topical application comprising at least 5% by weight, relative to the total weight of the composition, of a fatty phase dispersed in an aqueous phase, hydrophobic silica aerogel particles with a specific surface area per unit of mass (S M ) ranging from 500 to 1500 m 2 /g and a size expressed as the volume-mean diameter (D[0.5]) ranging from 1 to 1500 ⁇ , and at least one hydrophilic acrylic homopolymer or copolymer;
  • S M specific surface area per unit of mass
  • D[0.5] volume-mean diameter
  • composition A Composition A
  • Polysorbate 80 (Tween 80-LQ-(WL) from Croda)
  • Carbomer (Carbopol 981 from Lubrizol) 0.15
  • Glyceryl stearate (and) PEG-100 stearate (Arlacel 165-FL
  • Polysorbate 80 (Tween 80-LQ-(WL) from Croda) 1 .00
  • Carbomer (Carbopol 981 from Lubrizol) 0.15
  • Glyceryl stearate (and) PEG-100 stearate (Arlacel 165-FL
  • Ammonium polyacryloyldimethyl taurate (Hostacerin 1 .60 AMPS® from Clariant)
  • Hydrophobic silica aerogel particles (VM-2270 from
  • a subject of the present invention is a composition for topical application comprising at least 5% by weight, relative to the total weight of the composition, of a fatty phase dispersed in an aqueous phase; hydrophobic silica aerogel particles with a specific surface area per unit of mass (S M ) ranging from 500 to 1500 m 2 /g, preferably from 600 to 1200 m 2 /g and better still from 600 to 800 m 2 /g, and a size expressed as the mean volume diameter (D[0.5]) ranging from 1 to 1500 ⁇ , better still from 1 to 1000 ⁇ , even more preferentially from 1 to 100 ⁇ , in particular from 1 to 30 ⁇ , more preferably from 5 to 25 ⁇ , better still from 5 to 20 ⁇ and even better still from 5 to 15 ⁇ ;
  • S M specific surface area per unit of mass
  • composition being different from:
  • a cosmetic composition comprising a mixture of hydrophobic silica aerogel particles with a specific surface area per unit of mass (S M ) ranging from 500 to 1500 m 2 /g and a size expressed as the mean volume diameter (D[0.5]) ranging from 1 to 1500 ⁇ , of at least a first linear silicone oil with a viscosity of greater than 50 mm 2 /s and of at least second and third linear silicone oils each with a viscosity of less than or equal to 50 mm 2 /s, and of an acrylamidomethylpropanesulfonic acid homopolymer ; and
  • a cosmetic composition comprising a mixture of hydrophobic silica aerogel particles with a specific surface area per unit of mass (S M ) ranging from 500 to 1500 m 2 /g and a size expressed as the mean volume diameter (D[0.5]) ranging from 1 to 1500 ⁇ , of at least a first hydrocarbon-based oil, of at least a second hydrocarbon-based oil chosen from pentaerythritol esters, hydrogenated polyolefins and fatty acid triglycerides, and mixtures thereof, the first hydrocarbon-based oil being present in a content of greater than or equal to 40% by weight of the mixture of the first and second oils, and of an acrylamidomethylpropanesulfonic acid homopolymer.
  • S M specific surface area per unit of mass
  • D[0.5] mean volume diameter
  • a subject of the present invention is a composition for topical application comprising at least 5% by weight, relative to the total weight of the composition, of a fatty phase dispersed in an aqueous phase, hydrophobic silica aerogel particles with a specific surface area per unit of mass (S M ) ranging from 500 to 1500 m 2 /g and a size expressed as the volume-mean diameter (D[0.5]) ranging from 1 to 1500 ⁇ , and at least one acrylic polymer chosen from non-superabsorbent and at least partially neutralized acrylic acid homopolymers or copolymers and copolymers comprising at least one monomer bearing a sulfonic group.
  • S M specific surface area per unit of mass
  • D[0.5] volume-mean diameter
  • composition of the invention is intended for topical application to the skin or the integuments, it comprises a physiologically acceptable medium, i.e. a medium that is compatible with all keratin materials such as the skin, the nails, mucous membranes and keratin fibres (such as the hair or the eyelashes).
  • a physiologically acceptable medium i.e. a medium that is compatible with all keratin materials such as the skin, the nails, mucous membranes and keratin fibres (such as the hair or the eyelashes).
  • composition according to the invention is in cream-gel form, is stable and has a pleasant texture, and in particular affords a fresh, aqueous sensation on application.
  • a subject of the invention is also a cosmetic treatment process for keratin materials, which consists in applying to the keratin materials a composition as defined above.
  • a subject of the invention is also the use of the said composition in cosmetics or dermatology, and in particular for caring for, protecting and/or making up bodily or facial skin, or for haircare.
  • Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air.
  • sol-gel processes are generally synthesized via a sol-gel process in liquid medium and then dried, usually by extraction of a supercritical fluid, the one most commonly used being supercritical C0 2 . This type of drying makes it possible to avoid shrinkage of the pores and of the material.
  • the sol-gel process and the various drying operations are described in detail in Brinker C.J. and Scherer G.W., Sol-Gel Science, New York, Academic Press, 1990.
  • the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of mass (S M ) ranging from 500 to 1500 m 2 /g, preferably from 600 to 1200 m 2 /g and better still from 600 to 800 m 2 /g, and a size expressed as the volume- average diameter (D[0.5]) ranging from 1 to 1500 ⁇ , better still from 1 to 1000 ⁇ , preferably from 1 to 100 ⁇ , in particular from 1 to 30 ⁇ , more preferably from 5 to 25 ⁇ , better still from 5 to 20 ⁇ and even better still from 5 to 15 ⁇ .
  • S M specific surface area per unit of mass
  • D[0.5] volume- average diameter
  • the hydrophobic silica aerogel particles used in the present invention have a size, expressed as volume-average diameter (D[0.5]), ranging from 1 to 30 ⁇ , preferably from 5 to 25 ⁇ , better still from 5 to 20 ⁇ and even better still from 5 to 15 ⁇ .
  • D[0.5] volume-average diameter
  • the specific surface per unit of weight can be determined by the nitrogen absorption method, known as the BET (Brunauer-Emmett-Teller) method, described in The Journal of the American Chemical Society, Vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (appendix D).
  • BET Brunauer-Emmett-Teller
  • the BET specific surface corresponds to the total specific surface of the particles under consideration.
  • the sizes of the silica aerogel particles may be measured by static light scattering using a commercial particle size analyser such as the MasterSizer 2000 machine from Malvern.
  • the data are processed on the basis of the Mie scattering theory.
  • This theory which is exact for isotropic particles, makes it possible to determine, in the case of non- spherical particles, an "effective" particle diameter.
  • This theory is described in particular in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957.
  • the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of mass (S M ) ranging from 600 to 800 m 2 /g and a size expressed as the volume-mean diameter (D[0.5]) ranging from 5 to 20 ⁇ and even better still from 5 to 15 ⁇ .
  • the silica aerogel particles used in the present invention may advantageously have a tamped density (p) ranging from 0.04 g/cm 3 to 0.10 g/cm 3 and preferably from 0.05 g/cm 3 to 0.08 g/cm 3 .
  • this density known as the tamped density, may be assessed according to the following protocol:
  • the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of volume S v ranging from 5 to 60 m 2 /cm 3 , preferably from 10 to 50 m 2 /cm 3 and better still from 15 to 40 m 2 /cm 3 .
  • the hydrophobic silica aerogel particles according to the invention have an oil absorption capacity, measured at the wet point, ranging from 5 to 18 ml/g, preferably from 6 to 15 ml/g and better still from 8 to 12 ml/g.
  • the oil-absorbing capacity measured at the wet point, noted Wp corresponds to the amount of water that needs to be added to 100 g of particles in order to obtain a homogeneous paste.
  • the oil uptake corresponds to the ratio Vs/m.
  • the aerogels used according to the present invention are hydrophobic silica aerogels, preferably of silyl silica (INCI name: silica silylate).
  • hydrophobic silica means any silica whose surface is treated with silylating agents, for example halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups Si-Rn, for example trimethylsilyl groups.
  • silylating agents for example halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes
  • hydrophobic silica aerogel particles surface-modified with trimethylsilyl groups (trimethylsiloxyl silica).
  • hydrophobic silica aerogels which can be used in the invention, for example, of the aerogel sold under the name VM-2260 (INCI name: Silica silylate) by the company Dow Corning, the particles of which have an average size of approximately 1000 microns and a specific surface area per unit of mass ranging from 600 to 800 m 2 /g. Mention may also be made of the aerogels sold by the company Cabot under the references Aerogel TLD 201 , Aerogel OGD 201 and Aerogel TLD 203, Enova® Aerogel MT 1 100 and Enova Aerogel MT 1200.
  • the hydrophobic silica aerogel particles may be present in the composition according to the invention in a content ranging from 0.05% to 10% by weight, preferably from 0.05% to 5% by weight, better still from 0.1 % to 5% by weight and more preferably from 0.5% to 2% by weight relative to the total weight of the composition.
  • composition according to the invention comprises at least one hydrophilic acrylic homopolymer or copolymer.
  • hydrophilic acrylic homopolymer or copolymer means a crosslinked or non-crosslinked polymer of the polyacrylic family, which is capable of forming a gel in pure water.
  • the hydrophilic acrylic homopolymer(s) or copolymer(s) are chosen from non-superabsorbent and at least partially neutralized acrylic acid homopolymers or copolymers and homopolymers or copolymers comprising at least one monomer bearing a sulfonic group.
  • the hydrophilic acrylic homopolymer(s) or copolymer(s) are chosen from non- superabsorbent and at least partially neutralized acrylic acid homopolymers or copolymers and copolymers comprising at least one monomer bearing a sulfonic group.
  • Any non-superabsorbent acrylic acid homopolymer or copolymer is suitable for use in the present invention provided that it is hydrophilic and is used in an at least partially neutralized form.
  • non-superabsorbent polymer is a polymer that does not correspond to the definition given below for superabsorbent polymers.
  • hydrophilic polymer means a polymer that is dispersible in water.
  • non-superabsorbent acrylic homopolymers or copolymers that are suitable for the invention may be present in the composition in a particulate or non-particulate form.
  • their average size in the hydrated state is preferably less than or equal to 10 ⁇ and even more preferentially less than or equal to 5 ⁇ .
  • Their average size in the nonhydrated state is preferably less than or equal to 2 ⁇ , preferably less than or equal to 1 ⁇ .
  • non-superabsorbent acrylic polymers already neutralized before use, or otherwise, examples that may be mentioned include:
  • Cosmedia SP ® containing 90% solids and 10% water
  • Cosmedia SPL ® as an inverse emulsion containing about 60% dry active material, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by the company Cognis;
  • a non-superabsorbent acrylic acid polymer in accordance with the present invention which has not been neutralized beforehand, may be neutralized by any suitable means and in particular by adding sodium hydroxide. Sodium polyacrylates are thus obtained. Potassium polyacrylates are also suitable for the present invention.
  • the neutralization may be performed prior to use in the composition of the invention if the polymer in question is sold in a non-neutralized form.
  • neutralization is inherent in the raw material. This is the case in particular for Luvigel ® EM and for the products called Cosmedia ® SP and SPL, which are already partially neutralized.
  • the neutralization step for example with sodium or potassium counterions, is important for giving the acidic polymers their properties of the gelling and thus stabilizing of the composition.
  • Said acrylic polymers are converted into the corresponding acrylate polymers during this neutralization step.
  • Said acrylic monomers of the acrylic polymer according to the invention may be neutralized in a proportion of from 5% to 80%.
  • the acrylic polymer in accordance with the invention may comprise nonionic monomers.
  • nonionic monomers use may be made of acrylamide, methacrylamide, vinylpyrrolidone, vinylimidazole, vinylcaprolactam and hydroxy(CrC 4 )alkyl esters of carboxylic acids, such as hydroxyethyl acrylates.
  • the acrylic acid homopolymer or copolymer may be in the form of a water-in-oil emulsion, known as an inverse emulsion.
  • This inverse emulsion may be obtained, for example, by inverse emulsion polymerization.
  • the polymer used is a partially neutralized sodium polyacrylate that is in the form of an inverse emulsion comprising at least one polar oil.
  • oils mention may be made of fatty acid esters.
  • fatty acid esters examples include isopropyl esters of fatty acids, such as isopropyl palmitate or isopropyl myristate, or fatty acid polyglycerides, in particular of fatty acid mixtures comprising at least 50% of capric and/or caprylic acid.
  • fatty acid esters such as isopropyl palmitate or isopropyl myristate
  • fatty acid polyglycerides in particular of fatty acid mixtures comprising at least 50% of capric and/or caprylic acid.
  • water-in-oil emulsions are described in document US 6 197 283.
  • the oily phase may consist of one or more fatty acid esters, one or more fatty acid polyglycerides based on a mixture of polyglycerides, which contains diglycerides and triglycerides, with mixtures of fatty acids, which contain caprylic acid and/or capric acid, preferably in a proportion of at least 50% by weight relative to the total weight of fatty acids.
  • the oil content of the inverse emulsion is between 15% and 70% by weight and in particular between 20% and 35% by weight relative to the total weight of the inverse emulsion.
  • Luvigel ® EM the oily phase of which comprises 26% of oil phase consisting of C 8 -Ci 0 triglycerides, that is to say the fatty acids of which are a mixture of caprylic and capric acid.
  • the water-in-oil emulsion may contain from 0.25% to 7% by weight and preferably from 0.5% to 5% by weight of a surfactant.
  • the at least partially neutralized acrylic polymer may be present in the inverse emulsion in a content ranging from 20% to 70% by weight, in particular from 20% to 65% by weight, for example from 20% to 62% by weight relative to the total weight of the inverse emulsion.
  • the acrylic polymer may be present in the inverse emulsion in a content ranging from 20% to 30% by weight relative to the total weight of the inverse emulsion.
  • the acrylic polymer may be present in the inverse emulsion in a content ranging from 50% to 62% by weight relative to the total weight of the composition.
  • the non-superabsorbent polymers may consist of:
  • the oily phase may then consist of one or more fatty acid esters as described previously.
  • the non-superabsorbent homopolymer(s) or copolymer(s) which are at least partially neutralized may be crosslinked or non-crosslinked.
  • crosslinking of the acrylic acid may be obtained according to any method known to those skilled in the art, especially according to the description of document US 6 197 283 or according to the description of document US 6 444 785, which mention the crosslinking agents that may be used.
  • crosslinking agents are in particular methylenebisacrylamide, divinylpyrrolidone, alkyl (meth)acrylate, triallylamine, ethylene glycol diacrylates (up to 50 EO), (meth)acrylic esters with di- or polyhydric alcohols such as trimethylolpropane triacrylate or pentaerythrityl tetraacrylate.
  • the crosslinking agent is water-soluble.
  • the crosslinking agent is triallylamine.
  • the preparation of W/O emulsions comprising a polymer in accordance with the present invention may be performed according to the teaching of document US 6 444 785.
  • the object of this process is to lower the content of remaining monomers by post-treatment with a redox initiator system.
  • the post-treatment of the W/O emulsion is performed by addition of a redox initiator system which comprises essentially a) 0.001 % to 5% by weight, relative to the total amount of monomers used for the preparation of the polymer,
  • R 1 denotes hydrogen, a Ci to C 8 alkyl group or a C 6 to Ci 2 aryl group, and/or a2) of a compound that releases hydrogen peroxide in aqueous medium
  • R2 hydrogen, or a C1-C12 alkyl group, optionally containing functional groups and/or possibly comprising olefinic unsaturations,
  • R3 hydrogen, OH, or a C1-C12 alkyl group, optionally containing functional groups and/or possibly comprising olefinic unsaturations, and whereas R2 and R3 may form a cyclic structure, which may contain a heteroatom and/or functional groups, and/or may comprise olefinic unsaturations, and/or
  • the polymers comprising at least one monomer bearing a sulfonic group that are used in the composition of the invention are water-dispersible or water-swellable.
  • the polymers used in accordance with the invention may be homopolymers or copolymers and may be obtained from at least one ethylenically unsaturated monomer bearing a sulfonic group, which may be in free form or partially or totally neutralized form. These polymers may optionally comprise at least one hydrophobic group and then constitute an amphiphilic polymer (or hydrophobic modified polymer).
  • the polymers in accordance with the invention 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.
  • a mineral base sodium hydroxide, potassium hydroxide or aqueous ammonia
  • 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.
  • neutralized refers to polymers that are totally or virtually totally neutralized, i.e. at least 90% neutralized.
  • the polymers used in the composition of the invention generally have a number-average molecular weight ranging from 1000 to 20 000 000 g/mol, preferably ranging from 20 000 to 5 000 000 g/mol and even more preferentially from 100 000 to 1 500 000 g/mol.
  • These polymers according to the invention may be crosslinked or non-crosslinked.
  • the monomers bearing a sulfonic group of the polymer used in the composition of the invention are especially chosen from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci-C 2 2)alkylsulfonic acids, N-(Ci-C 2 2)alkyl(meth)acrylamido(Ci- C 2 2)alkylsulfonic acids such as undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof, and mixtures thereof.
  • the monomers bearing a sulfonic group are chosen from (meth)acrylamido(Ci-C 2 2)alkylsulfonic acids, for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2- methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2- acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid and 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, and mixtures thereof. More particularly, use is made of 2-acrylamido-2-methylpropanesulfonic acid and also partially or totally neutralized forms thereof.
  • the crosslinking agents may be chosen from the polyolefinically unsaturated compounds commonly used for crosslinking polymers obtained by radical polymerization.
  • crosslinking agents examples 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 allylic or vinyl ethers of polyfunctional alcohols, and also the allylic esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.
  • the crosslinking agent is chosen from methylenebisacrylamide, allyl methacrylate and trimethylolpropane triacrylate (TMPTA).
  • TMPTA trimethylolpropane triacrylate
  • 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.
  • the polymers used are homopolymers, they only comprise monomers containing a sulfonic group and, if they are crosslinked, one or more crosslinking agents.
  • the preferred 2-acrylamido-2-methylpropanesulfonic acid homopolymers are generally characterized in that they comprise, randomly distributed:
  • X denotes a proton, an alkali metal cation, an alkaline-earth metal cation or the ammonium ion, not more than 10 mol% of the cations X + possibly being protons H + ; b) from 0.01 % to 10% by weight of crosslinking units originating from at least one monomer bearing at least two olefinic double bonds; the weight proportions being defined relative to the total weight of the polymer.
  • the homopolymers according to the invention that are more particularly preferred comprise from 98% to 99.5% by weight of units of formula (II) and from 0.2% to 2% by weight of crosslinking units.
  • 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).
  • the polymer may also be an amphiphilic homopolymer (or hydrophobic modified homopolymer) selected from random amphiphilic 2-acrylamido-2-methylpropanesulfonic acid polymers modified by reaction with a C 6 -C 2 2 n-monoalkylamine or di-n-alkylamine, such as those described in document WO A 00/31 154, which are graft homopolymers.
  • an amphiphilic homopolymer or hydrophobic modified homopolymer selected from random amphiphilic 2-acrylamido-2-methylpropanesulfonic acid polymers modified by reaction with a C 6 -C 2 2 n-monoalkylamine or di-n-alkylamine, such as those described in document WO A 00/31 154, which are graft homopolymers.
  • the polymers used are copolymers they can be obtained from ethylenically unsaturated monomers containing a sulfonic group and other ethylenically unsaturated monomers, i.e. ethylenically unsaturated monomers without a sulfonic group.
  • the ethylenically unsaturated monomers containing a sulfonic group are chosen from those described above.
  • the ethylenically unsaturated monomers without a sulfonic group may be chosen from ethylenically unsaturated hydrophilic monomers, ethylenically unsaturated hydrophobic monomers and mixtures thereof.
  • hydrophobic monomers it constitutes an amphiphilic polymer (also referred to as hydrophobic modified polymer).
  • the ethylenically unsaturated hydrophilic monomers may be selected for example from (meth)acrylic acids, ⁇ -substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or monoalkylene or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, vinylformamide, maleic anhydride, itaconic acid, maleic acid or mixtures of these compounds.
  • the polymer of the composition according to the invention is a copolymer that can be obtained from ethylenically unsaturated monomers bearing a sulfonic group and from ethylenically unsaturated hydrophilic monomers, it may especially be chosen from:
  • copolymers of (meth)acrylic acid or (meth)acrylate and of 2-acrylamido-2- methylpropanesulfonic acid in particular the optionally salified copolymers of 2- acrylamido-2-methylpropanesulfonic acid and of hydroxylated C 2 -C 4 alkyl (meth)acrylate.
  • the hydroxylated C 2 -C 4 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 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 salt.
  • an alkali metal salt such as, for example, the sodium or potassium salt
  • an ammonium salt or in the form of a salt of an amino alcohol, such as, for example, the monoethanolamine salt
  • an amino acid salt such as, for example, the lysine salt.
  • the copolymer is salified in sodium salt form.
  • the composition comprises the copolymer of 2-acrylamido-2- methylpropanesulfonic acid and of 2-hydroxyethyl acrylate, in particular in sodium salt form, for instance those sold under the trade names Sepinov® EMT 10 or Simulgel® NS (sodium 2-acrylamido-2-methylpropanesulfonate/hydroxyethyl acrylate copolymer as a 40% inverse emulsion in Polysorbate 60 and squalane) (CTFA name: hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer/squalane/polysorbate 60) by the company SEPPIC (INCI name: Hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer).
  • Simulgel EG sold by the company SEPPIC (copolymer of acrylic acid/acrylamido-2-methylpropanesulfonic acid in sodium salt form, as a 45% inverse emulsion in isohexadecane/water)
  • CTFA name : Sodium acrylate/Sodium acryloyldimethyl taurate copolymer/lsohexadecane/Polysorbate 80
  • copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of vinylpyrrolidone or vinylformamide such as the product sold under the name Aristoflex AVC by the company Clariant.
  • the polymer obtained is amphiphilic, i.e. it comprises both a hydrophilic portion and a hydrophobic portion.
  • Such polymers are also referred to as hydrophobic modified polymers.
  • hydrophobic modified polymers may also contain one or more monomers comprising neither a sulfonic group nor a fatty chain, such as (meth)acrylic acids, ⁇ - substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or monoalkylene or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, vinylformamide, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
  • monomers comprising neither a sulfonic group nor a fatty chain, such as (meth)acrylic acids, ⁇ - substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or monoalkylene or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, vinylformamide, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
  • hydrophobic modified polymers use may be made in particular of those that may be obtained from 2-acrylamido-2-methylpropanesulfonic acid and at least one ethylenically unsaturated hydrophobic monomer comprising at least one group containing 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 12 to 18 carbon atoms.
  • the ethylenically unsaturated hydrophobic monomers of these particular copolymers are preferably selected from the acrylates, alkylacrylates, acrylamides or alkylacrylamides of formula (III) below:
  • R-i and R 3 which may be identical or different, denote a hydrogen atom or a substantially linear or branched Ci-C 6 alkyl radical (preferably methyl);
  • Y denotes O or NH;
  • R 2 denotes a hydrocarbon-based radical containing 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 0 to 100.
  • the R 2 radical is preferably selected from substantially linear C 6 -Ci 8 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl or lauryl, or n-octadecyl or stearyl radicals); branched or cyclic C 6 -Ci 8 alkyl radicals (for example cyclododecane (C12) or adamantane (C10) radicals); C 6 -Ci 8 alkylperfluoro radicals (for example the group of formula -(CH 2 )2-(CF 2 )9-CF 3 ); the cholesteryl (C27) radical or a cholesterol ester residue, such as the cholesteryl oxyhexanoate group; or polycyclic aromatic groups, such as naphthalene or pyrene.
  • C 6 -Ci 8 alkyl radicals
  • the ones that are more particularly preferred are substantially linear alkyl radicals and more particularly the n- dodecyl, n-hexadecyl or n-octadecyl radical, and mixtures thereof.
  • the monomer of formula (III) comprises at least one alkylene oxide unit (x > 1 ) and preferably several alkylene oxide units (x > 1 ) forming a polyoxyalkylene chain.
  • the polyoxyalkylene chain is preferentially formed from ethylene oxide units and/or propylene oxide units and even more particularly formed from ethylene oxide units.
  • the number of oxyalkylene units (or number of moles of alkylene oxide) generally ranges from 3 to 100, more preferably from 3 to 50 and more preferably still from 7 to 25.
  • - terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of 2-acrylamido-2-methylpropanesulfonic acid units and from 5 mol% to 80 mol% of n-(C 6 -Ci 8 )alkylacrylamide units relative to the polymer, such as those described in patent US-A-5 089 578.
  • hydrophobic modified polymers mention may be made more particularly of copolymers consisting of (i) 2-acrylamido-2-methylpropanesulfonic acid units of formula (II) indicated above, in which X + is a proton, an alkali metal cation, an alkaline-earth metal cation or the ammonium ion, and (ii) units of formula (IV) below: in which x denotes an integer varying from 3 to 100, preferably from 3 to 50, and more preferably from 7 to 25; Ri has the same meaning as that indicated above in formula (III) and R 4 denotes a linear or branched alkyl radical comprising from 6 to 22 carbon atoms and preferably from 10 to 22 carbon atoms.
  • the polymers for which X + denotes sodium or ammonium are more particularly preferred.
  • the preferred hydrophobic modified polymers that may be used in the composition in accordance with the invention may be obtained according to conventional radical polymerization processes in the presence of one or more initiators such as, for example, azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile, 2,2-azobis[2-amidinopropane] hydrochloride (ABAH), organic peroxides such as dilauryl peroxide, benzoyl peroxide, fe/f-butyl hydroperoxide, etc., mineral peroxide compounds such as potassium persulfate or ammonium persulfate, or H 2 0 2 optionally in the presence of reducing agents.
  • initiators such as, for example, azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile, 2,2-azobis[2-amidinopropane] hydrochloride (ABAH), organic peroxides such as dilauryl peroxide, benzoyl peroxide
  • hydrophobic modified polymers may be obtained especially by radical polymerization in a ie f-butanol medium, in which they precipitate.
  • precipitation polymerization in ie f-butanol it is possible to obtain a size distribution of the polymer particles that is particularly favourable for its uses.
  • the reaction may be performed at a temperature of between 0 and 150°C and preferably between 10 and 100°C, either at atmospheric pressure or under reduced pressure. It may also be performed under inert atmosphere, and preferably under nitrogen.
  • hydrophobic modified polymers are in particular those described in document EP-1 069 142, and especially those obtained by polymerization of 2- acrylamido-2-methylpropanesulfonic acid or a sodium or ammonium salt thereof with a (meth)acrylic acid ester and
  • the molar percentage concentration of units of formula (II) and of units of formula (IV) in the polymers according to the invention varies as a function of the desired cosmetic application and of the rheological properties sought for the formulation. It can range between 0.1 mol% and 99.9 mol%.
  • the molar proportion of units of formula (II) or (IV) ranges from 50.1 % to 99.9%, more particularly from 70% to 95% and more particularly still from 80% to 90%.
  • the molar proportion of units of formula (II) or (IV) varies from 0.1 % to 50%, more particularly from 5% to 25% and more particularly still from 10% to 20%.
  • the distribution of the monomers in the polymers of the invention may be, for example, alternate, block (including multiblock) or random.
  • hydrophobic modified polymers of this type mention may be made especially of the copolymer of 2-acrylamido-2-methylpropanesulfonic acid and of ethoxylated C12-C14 alcohol methacrylate (non-crosslinked copolymer obtained from Genapol LA-070 and from 2-acrylamido-2-methylpropanesulfonic acid) (CTFA name: Ammonium acryloyldimethyltaurate/Laureth-7 methacrylate copolymer) sold under the name Aristoflex LNC by the company Clariant, and the copolymer of 2-acrylamido-2- methylpropanesulfonic acid and of ethoxylated (25 EO) stearyl methacrylate (copolymer crosslinked with trimethylolpropane triacrylate, obtained from Genapol T-250 and 2- acrylamido-2-methylpropa
  • the polymer bearing a sulfonic group is chosen from copolymers of 2- acrylamido-2-methylpropanesulfonic acid, preferably chosen from the copolymers of (meth)acrylic acid or (meth)acrylate, and of 2-acrylamido-2-methylpropanesulfonic acid, as described above, in particular the optionally salified copolymers of 2-acrylamido-2- methylpropanesulfonic acid and of hydroxylated C 2 -C 4 alkyl (meth)acrylate.
  • the polymer bearing a sulfonic group is chosen from copolymers of 2-acrylamido-2-methylpropanesulfonic acid and 2- hydroxyethyl acrylate, especially in salt form, hydrophobic modified polymers obtained by polymerization of 2-acrylamido-2-methylpropanesulfonic acid or a sodium or ammonium salt thereof with a (meth)acrylic acid ester and of a Ci 6 -Ci 8 alcohol oxyethylenated with 25 mol of ethylene oxide, and a mixture thereof.
  • hydrophilic acrylic homopolymer(s) or copolymer(s) may be present in the composition of the invention in an active material content ranging, for example, from 0.02% to 5% by weight, preferably ranging from 0.05% to 3% by weight and preferentially ranging from 0.05% to 2% by weight relative to the total weight of the composition.
  • active material content ranging, for example, from 0.02% to 5% by weight, preferably ranging from 0.05% to 3% by weight and preferentially ranging from 0.05% to 2% by weight relative to the total weight of the composition.
  • composition according to the invention may comprise at least one superabsorbent polymer.
  • superabsorbent polymer means a polymer that is capable in its dry form of spontaneously absorbing at least 20 times its own weight of aqueous fluid, in particular of water and especially distilled water. Such superabsorbent polymers are described in the publication "Absorbent polymer technology, Studies in polymer science 8" by L. Brannon-Pappas and R. Harland, published by Elsevier, 1990.
  • polymers have a large capacity for absorbing and retaining water and aqueous fluids. After absorption of the aqueous liquid, the polymer particles thus engorged with aqueous fluid remain insoluble in the aqueous fluid and thus conserve their individualized particulate state.
  • the superabsorbent polymer may have a water-absorbing capacity ranging from 20 to 2000 times its own weight (i.e. 20 g to 2000 g of absorbed water per gram of absorbent polymer), preferably from 30 to 1500 times and better still from 50 to 1000 times. These water absorption characteristics are defined under standard temperature (25°C) and pressure (760 mmHg, i.e. 100 000 Pa) conditions and for distilled water.
  • the value of the water-absorbing capacity of a polymer may be determined by dispersing 0.5 g of polymer(s) in 150 g of a water solution, waiting for 20 minutes, filtering the unabsorbed solution through a 150 ⁇ filter for 20 minutes and weighing the unabsorbed water.
  • the superabsorbent polymer used in the composition of the invention is in the form of particles.
  • the superabsorbent polymer has, in the dry or nonhydrated state, an average size of less than or equal to 100 ⁇ , preferably less than or equal to 50 ⁇ , ranging for example from 10 to 100 ⁇ , preferably from 15 to 50 ⁇ , and better still from 20 to 30 ⁇ .
  • the average size of the particles corresponds to the weight-average diameter (D 50 ) measured by laser particle size analysis or another equivalent method known to those skilled in the art.
  • These particles once hydrated, swell and form soft particles which have an average size that can range from 10 ⁇ to 1000 ⁇ , preferably from 20 ⁇ to 500 ⁇ , and more preferably from 50 ⁇ to 400 ⁇ .
  • the superabsorbent polymers used in the present invention are in the form of spherical particles.
  • absorbent polymers chosen from:
  • the superabsorbent polymers used in the present invention may be crosslinked or non- crosslinked. They are preferably chosen from crosslinked polymers.
  • the superabsorbent polymers used in the present invention are preferably crosslinked acrylic homopolymers or copolymers, which are preferably neutralized, and which are in particulate form.
  • the superabsorbent polymer is chosen from crosslinked sodium polyacrylates, preferably in the form of particles with an average size (or average diameter) of less than or equal to 100 microns, more preferably in the form of spherical particles.
  • These polymers preferably have a capacity to absorb water at 0,9 % of NaCI from 10 to 100 g/g, preferably from 20 to 80 g/g and better still from 30 to 80 g/g.
  • composition according to the invention comprises one or more superabsorbent polymers
  • they may be present in an active material content ranging, for example, from 0.05% to 15% by weight, preferably from 0.1 % to 10% by weight, preferably ranging from 0.1 % to 5% by weight, preferentially ranging from 0.1 % to 3% by weight or even from 0.1 % to 2% by weight relative to the total weight of the composition.
  • composition according to the invention may be in various galenical forms conventionally used for topical applications and especially in the form of dispersions of the lotion or serum type, emulsions of liquid or semi-liquid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase (O/W), or suspensions or emulsions of soft, semi-solid or solid consistency of the cream and/or gel type.
  • dispersions of the lotion or serum type emulsions of liquid or semi-liquid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase (O/W), or suspensions or emulsions of soft, semi-solid or solid consistency of the cream and/or gel type.
  • O/W aqueous phase
  • suspensions or emulsions of soft, semi-solid or solid consistency of the cream and/or gel type are prepared according to the usual methods.
  • the composition is in the form of an emulsion, and in particular an O/W emulsion or a cream gel.
  • compositions used according to the invention may be more or less fluid and may have the appearance of a white or coloured gel, cream-gel or cream, an ointment, a milk, a lotion, a serum, a paste or a mousse.
  • the composition preferably has a skin-friendly pH that generally ranges from 3 to 8 and preferably from 4.5 to 7.
  • the aqueous phase of the composition in accordance with the invention comprises at least water.
  • the amount of aqueous phase may range from 0.1 % to 95% by weight, preferably from 0.5% to 95% by weight, better still from 30% to 95% by weight and even better still from 40% to 95% by weight relative to the total weight of the composition.
  • the amount of water can represent all or a portion of the aqueous phase and it is generally at least 30% by weight relative to the total weight of the composition, preferably at least 50% by weight, better still at least 60% by weight.
  • the aqueous phase may comprise at least one hydrophilic solvent other than the polyols as defined above, for instance substantially linear or branched lower monoalcohols having from 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol or isobutanol.
  • the composition according to the invention comprises at least 5% by weight, relative to the total weight of the composition, of a fatty phase.
  • the proportion of the fatty phase of the emulsion ranges from 5% to 80% by weight, preferably from 5% to 50% by weight and better still from 5% to 30% by weight relative to the total weight of the composition.
  • the nature of the fatty phase of the composition is not critical.
  • the fatty phase may thus consist of any fatty substance conventionally used in cosmetics or dermatology; it in particular comprises at least one oil (fatty substance that is liquid at 25°C).
  • oils which can be used in the composition of the invention for example, of:
  • hydrocarbon oils of vegetable origin such as liquid triglycerides of fatty acids comprising from 4 to 10 carbon atoms, such as heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, maize oil, soybean oil, cucumber oil, grape seed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, such as those sold by Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by Dynamit Nobel, jojoba oil and shea butter oil;
  • esters and ethers in particular of fatty acids, such as oils of formulae R a COOR b and R a OR b in which R a represents the residue of a fatty acid comprising from 8 to 29 carbon atoms and R b represents a branched or unbranched hydrocarbon-based chain containing from 3 to 30 carbon atoms, such as, for example, purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2- octyldodecyl erucate or isostearyl isostearate; hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, fatty alcohol heptanoates
  • substantially linear or branched hydrocarbons of mineral or synthetic origin such as volatile or non-volatile liquid paraffins, and derivatives thereof, petroleum jelly, polydecenes, isohexadecane, isododecane, and hydrogenated polyisobutene such as Parleam® oil;
  • - fatty alcohols having from 8 to 26 carbon atoms such as cetyl alcohol, stearyl alcohol and their mixture (cetearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol, oleyl alcohol or linoleyl alcohol; - alkoxylated and in particular ethoxylated fatty alcohols, such as oleth-12, ceteareth-12 and ceteareth-20;
  • Fluoro oils that may also be mentioned include perfluoromethylcyclopentane and perfluoro-1 ,3-dimethylcyclohexane, sold under the names Flutec PC1 ® and Flutec PC3 ® by the company BNFL Fluorochemicals; perfluoro- 1 ,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050 ® and PF 5060 ® by the company 3M, or bromoperfluorooctyl sold under the name Foralkyl ® by the company Atochem; nonafluoromethoxybutane sold under the name MSX 4518 by the company 3M and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such
  • silicone oils for instance volatile or non-volatile polymethylsiloxanes (PDMS) with a substantially linear or cyclic silicone chain, which are liquid or pasty at room temperature, especially cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexadimethylsiloxane and cyclopentadimethylsiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenylsilicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes or 2-phenylethyl trimethylsiloxy silicates, and polymethylphenylsiloxanes
  • hydrocarbon oil is understood to mean any oil predominantly comprising carbon and hydrogen atoms, and optionally ester, ether, fluoro, carboxylic acid and/or alcohol groups.
  • the emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture.
  • the emulsifiers are generally present in the composition in a proportion ranging from 0.1 % to 30% by weight and preferably from 0.2% to 20% by weight relative to the total weight of the composition.
  • emulsifiers examples include nonionic surfactants, and especially esters of polyols and of fatty acids with a saturated or unsaturated chain containing, for example, from 8 to 24 carbon atoms and better still from 12 to 22 carbon atoms, and the oxyalkylenated derivatives thereof, i.e.
  • derivatives containing oxyethylenated and/or oxypropylenated units such as the glyceryl esters of C 8 -C 2 4 fatty acids, and the oxyalkylenated derivatives thereof; the polyethylene glycol esters of C 8 - C 2 4 fatty acids, and the oxyalkylenated derivatives thereof; the sorbitol esters of C 8 -C 2 4 fatty acids, and the oxyalkylenated derivatives thereof; fatty alcohol ethers; the sugar ethers of C 8 -C 2 4 fatty alcohols, and mixtures thereof.
  • Glyceryl esters of fatty acids that may especially be mentioned include glyceryl stearate (glyceryl monostearate, distearate and/or tristearate) (CTFA name: glyceryl stearate) or glyceryl ricinoleate, and mixtures thereof.
  • CFA name glyceryl stearate
  • glyceryl ricinoleate glyceryl ricinoleate
  • Polyethylene glycol esters of fatty acids that may especially be mentioned include polyethylene glycol stearate (polyethylene glycol monostearate, distearate and/or tristearate) and more especially polyethylene glycol 50 OE monostearate (CTFA name: PEG-50 stearate) and polyethylene glycol 100 OE monostearate (CTFA name: PEG-100 stearate), and mixtures thereof.
  • polyethylene glycol stearate polyethylene glycol monostearate, distearate and/or tristearate
  • CTFA name polyethylene glycol 50 OE monostearate
  • CTFA name polyethylene glycol 100 OE monostearate
  • Mixtures of these surfactants may also be used, for instance the product containing glyceryl stearate and PEG-100 stearate, sold under the name Arlacel 165 by the company Uniqema, and the product containing glyceryl stearate (glyceryl mono- distearate) and potassium stearate, sold under the name Tegin by the company Goldschmidt (CTFA name: glyceryl stearate SE).
  • CTFA name glyceryl stearate SE
  • fatty alcohol ethers examples include polyethylene glycol ethers of fatty alcohols containing from 8 to 30 carbon atoms and especially from 10 to 22 carbon atoms, such as polyethylene glycol ethers of cetyl alcohol, of stearyl alcohol or of cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol).
  • ethers comprising from 1 to 200 and preferably from 2 to 100 oxyethylene groups, such as those of CTFA name Ceteareth-20 and Ceteareth-30, and mixtures thereof.
  • lipoamino acids and salts thereof such as monosodium and disodium acylglutamates, for instance the monosodium stearoyl glutamate sold under the name Amisoft HS-1 1 PF and the disodium stearoyl glutamate sold under the name Amisoft HS-21 P by the company Ajinomoto.
  • compositions of the invention may contain one or more adjuvants that are common in cosmetics and dermatology: hydrophilic or lipophilic gelling agents and/or thickeners; moisturizers; emollients; hydrophilic or lipophilic active agents; free-radical scavengers; sequestrants; antioxidants; preserving agents; acidifying or basifying agents; fragrances; film-forming agents; fillers; and mixtures thereof.
  • the amounts of these various adjuvants are those conventionally used in the fields under consideration.
  • the amounts of active agents vary according to the desired objective and are those conventionally used in the fields under consideration, and for example from 0.1 % to 20%, and preferably from 0.5% to 10% by weight of the total weight of the composition.
  • Non-limiting examples of active agents include ascorbic acid and derivatives thereof such as 5,6-di-O-dimethylsilyl ascorbate (sold by the company Exsymol under the reference Pro-AA), D,L-otocopheryl-21 -ascorbyl phosphate potassium salt (sold by the company Senju Pharmaceutical under the reference Sepivital EPC), magnesium ascorbyl phosphate, sodium ascorbyl phosphate (sold by the company Roche under the reference Stay-C 50); phloroglucinol; enzymes; and mixtures thereof.
  • ascorbic acid is used among the oxidation-sensitive hydrophilic active agents.
  • the ascorbic acid may be of any nature. Thus, it may be of natural origin in powder form or in the form of orange juice, preferably orange juice concentrate. It may also be of synthetic origin, preferably in powder form.
  • active agents include moisturizing agents, such as protein hydrolysates and polyols, for instance glycerol, glycols, for instance polyethylene glycols; natural extracts; anti-inflammatory agents; oligomeric proanthocyanidins; vitamins such as vitamin A
  • retinol vitamin E (tocopherol), vitamin B5 (panthenol), vitamin B3 (niacinamide), derivatives of these vitamins (in particular esters) and mixtures thereof; urea; caffeine; depigmenting agents such as kojic acid, hydroquinone and caffeic acid; salicylic acid and derivatives thereof; ohydroxy acids, such as lactic acid and glycolic acid and derivatives thereof; retinoids, such as carotenoids and vitamin A derivatives; hydrocortisone; melatonin; extracts of algae, of fungi, of plants, of yeasts, of bacteria; steroids; antibacterial active agents, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether (or triclosan), 3,4,4'-trichlorocarbanilide (or triclocarban) and the acids indicated above, and in particular salicylic acid and derivatives thereof; matting agents, for instance fibres; tensioning agents; UV-screening agents; and mixtures thereof.
  • the "aqueous sensation" is evaluated according to the following protocols.
  • the aqueous sensation on application is evaluated, monadically, by a panel of experts trained in the description of care products.
  • the sensory evaluation of the care products by this panel is performed as follows: The products are conditioned in standard 15 ml_ transparent jars that are coded. Within the same session, the samples are presented in random order to each panellist. 15 descriptors are evaluated in four steps: appearance of the product in the jar (after smoothing the product), uptake, during application to the hand (onto a hand that has been cleaned beforehand with water and liquid soap and wiped with a paper handkerchief). 0.05 ml of product is applied to the top half of the hand (5 passes with the index and the middle finger). The product is evaluated during the five passes, and 2 minutes after application. Each descriptor is evaluated on a non- linear scale, at five levels: poor, sparingly, moderately, quite, very.
  • aqueous sensation on application is more particularly of interest here, and is defined as being the visualizations of droplets, drops or liquid pools at the surface of the skin (independently of the colour and of the texture).
  • phase B While mixing with a Rayneri blender, add phase B to phase A and leave to swell.
  • phase C2 While mixing with a Rayneri blender, add phase C2 to phase C1 , and then phase C3 to phase C2 + C1 .
  • compositions A and C according to the invention are more aqueous on application than the equivalent compositions (B and D, respectively), but which do not contain any aerogel.
  • composition according to the invention is more opalescent (in the sense that it is more transparent) and more aqueous on application than the equivalent composition F not containing any aerogel.
  • composition according to the invention Moisturizing cream-gel
  • composition G affords an aqueous sensation on application.
  • Preserving agent(s) 0.4 0.4
  • Composition H according to the invention is more opalescent (in the sense that it is more transparent) and more aqueous on application than the equivalent composition I not containing any aerogel.
  • composition according to the invention Moisturizing cream-gel
  • composition J according to the invention affords an aqueous sensation on application.

Abstract

The present invention relates to a composition for topical application comprising at least 5% by weight, relative to the total weight of the composition, of a fatty phase dispersed in an aqueous phase, hydrophobic silica aerogel particles with a specific surface area per unit of mass (SM) ranging from 500 to 1500 m2/g and a size expressed as the volume-mean diameter (D[0.5]) ranging from 1 to 1500 µm, and at least one hydrophilic acrylic homopolymer or copolymer. The invention also relates to a cosmetic process for treating keratin materials, which consists in applying to the keratin materials a composition as defined above, and also the use of this composition in cosmetics or dermatology, and in particular for caring for, protecting and/or making up bodily or facial skin, or for haircare. The composition according to the invention is in cream-gel form, is stable and has a pleasant texture, and in particular affords a fresh, aqueous sensation on application.

Description

Composition comprising silica aerogel particles and a hydrophilic acrylic
homopolymer or copolymer
The present patent application relates to a composition for topical application comprising at least 5% by weight, relative to the total weight of the composition, of a fatty phase dispersed in an aqueous phase, hydrophobic silica aerogel particles and at least one hydrophilic acrylic homopolymer or copolymer, and to the use of the said composition in cosmetics and dermatology, in particular for caring for or treating keratin materials.
In the field of cosmetics, and more particularly in the field of skincare and photoprotection, it is common practice to use galenical forms of cream-gel type, i.e. oil- in-water compositions in the form of a dispersion of a fatty phase in an aqueous gel, containing little or no emulsifier. These galenical forms are appreciated for their harmlessness, but also for their sensory effects. Specifically, they afford an opalescent appearance, and a fresh, aqueous feel on application.
Galenical forms of this type may be obtained with hydrophilic acrylic homopolymers or copolymers such as non-superabsorbent and at least partially neutralized acrylic acid homopolymers or copolymers and amphiphilic homopolymers or copolymers comprising at least one monomer bearing a sulfonic group.
However, once a substantial fatty phase is introduced into these cream-gels, the compositions obtained are not very stable. To stabilize them, it is necessary to use emulsifying systems combined with large contents of surfactants and/or thickeners, which have the drawback of making the textures sensorily lank and of giving a tacky, sticky feel and a certain irritant potential, in particular for people with sensitive or reactive skin. Moreover, the compositions lose their opalescent appearance.
Patent application FR 2 925 360 proposes to combine an inulin modified with hydrophobic chains with a hydrophilic acrylic polymer in order to obtain stable emulsions that are sensorily pleasant, when the compositions contain more than 5% by weight of fatty substance relative to the total weight of the composition, even without added surfactant. However, the opalescent appearance and the fresh, aqueous sensation obtained on applying these compositions is not entirely satisfactory, in particular when the fatty phase content is large.
There is thus still a need to prepare stable cosmetic compositions in cream-gel form containing a fatty phase, which have pleasant, aqueous and fresh textures on application.
The Applicant has discovered that cosmetic compositions comprising hydrophobic silica aerogel particles and at least one hydrophilic acrylic homopolymer or copolymer make it possible to produce cream-gels with an opalescent appearance that afford a fresh, aqueous sensation on application, in the presence of a fatty phase, even in an amount of greater than or equal to 5%.
Thus, one subject of the present invention is a composition for topical application comprising at least 5% by weight, relative to the total weight of the composition, of a fatty phase dispersed in an aqueous phase, hydrophobic silica aerogel particles with a specific surface area per unit of mass (SM) ranging from 500 to 1500 m2/g and a size expressed as the volume-mean diameter (D[0.5]) ranging from 1 to 1500 μηη, and at least one hydrophilic acrylic homopolymer or copolymer;
with the exception of the following compositions:
Composition A
Phase INCI name
A Water qs 100
Glycerol 5.00
Disodium EDTA 0.05
Propylene glycol 6.60
B Caprylyl glycol 0.15
Isohexadecane 3.50
1.00
Polysorbate 80 (Tween 80-LQ-(WL) from Croda)
Dimethicone (and) Ceteth-10 (and) Laureth-4 (Dow
1.50
Corning 7-3099 Dimethicone HIP Emulsion)
Dimethicone 350 cSt
0.3
Dimethicone 10 cSt
4.25
Dimethicone 5 cSt
4.75
C Isohexadecane 2.00
Carbomer (Carbopol 981 from Lubrizol) 0.15
D Sodium Hydroxide 0.06
Water 0.54
Ammonium polyacryloyldimethyl taurate (Hostacerin AMPS®
1.80
from Clariant)
E Nylon-12 (Orgasol 2002 EXD NAT COS from Arkema) 0.50
Ethanol 5.00 Hydrophobic silica aerogel particles (VM-2270 from Dow
Corning)
Composition B
Phase INCI name
A1 Water qs 100
Butylene glycol 5.00
Glycerol 5.00
Tetrasodium EDTA 0.20
Phenoxyethanol 0.70
Glyceryl stearate (and) PEG-100 stearate (Arlacel 165-FL
B 2.00 from Croda)
Cetyl alcohol 0.50
Methylparaben 0.25
PEG-20 stearate (Myrj S20-PA-(WL) from Croda) 0.80
Stearyl alcohol 0.50
Stearic acid 3.00
Capryloylsalicylic acid (Mexoryl SAB from Chimex) 0.05
Ammonium polyacryloyldimethyl taurate (Hostacerin AMPS® 1.60 from Clariant)
Dimethicone 350 cSt 0.15
Dimethicone 10 cSt 3.64
Dimethicone 5 cSt 3.64
B2 Triethanolamine 0.30
Hydrophobic silica aerogel particles (VM-2270 from Dow
B3 0.56 Corning)
Composition C
Phase INCI name
A Water qs 100
Glycerol 5.00
Disodium EDTA 0.05
Propylene glycol 6.60 B Caprylyl glycol 0.15
Isohexadecane 9.06
Polysorbate 80 (Tween 80-LQ-(WL) from Croda) 1 .00
Dimethicone (and) Ceteth-10 (and) Laureth-4 (Dow 1 .50
Corning 7-3099 Dimethicone HIP Emulsion)
Pentaerythrityl tetraoctanoate 3.68
C Isohexadecane 1 .00
Carbomer (Carbopol 981 from Lubrizol) 0.15
D Sodium hydroxide 0.06
Water 0.54
Ammonium polyacryloyldimethyl taurate (Hostacerin AMPS®
1 .80 from Clariant)
E Nylon-12 (Orgasol 2002 EXD NAT COS from Arkema) 0.50
Ethanol 5.00
Hydrophobic silica aerogel particles (VM-2270 from Dow
G 0.8 Corning)
Composition D
Phase INCI name
A1 Water qs 100
Butylene glycol 5.00
Glycerol 5.00
Tetrasodium EDTA 0.20
Phenoxyethanol 0.70
Glyceryl stearate (and) PEG-100 stearate (Arlacel 165-FL
B 2.00 from Croda)
Cetyl alcohol 0.50
Methylparaben 0.25
PEG-20 stearate (Myrj S20-PA-(WL) from Croda) 0.80
Stearyl alcohol 0.50
Stearic acid 3.00
Capryloylsalicylic acid (Mexoryl SAB from Chimex) 0.05
Ammonium polyacryloyldimethyl taurate (Hostacerin 1 .60 AMPS® from Clariant)
Isohexadecane 4.41
Parleam 2.94
B2 Triethanolamine 0.30
Hydrophobic silica aerogel particles (VM-2270 from
B3 0.64
Dow Corning)
According to one particular embodiment, a subject of the present invention is a composition for topical application comprising at least 5% by weight, relative to the total weight of the composition, of a fatty phase dispersed in an aqueous phase; hydrophobic silica aerogel particles with a specific surface area per unit of mass (SM) ranging from 500 to 1500 m2/g, preferably from 600 to 1200 m2/g and better still from 600 to 800 m2/g, and a size expressed as the mean volume diameter (D[0.5]) ranging from 1 to 1500 μηη, better still from 1 to 1000 μηη, even more preferentially from 1 to 100 μηη, in particular from 1 to 30 μηη, more preferably from 5 to 25 μηη, better still from 5 to 20 μηη and even better still from 5 to 15 μηι;
and at least one hydrophilic acrylic homopolymer or copolymer;
the said composition being different from:
a) a cosmetic composition comprising a mixture of hydrophobic silica aerogel particles with a specific surface area per unit of mass (SM) ranging from 500 to 1500 m2/g and a size expressed as the mean volume diameter (D[0.5]) ranging from 1 to 1500 μηη, of at least a first linear silicone oil with a viscosity of greater than 50 mm2/s and of at least second and third linear silicone oils each with a viscosity of less than or equal to 50 mm2/s, and of an acrylamidomethylpropanesulfonic acid homopolymer ; and
b) a cosmetic composition comprising a mixture of hydrophobic silica aerogel particles with a specific surface area per unit of mass (SM) ranging from 500 to 1500 m2/g and a size expressed as the mean volume diameter (D[0.5]) ranging from 1 to 1500 μηη, of at least a first hydrocarbon-based oil, of at least a second hydrocarbon-based oil chosen from pentaerythritol esters, hydrogenated polyolefins and fatty acid triglycerides, and mixtures thereof, the first hydrocarbon-based oil being present in a content of greater than or equal to 40% by weight of the mixture of the first and second oils, and of an acrylamidomethylpropanesulfonic acid homopolymer.
According to one particular embodiment, a subject of the present invention is a composition for topical application comprising at least 5% by weight, relative to the total weight of the composition, of a fatty phase dispersed in an aqueous phase, hydrophobic silica aerogel particles with a specific surface area per unit of mass (SM) ranging from 500 to 1500 m2/g and a size expressed as the volume-mean diameter (D[0.5]) ranging from 1 to 1500 μηη, and at least one acrylic polymer chosen from non-superabsorbent and at least partially neutralized acrylic acid homopolymers or copolymers and copolymers comprising at least one monomer bearing a sulfonic group.
Since the composition of the invention is intended for topical application to the skin or the integuments, it comprises a physiologically acceptable medium, i.e. a medium that is compatible with all keratin materials such as the skin, the nails, mucous membranes and keratin fibres (such as the hair or the eyelashes).
The composition according to the invention is in cream-gel form, is stable and has a pleasant texture, and in particular affords a fresh, aqueous sensation on application. A subject of the invention is also a cosmetic treatment process for keratin materials, which consists in applying to the keratin materials a composition as defined above.
A subject of the invention is also the use of the said composition in cosmetics or dermatology, and in particular for caring for, protecting and/or making up bodily or facial skin, or for haircare.
In the text hereinbelow, the expression "at least one" is equivalent to "one or more" and, unless otherwise indicated, the limits of a range of values are included in that range. Hydrophobic silica aerogels
Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air.
They are generally synthesized via a sol-gel process in liquid medium and then dried, usually by extraction of a supercritical fluid, the one most commonly used being supercritical C02. This type of drying makes it possible to avoid shrinkage of the pores and of the material. The sol-gel process and the various drying operations are described in detail in Brinker C.J. and Scherer G.W., Sol-Gel Science, New York, Academic Press, 1990.
The hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of mass (SM) ranging from 500 to 1500 m2/g, preferably from 600 to 1200 m2/g and better still from 600 to 800 m2/g, and a size expressed as the volume- average diameter (D[0.5]) ranging from 1 to 1500 μηη, better still from 1 to 1000 μηη, preferably from 1 to 100 μηη, in particular from 1 to 30 μηη, more preferably from 5 to 25 μηη, better still from 5 to 20 μηη and even better still from 5 to 15 μηη.
According to one embodiment, the hydrophobic silica aerogel particles used in the present invention have a size, expressed as volume-average diameter (D[0.5]), ranging from 1 to 30 μηη, preferably from 5 to 25 μηη, better still from 5 to 20 μηη and even better still from 5 to 15 μηη.
The specific surface per unit of weight can be determined by the nitrogen absorption method, known as the BET (Brunauer-Emmett-Teller) method, described in The Journal of the American Chemical Society, Vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (appendix D). The BET specific surface corresponds to the total specific surface of the particles under consideration.
The sizes of the silica aerogel particles may be measured by static light scattering using a commercial particle size analyser such as the MasterSizer 2000 machine from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non- spherical particles, an "effective" particle diameter. This theory is described in particular in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957.
According to one advantageous embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of mass (SM) ranging from 600 to 800 m2/g and a size expressed as the volume-mean diameter (D[0.5]) ranging from 5 to 20 μηη and even better still from 5 to 15 μηη.
The silica aerogel particles used in the present invention may advantageously have a tamped density (p) ranging from 0.04 g/cm3 to 0.10 g/cm3 and preferably from 0.05 g/cm3 to 0.08 g/cm3.
In the context of the present invention, this density, known as the tamped density, may be assessed according to the following protocol:
40 g of powder are poured into a measuring cylinder; the measuring cylinder is then placed on a Stav 2003 machine from Stampf Volumeter; the measuring cylinder is then subjected to a series of 2500 packing motions (this operation is repeated until the difference in volume between two consecutive tests is less than 2%); the final volume Vf of packed powder is then measured directly on the measuring cylinder. The tamped density is determined by the ratio m/Vf, in this instance 40/Vf (Vf being expressed in cm3 and m in g).
According to one embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of volume Sv ranging from 5 to 60 m2/cm3, preferably from 10 to 50 m2/cm3 and better still from 15 to 40 m2/cm3.
The specific surface per unit of volume is given by the relationship: Sv = SM x p where p is the tamped density expressed in g/cm3 and SM is the specific surface area per unit of mass expressed in m2/g, as defined above. Preferably, the hydrophobic silica aerogel particles according to the invention have an oil absorption capacity, measured at the wet point, ranging from 5 to 18 ml/g, preferably from 6 to 15 ml/g and better still from 8 to 12 ml/g.
The oil-absorbing capacity measured at the wet point, noted Wp, corresponds to the amount of water that needs to be added to 100 g of particles in order to obtain a homogeneous paste.
It is measured according to the "wet point" method or method for determining the oil uptake of a powder described in Standard NF T 30-022. It corresponds to the amount of oil adsorbed onto the available surface of the powder and/or absorbed by the powder by measurement of the wet point, described below:
An amount m = 2 g of powder is placed on a glass plate, and the oil (isononyl isononanoate) is then added dropwise. After addition of 4 to 5 drops of oil to the powder, mixing is carried out using a spatula, and addition of oil is continued until conglomerates of oil and powder have formed. From this point, the oil is added at the rate of one drop at a time and the mixture is subsequently triturated with the spatula. The addition of oil is stopped when a firm, smooth paste is obtained. This paste must be able to be spread over the glass plate without cracks or the formation of lumps. The volume Vs (expressed in ml) of oil used is then noted.
The oil uptake corresponds to the ratio Vs/m.
The aerogels used according to the present invention are hydrophobic silica aerogels, preferably of silyl silica (INCI name: silica silylate).
The term "hydrophobic silica" means any silica whose surface is treated with silylating agents, for example halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups Si-Rn, for example trimethylsilyl groups.
As regards the preparation of hydrophobic silica aerogels particles that have been surface-modified by silylation, reference may be made to document US 7 470 725.
Use will be made in particular of hydrophobic silica aerogel particles surface-modified with trimethylsilyl groups (trimethylsiloxyl silica).
Mention may be made, as hydrophobic silica aerogels which can be used in the invention, for example, of the aerogel sold under the name VM-2260 (INCI name: Silica silylate) by the company Dow Corning, the particles of which have an average size of approximately 1000 microns and a specific surface area per unit of mass ranging from 600 to 800 m2/g. Mention may also be made of the aerogels sold by the company Cabot under the references Aerogel TLD 201 , Aerogel OGD 201 and Aerogel TLD 203, Enova® Aerogel MT 1 100 and Enova Aerogel MT 1200.
Use will be made more particularly of the aerogel sold under the name VM-2270 (INCI name: Silica silylate), by the company Dow Corning, the particles of which have an average size ranging from 5-15 microns and a specific surface area per unit of mass ranging from 600 to 800 m2/g.
The hydrophobic silica aerogel particles may be present in the composition according to the invention in a content ranging from 0.05% to 10% by weight, preferably from 0.05% to 5% by weight, better still from 0.1 % to 5% by weight and more preferably from 0.5% to 2% by weight relative to the total weight of the composition.
Hydrophilic acrylic homopolymers or copolymers
The composition according to the invention comprises at least one hydrophilic acrylic homopolymer or copolymer.
For the purposes of the present invention, the term "hydrophilic acrylic homopolymer or copolymer" means a crosslinked or non-crosslinked polymer of the polyacrylic family, which is capable of forming a gel in pure water.
According to one particular embodiment of the invention, the hydrophilic acrylic homopolymer(s) or copolymer(s) are chosen from non-superabsorbent and at least partially neutralized acrylic acid homopolymers or copolymers and homopolymers or copolymers comprising at least one monomer bearing a sulfonic group. Preferably the hydrophilic acrylic homopolymer(s) or copolymer(s) are chosen from non- superabsorbent and at least partially neutralized acrylic acid homopolymers or copolymers and copolymers comprising at least one monomer bearing a sulfonic group. Any non-superabsorbent acrylic acid homopolymer or copolymer is suitable for use in the present invention provided that it is hydrophilic and is used in an at least partially neutralized form.
In the context of the invention, a "non-superabsorbent polymer" is a polymer that does not correspond to the definition given below for superabsorbent polymers.
The term "hydrophilic polymer" means a polymer that is dispersible in water.
The non-superabsorbent acrylic homopolymers or copolymers that are suitable for the invention may be present in the composition in a particulate or non-particulate form.
When they are present in a particulate form, their average size in the hydrated state is preferably less than or equal to 10 μηη and even more preferentially less than or equal to 5 μηι. Their average size in the nonhydrated state is preferably less than or equal to 2 μηι, preferably less than or equal to 1 μηι.
As regards these non-superabsorbent acrylic polymers already neutralized before use, or otherwise, examples that may be mentioned include:
- sodium polyacrylates such as those sold under the name Cosmedia SP® containing 90% solids and 10% water, or Cosmedia SPL® as an inverse emulsion containing about 60% dry active material, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by the company Cognis;
- partially neutralized sodium polyacrylates that are in the form of an inverse emulsion comprising at least one polar oil, for example the product sold under the name Luvigel®
EM sold by the company BASF, and
- mixtures thereof.
A non-superabsorbent acrylic acid polymer in accordance with the present invention, which has not been neutralized beforehand, may be neutralized by any suitable means and in particular by adding sodium hydroxide. Sodium polyacrylates are thus obtained. Potassium polyacrylates are also suitable for the present invention.
The neutralization may be performed prior to use in the composition of the invention if the polymer in question is sold in a non-neutralized form. On the other hand, for some of them, neutralization is inherent in the raw material. This is the case in particular for Luvigel® EM and for the products called Cosmedia® SP and SPL, which are already partially neutralized.
The neutralization step, for example with sodium or potassium counterions, is important for giving the acidic polymers their properties of the gelling and thus stabilizing of the composition. Said acrylic polymers are converted into the corresponding acrylate polymers during this neutralization step. Said acrylic monomers of the acrylic polymer according to the invention may be neutralized in a proportion of from 5% to 80%.
According to one particular embodiment of the invention, the acrylic polymer in accordance with the invention may comprise nonionic monomers. By way of nonionic monomers, use may be made of acrylamide, methacrylamide, vinylpyrrolidone, vinylimidazole, vinylcaprolactam and hydroxy(CrC4)alkyl esters of carboxylic acids, such as hydroxyethyl acrylates. However, in the context of the present invention, preference is given to acrylic polymers comprising more than 90% of acrylic acid monomers, or even comprising no nonionic monomer (acrylic acid homopolymers).
According to one particular embodiment, the acrylic acid homopolymer or copolymer may be in the form of a water-in-oil emulsion, known as an inverse emulsion. This inverse emulsion may be obtained, for example, by inverse emulsion polymerization. According to one particular embodiment of the invention, the polymer used is a partially neutralized sodium polyacrylate that is in the form of an inverse emulsion comprising at least one polar oil. Among the oils, mention may be made of fatty acid esters. Examples of these fatty acid esters are isopropyl esters of fatty acids, such as isopropyl palmitate or isopropyl myristate, or fatty acid polyglycerides, in particular of fatty acid mixtures comprising at least 50% of capric and/or caprylic acid. Such water-in-oil emulsions are described in document US 6 197 283.
According to this embodiment, the oily phase may consist of one or more fatty acid esters, one or more fatty acid polyglycerides based on a mixture of polyglycerides, which contains diglycerides and triglycerides, with mixtures of fatty acids, which contain caprylic acid and/or capric acid, preferably in a proportion of at least 50% by weight relative to the total weight of fatty acids.
According to one embodiment of the invention, the oil content of the inverse emulsion is between 15% and 70% by weight and in particular between 20% and 35% by weight relative to the total weight of the inverse emulsion.
In this respect, mention may be made in particular of Luvigel® EM, the oily phase of which comprises 26% of oil phase consisting of C8-Ci0 triglycerides, that is to say the fatty acids of which are a mixture of caprylic and capric acid.
Moreover, the water-in-oil emulsion may contain from 0.25% to 7% by weight and preferably from 0.5% to 5% by weight of a surfactant.
The at least partially neutralized acrylic polymer may be present in the inverse emulsion in a content ranging from 20% to 70% by weight, in particular from 20% to 65% by weight, for example from 20% to 62% by weight relative to the total weight of the inverse emulsion.
In particular, according to one embodiment, the acrylic polymer may be present in the inverse emulsion in a content ranging from 20% to 30% by weight relative to the total weight of the inverse emulsion. According to yet another embodiment, the acrylic polymer may be present in the inverse emulsion in a content ranging from 50% to 62% by weight relative to the total weight of the composition.
According to one particular embodiment of the invention, the non-superabsorbent polymers may consist of:
a) from 35% to 100% by weight of acrylic acid monomers, these monomers being 5-80% neutralized,
b) from 0 to 65% by weight of nonionic monomers,
c) from 0.3 mol% to 1 mol%, relative to a) and b), of at least one at least bifunctional monomer. In the water-in-oil formulation of such a polymer, the oily phase may then consist of one or more fatty acid esters as described previously.
The non-superabsorbent homopolymer(s) or copolymer(s) which are at least partially neutralized may be crosslinked or non-crosslinked.
When they are crosslinked, the crosslinking of the acrylic acid may be obtained according to any method known to those skilled in the art, especially according to the description of document US 6 197 283 or according to the description of document US 6 444 785, which mention the crosslinking agents that may be used.
Among these, mention may be made of unsaturated compounds that are soluble in water or in oil. Such crosslinking agents are in particular methylenebisacrylamide, divinylpyrrolidone, alkyl (meth)acrylate, triallylamine, ethylene glycol diacrylates (up to 50 EO), (meth)acrylic esters with di- or polyhydric alcohols such as trimethylolpropane triacrylate or pentaerythrityl tetraacrylate.
According to one embodiment, the crosslinking agent is water-soluble.
According to another embodiment, the crosslinking agent is triallylamine.
The preparation of W/O emulsions comprising a polymer in accordance with the present invention may be performed according to the teaching of document US 6 444 785. The object of this process is to lower the content of remaining monomers by post-treatment with a redox initiator system. According to this process, the post-treatment of the W/O emulsion is performed by addition of a redox initiator system which comprises essentially a) 0.001 % to 5% by weight, relative to the total amount of monomers used for the preparation of the polymer,
a1 ) of an oxidizing agent R1OOH,
in which R1 denotes hydrogen, a Ci to C8 alkyl group or a C6 to Ci2 aryl group, and/or a2) of a compound that releases hydrogen peroxide in aqueous medium, and
b) 0.005% to 5% by weight, relative to the total amount of monomers used for the preparation of the polymer,
b1 ) of an ohydroxycarbonyl compound having the following formula:
O OH
R2^ ' R3
in which the groups have, independently of each other, the following meaning:
R2: hydrogen, or a C1-C12 alkyl group, optionally containing functional groups and/or possibly comprising olefinic unsaturations,
R3: hydrogen, OH, or a C1-C12 alkyl group, optionally containing functional groups and/or possibly comprising olefinic unsaturations, and whereas R2 and R3 may form a cyclic structure, which may contain a heteroatom and/or functional groups, and/or may comprise olefinic unsaturations, and/or
b2) of a compound that releases such an ohydroxycarbonyl compound in aqueous medium, and
c) catalytic amounts of a multivalent metal ion that may be in several valency states.
The polymers comprising at least one monomer bearing a sulfonic group that are used in the composition of the invention are water-dispersible or water-swellable. The polymers used in accordance with the invention may be homopolymers or copolymers and may be obtained from at least one ethylenically unsaturated monomer bearing a sulfonic group, which may be in free form or partially or totally neutralized form. These polymers may optionally comprise at least one hydrophobic group and then constitute an amphiphilic polymer (or hydrophobic modified polymer). Preferentially, the polymers in accordance with the invention 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 polymers used in the composition of the invention generally have a number-average molecular weight ranging from 1000 to 20 000 000 g/mol, preferably ranging from 20 000 to 5 000 000 g/mol and even more preferentially from 100 000 to 1 500 000 g/mol.
These polymers according to the invention may be crosslinked or non-crosslinked. The monomers bearing a sulfonic group of the polymer used in the composition of the invention are especially chosen from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci-C22)alkylsulfonic acids, N-(Ci-C22)alkyl(meth)acrylamido(Ci- C22)alkylsulfonic acids such as undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof, and mixtures thereof. According to one preferred embodiment of the invention, the monomers bearing a sulfonic group are chosen from (meth)acrylamido(Ci-C22)alkylsulfonic acids, for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2- methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2- acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid and 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, and mixtures thereof. More particularly, use is made of 2-acrylamido-2-methylpropanesulfonic acid and also partially or totally neutralized forms thereof.
When the polymers are crosslinked, the crosslinking agents 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 allylic 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.
When the polymers used are homopolymers, they only comprise monomers containing a sulfonic group and, if they are crosslinked, one or more crosslinking agents.
The preferred 2-acrylamido-2-methylpropanesulfonic acid homopolymers are generally characterized in that they comprise, randomly distributed:
a) from 90% to 99.9% by weight of units of general formula (II) below:
Figure imgf000016_0001
in which X denotes a proton, an alkali metal cation, an alkaline-earth metal cation or the ammonium ion, not more than 10 mol% of the cations X+ possibly being protons H+; b) from 0.01 % to 10% by weight of crosslinking units originating from at least one monomer bearing at least two olefinic double bonds; the weight proportions being defined relative to the total weight of the polymer. The homopolymers according to the invention that are more particularly preferred comprise from 98% to 99.5% by weight of units of formula (II) and from 0.2% to 2% by weight of crosslinking units.
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).
The polymer may also be an amphiphilic homopolymer (or hydrophobic modified homopolymer) selected from random amphiphilic 2-acrylamido-2-methylpropanesulfonic acid polymers modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine, such as those described in document WO A 00/31 154, which are graft homopolymers.
When the polymers used are copolymers they can be obtained from ethylenically unsaturated monomers containing a sulfonic group and other ethylenically unsaturated monomers, i.e. ethylenically unsaturated monomers without a sulfonic group.
The ethylenically unsaturated monomers containing a sulfonic group are chosen from those described above. The ethylenically unsaturated monomers without a sulfonic group may be chosen from ethylenically unsaturated hydrophilic monomers, ethylenically unsaturated hydrophobic monomers and mixtures thereof. When the polymer contains hydrophobic monomers it constitutes an amphiphilic polymer (also referred to as hydrophobic modified polymer).
The ethylenically unsaturated hydrophilic monomers may be selected for example from (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or monoalkylene or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, vinylformamide, maleic anhydride, itaconic acid, maleic acid or mixtures of these compounds.
When the polymer of the composition according to the invention is a copolymer that can be obtained from ethylenically unsaturated monomers bearing a sulfonic group and from ethylenically unsaturated hydrophilic monomers, it may especially be chosen from:
(1 ) crosslinked anionic copolymers of acrylamide or methacrylamide and of 2- acrylamido-2-methyl-propanesulfonic acid, especially those in the form of a W/O emulsion, such as those sold under the name Sepigel 305 by the company SEPPIC (CTFA name: Polyacrylamide/C13-14 lsoparaffin/Laureth-7), under the name Simulgel 600 by the company SEPPIC (CTFA name: Acrylamide/Sodium acryloyldimethyltaurate copolymer/lsohexadecane/Polysorbate 80);
(2) copolymers of (meth)acrylic acid or (meth)acrylate and of 2-acrylamido-2- methylpropanesulfonic acid, in particular the optionally salified copolymers of 2- acrylamido-2-methylpropanesulfonic acid and of 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 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 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, in particular in sodium salt form, for instance those sold under the trade names Sepinov® EMT 10 or Simulgel® NS (sodium 2-acrylamido-2-methylpropanesulfonate/hydroxyethyl acrylate copolymer as a 40% inverse emulsion in Polysorbate 60 and squalane) (CTFA name: hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer/squalane/polysorbate 60) by the company SEPPIC (INCI name: Hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer).
Such polymers are described in application FR-A-2856691 .
Mention may also be made of Simulgel EG sold by the company SEPPIC (copolymer of acrylic acid/acrylamido-2-methylpropanesulfonic acid in sodium salt form, as a 45% inverse emulsion in isohexadecane/water) (CTFA name: : Sodium acrylate/Sodium acryloyldimethyl taurate copolymer/lsohexadecane/Polysorbate 80), and (3) copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of vinylpyrrolidone or vinylformamide, such as the product sold under the name Aristoflex AVC by the company Clariant.
When the monomers containing a sulfonic group are copolymerized with ethylenically unsaturated hydrophobic monomers comprising a hydrophobic chain, also referred to as a fatty chain (C6-C50 chain), the polymer obtained is amphiphilic, i.e. it comprises both a hydrophilic portion and a hydrophobic portion. Such polymers are also referred to as hydrophobic modified polymers.
These hydrophobic modified polymers may also contain one or more monomers comprising neither a sulfonic group nor a fatty chain, such as (meth)acrylic acids, β- substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or monoalkylene or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, vinylformamide, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
As hydrophobic modified polymers, use may be made in particular of those that may be obtained from 2-acrylamido-2-methylpropanesulfonic acid and at least one ethylenically unsaturated hydrophobic monomer comprising at least one group containing 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 12 to 18 carbon atoms.
These polymers are described especially in documents EP-A-750 899, US-A-5 089 578 and WO-A-2002/43689, 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 hydrophobic monomers of these particular copolymers are preferably selected from the acrylates, alkylacrylates, acrylamides or alkylacrylamides of formula (III) below:
CH2 C
O=C
Y -CH2-CH(R3)-O-
in which R-i and R3, which may be identical or different, denote a hydrogen atom or a substantially linear or branched Ci-C6 alkyl radical (preferably methyl); Y denotes O or NH; R2 denotes a hydrocarbon-based radical containing 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 0 to 100. The R2 radical is preferably selected from substantially linear C6-Ci8 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl or lauryl, or n-octadecyl or stearyl radicals); branched or cyclic C6-Ci8 alkyl radicals (for example cyclododecane (C12) or adamantane (C10) radicals); C6-Ci8 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 substantially linear alkyl radicals and more particularly the n- dodecyl, n-hexadecyl or n-octadecyl radical, and mixtures thereof. According to one particularly preferred form of the invention, the monomer of formula (III) comprises at least one alkylene oxide unit (x > 1 ) and preferably several alkylene oxide units (x > 1 ) forming a polyoxyalkylene chain. The polyoxyalkylene chain is preferentially formed from ethylene oxide units and/or propylene oxide units and even more particularly formed from ethylene oxide units. The number of oxyalkylene units (or number of moles of alkylene oxide) generally ranges from 3 to 100, more preferably from 3 to 50 and more preferably still from 7 to 25.
Among these polymers, mention may be made of:
- crosslinked or non-crosslinked, neutralized or non-neutralized copolymers 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 (C8-Ci6)alkyl (meth)acrylate units relative to the polymer, such as those described in patent application EP-A 0 750 899;
- terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of 2-acrylamido-2-methylpropanesulfonic acid units and from 5 mol% to 80 mol% of n-(C6-Ci8)alkylacrylamide units relative to the polymer, such as those described in patent US-A-5 089 578.
- non-crosslinked copolymers of partially or totally neutralized 2-acrylamido-2- methylpropanesulfonic acid and of n-dodecyl methacrylate, n-hexadecyl methacrylate or n-octadecyl methacrylate, such as those described in the Morishima articles mentioned above;
- crosslinked or non-crosslinked copolymers of partially or totally neutralized 2- acrylamido-2-methylpropanesulfonic acid and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above. As hydrophobic modified polymers, mention may be made more particularly of copolymers consisting of (i) 2-acrylamido-2-methylpropanesulfonic acid units of formula (II) indicated above, in which X+ is a proton, an alkali metal cation, an alkaline-earth metal cation or the ammonium ion, and (ii) units of formula (IV) below:
Figure imgf000021_0001
in which x denotes an integer varying from 3 to 100, preferably from 3 to 50, and more preferably from 7 to 25; Ri has the same meaning as that indicated above in formula (III) and R4 denotes a linear or branched alkyl radical comprising from 6 to 22 carbon atoms and preferably from 10 to 22 carbon atoms.
The hydrophobic modified polymers of this type are especially those described in the Morishima articles mentioned above, for which x = 25, Ri denotes methyl and R4 represents n-dodecyl; or those described in document WO-A-02/43689, for which x = 8 or 25, Ri denotes methyl and R4 represents n-hexadecyl (Ci6), n-octadecyl (Ci8), or n- dodecyl (Ci2), or mixtures thereof. The polymers for which X+ denotes sodium or ammonium are more particularly preferred. The preferred hydrophobic modified polymers that may be used in the composition in accordance with the invention may be obtained according to conventional radical polymerization processes in the presence of one or more initiators such as, for example, azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile, 2,2-azobis[2-amidinopropane] hydrochloride (ABAH), organic peroxides such as dilauryl peroxide, benzoyl peroxide, fe/f-butyl hydroperoxide, etc., mineral peroxide compounds such as potassium persulfate or ammonium persulfate, or H202 optionally in the presence of reducing agents.
These hydrophobic modified polymers may be obtained especially by radical polymerization in a ie f-butanol medium, in which they precipitate. By using precipitation polymerization in ie f-butanol, it is possible to obtain a size distribution of the polymer particles that is particularly favourable for its uses.
The reaction may be performed at a temperature of between 0 and 150°C and preferably between 10 and 100°C, either at atmospheric pressure or under reduced pressure. It may also be performed under inert atmosphere, and preferably under nitrogen.
These preferred hydrophobic modified polymers are in particular those described in document EP-1 069 142, and especially those obtained by polymerization of 2- acrylamido-2-methylpropanesulfonic acid or a sodium or ammonium salt thereof with a (meth)acrylic acid ester and
- of a C -C alcohol oxyethylenated with 8 mol of ethylene oxide (Genapol® C-080 from the company Clariant),
- of a On oxo alcohol oxyethylenated with 8 mol of ethylene oxide (Genapol® UD-080 from the company Clariant),
- of a On oxo alcohol oxyethylenated with 7 mol of ethylene oxide (Genapol® UD-070 from the company Clariant),
- of a C12-C14 alcohol oxyethylenated with 7 mol of ethylene oxide (Genapol® LA-070 from the company Clariant),
- of a C12-C14 alcohol oxyethylenated with 9 mol of ethylene oxide (Genapol® LA-090 from the company Clariant),
- of a C12-C14 alcohol oxyethylenated with 1 1 mol of ethylene oxide (Genapol® LA-1 10 from the company Clariant),
- of a C16-C18 alcohol oxyethylenated with 8 mol of ethylene oxide (Genapol ®T-080 from the company Clariant),
- of a C16-C18 alcohol oxyethylenated with 15 mol of ethylene oxide (Genapol® T-150 from the company Clariant),
- of a C16-C18 alcohol oxyethylenated with 1 1 mol of ethylene oxide (Genapol® T-1 10 from the company Clariant),
- of a C16-C18 alcohol oxyethylenated with 20 mol of ethylene oxide (Genapol® T-200 from the company Clariant),
- of a C16-C18 alcohol oxyethylenated with 25 mol of ethylene oxide (Genapol® T-250 from the company Clariant),
- of a C18-C22 alcohol oxyethylenated with 25 mol of ethylene oxide and/or of a Ci6-Ci8 iso alcohol oxyethylenated with 25 mol of ethylene oxide.
The molar percentage concentration of units of formula (II) and of units of formula (IV) in the polymers according to the invention varies as a function of the desired cosmetic application and of the rheological properties sought for the formulation. It can range between 0.1 mol% and 99.9 mol%.
Preferably, for the most hydrophobic polymers, the molar proportion of units of formula (II) or (IV) ranges from 50.1 % to 99.9%, more particularly from 70% to 95% and more particularly still from 80% to 90%.
Preferably, for the polymers that are not very hydrophobic, the molar proportion of units of formula (II) or (IV) varies from 0.1 % to 50%, more particularly from 5% to 25% and more particularly still from 10% to 20%.
The distribution of the monomers in the polymers of the invention may be, for example, alternate, block (including multiblock) or random. As hydrophobic modified polymers of this type, mention may be made especially of the copolymer of 2-acrylamido-2-methylpropanesulfonic acid and of ethoxylated C12-C14 alcohol methacrylate (non-crosslinked copolymer obtained from Genapol LA-070 and from 2-acrylamido-2-methylpropanesulfonic acid) (CTFA name: Ammonium acryloyldimethyltaurate/Laureth-7 methacrylate copolymer) sold under the name Aristoflex LNC by the company Clariant, and the copolymer of 2-acrylamido-2- methylpropanesulfonic acid and of ethoxylated (25 EO) stearyl methacrylate (copolymer crosslinked with trimethylolpropane triacrylate, obtained from Genapol T-250 and 2- acrylamido-2-methylpropanesulfonic acid) (CTFA name: Ammonium acryloyldimethyltaurate/Steareth-25 methacrylate crosspolymer) sold under the name Aristoflex HMS by the company Clariant.
Preferably, the polymer bearing a sulfonic group is chosen from copolymers of 2- acrylamido-2-methylpropanesulfonic acid, preferably chosen from the copolymers of (meth)acrylic acid or (meth)acrylate, and of 2-acrylamido-2-methylpropanesulfonic acid, as described above, in particular the optionally salified copolymers of 2-acrylamido-2- methylpropanesulfonic acid and of hydroxylated C2-C4 alkyl (meth)acrylate.
According to an advantageous embodiment, the polymer bearing a sulfonic group is chosen from copolymers of 2-acrylamido-2-methylpropanesulfonic acid and 2- hydroxyethyl acrylate, especially in salt form, hydrophobic modified polymers obtained by polymerization of 2-acrylamido-2-methylpropanesulfonic acid or a sodium or ammonium salt thereof with a (meth)acrylic acid ester and of a Ci6-Ci8 alcohol oxyethylenated with 25 mol of ethylene oxide, and a mixture thereof.
The hydrophilic acrylic homopolymer(s) or copolymer(s) may be present in the composition of the invention in an active material content ranging, for example, from 0.02% to 5% by weight, preferably ranging from 0.05% to 3% by weight and preferentially ranging from 0.05% to 2% by weight relative to the total weight of the composition. Superabsorbent polymers
The composition according to the invention may comprise at least one superabsorbent polymer.
The term "superabsorbent polymer" means a polymer that is capable in its dry form of spontaneously absorbing at least 20 times its own weight of aqueous fluid, in particular of water and especially distilled water. Such superabsorbent polymers are described in the publication "Absorbent polymer technology, Studies in polymer science 8" by L. Brannon-Pappas and R. Harland, published by Elsevier, 1990.
These polymers have a large capacity for absorbing and retaining water and aqueous fluids. After absorption of the aqueous liquid, the polymer particles thus engorged with aqueous fluid remain insoluble in the aqueous fluid and thus conserve their individualized particulate state.
The superabsorbent polymer may have a water-absorbing capacity ranging from 20 to 2000 times its own weight (i.e. 20 g to 2000 g of absorbed water per gram of absorbent polymer), preferably from 30 to 1500 times and better still from 50 to 1000 times. These water absorption characteristics are defined under standard temperature (25°C) and pressure (760 mmHg, i.e. 100 000 Pa) conditions and for distilled water.
The value of the water-absorbing capacity of a polymer may be determined by dispersing 0.5 g of polymer(s) in 150 g of a water solution, waiting for 20 minutes, filtering the unabsorbed solution through a 150 μηη filter for 20 minutes and weighing the unabsorbed water.
The superabsorbent polymer used in the composition of the invention is in the form of particles. Preferably, the superabsorbent polymer has, in the dry or nonhydrated state, an average size of less than or equal to 100 μηι, preferably less than or equal to 50 μηι, ranging for example from 10 to 100 μηη, preferably from 15 to 50 μηη, and better still from 20 to 30 μπι. The average size of the particles corresponds to the weight-average diameter (D50) measured by laser particle size analysis or another equivalent method known to those skilled in the art.
These particles, once hydrated, swell and form soft particles which have an average size that can range from 10 μηη to 1000 μηη, preferably from 20 μηη to 500 μηη, and more preferably from 50 μηη to 400 μηη.
Preferably, the superabsorbent polymers used in the present invention are in the form of spherical particles.
Mention may be made especially of absorbent polymers chosen from:
- crosslinked sodium polyacrylates, for instance those sold under the brand names Octacare X100, X1 10 and RM100 by the company Innospec Active Chemicals, those sold under the names Flocare GB300 and Flosorb 500 by the company SNF, those sold under the names Luquasorb 1003, Luquasorb 1010, Luquasorb 1280 and Luquasorb 1 1 10 by the company BASF, those sold under the names Water Lock G400 and G430 (INCI name: Acrylamide/Sodium acrylate copolymer) by the company Grain Processing, or else Aquakeep® 10 SH NF proposed by the company Sumitomo Seika,
- hydrolyzed starches grafted with an acrylic polymer (homopolymer or copolymer) and especially acryloacrylamide/sodium acrylate copolymer, such as those sold under the names Water Lock A-240, A-180, B-204, D-223, A-100, C-200 and D-223 by the company Grain Processing (INCI name: Starch/acrylamide/sodium acrylate copolymer),
- polymers based on starch, gum and cellulose derivative, such as the product containing starch, guar gum and sodium carboxymethylcellulose, sold under the name Lysorb 220 by the company Lysac,
- and mixtures thereof.
The superabsorbent polymers used in the present invention may be crosslinked or non- crosslinked. They are preferably chosen from crosslinked polymers.
The superabsorbent polymers used in the present invention are preferably crosslinked acrylic homopolymers or copolymers, which are preferably neutralized, and which are in particulate form.
Preferably, the superabsorbent polymer is chosen from crosslinked sodium polyacrylates, preferably in the form of particles with an average size (or average diameter) of less than or equal to 100 microns, more preferably in the form of spherical particles. These polymers preferably have a capacity to absorb water at 0,9 % of NaCI from 10 to 100 g/g, preferably from 20 to 80 g/g and better still from 30 to 80 g/g.
When the composition according to the invention comprises one or more superabsorbent polymers, they may be present in an active material content ranging, for example, from 0.05% to 15% by weight, preferably from 0.1 % to 10% by weight, preferably ranging from 0.1 % to 5% by weight, preferentially ranging from 0.1 % to 3% by weight or even from 0.1 % to 2% by weight relative to the total weight of the composition.
The composition according to the invention may be in various galenical forms conventionally used for topical applications and especially in the form of dispersions of the lotion or serum type, emulsions of liquid or semi-liquid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase (O/W), or suspensions or emulsions of soft, semi-solid or solid consistency of the cream and/or gel type. These compositions are prepared according to the usual methods.
According to one preferred embodiment of the invention, the composition is in the form of an emulsion, and in particular an O/W emulsion or a cream gel.
In addition, the compositions used according to the invention may be more or less fluid and may have the appearance of a white or coloured gel, cream-gel or cream, an ointment, a milk, a lotion, a serum, a paste or a mousse.
The composition preferably has a skin-friendly pH that generally ranges from 3 to 8 and preferably from 4.5 to 7.
Aqueous phase
The aqueous phase of the composition in accordance with the invention comprises at least water. The amount of aqueous phase may range from 0.1 % to 95% by weight, preferably from 0.5% to 95% by weight, better still from 30% to 95% by weight and even better still from 40% to 95% by weight relative to the total weight of the composition. The amount of water can represent all or a portion of the aqueous phase and it is generally at least 30% by weight relative to the total weight of the composition, preferably at least 50% by weight, better still at least 60% by weight.
The aqueous phase may comprise at least one hydrophilic solvent other than the polyols as defined above, for instance substantially linear or branched lower monoalcohols having from 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol or isobutanol.
Fatty phase
The composition according to the invention comprises at least 5% by weight, relative to the total weight of the composition, of a fatty phase. According to one particular embodiment, the proportion of the fatty phase of the emulsion ranges from 5% to 80% by weight, preferably from 5% to 50% by weight and better still from 5% to 30% by weight relative to the total weight of the composition.
The nature of the fatty phase of the composition is not critical. The fatty phase may thus consist of any fatty substance conventionally used in cosmetics or dermatology; it in particular comprises at least one oil (fatty substance that is liquid at 25°C).
Mention may be made, as oils which can be used in the composition of the invention, for example, of:
- hydrocarbon-based oils of animal origin, such as perhydrosqualene;
- hydrocarbon oils of vegetable origin, such as liquid triglycerides of fatty acids comprising from 4 to 10 carbon atoms, such as heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, maize oil, soybean oil, cucumber oil, grape seed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, such as those sold by Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by Dynamit Nobel, jojoba oil and shea butter oil;
- synthetic esters and ethers, in particular of fatty acids, such as oils of formulae RaCOORb and RaORb in which Ra represents the residue of a fatty acid comprising from 8 to 29 carbon atoms and Rb represents a branched or unbranched hydrocarbon-based chain containing from 3 to 30 carbon atoms, such as, for example, purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2- octyldodecyl erucate or isostearyl isostearate; hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, fatty alcohol heptanoates, octanoates and decanoates; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters, such as pentaerythrityl tetraisostearate;
- substantially linear or branched hydrocarbons of mineral or synthetic origin, such as volatile or non-volatile liquid paraffins, and derivatives thereof, petroleum jelly, polydecenes, isohexadecane, isododecane, and hydrogenated polyisobutene such as Parleam® oil;
- fatty alcohols having from 8 to 26 carbon atoms, such as cetyl alcohol, stearyl alcohol and their mixture (cetearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol, oleyl alcohol or linoleyl alcohol; - alkoxylated and in particular ethoxylated fatty alcohols, such as oleth-12, ceteareth-12 and ceteareth-20;
- partially hydrocarbon-based and/or silicone-based fluoro oils, such as those described in the document JP-A-2-295 912. Fluoro oils that may also be mentioned include perfluoromethylcyclopentane and perfluoro-1 ,3-dimethylcyclohexane, sold under the names Flutec PC1® and Flutec PC3® by the company BNFL Fluorochemicals; perfluoro- 1 ,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050® and PF 5060® by the company 3M, or bromoperfluorooctyl sold under the name Foralkyl® by the company Atochem; nonafluoromethoxybutane sold under the name MSX 4518 by the company 3M and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4- trifluoromethylperfluoromorpholine sold under the name PF 5052® by the company 3M;
- silicone oils, for instance volatile or non-volatile polymethylsiloxanes (PDMS) with a substantially linear or cyclic silicone chain, which are liquid or pasty at room temperature, especially cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexadimethylsiloxane and cyclopentadimethylsiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenylsilicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes or 2-phenylethyl trimethylsiloxy silicates, and polymethylphenylsiloxanes;
- mixtures thereof.
In the list of the abovementioned oils, the term "hydrocarbon oil" is understood to mean any oil predominantly comprising carbon and hydrogen atoms, and optionally ester, ether, fluoro, carboxylic acid and/or alcohol groups.
The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture.
The emulsifiers are generally present in the composition in a proportion ranging from 0.1 % to 30% by weight and preferably from 0.2% to 20% by weight relative to the total weight of the composition.
Examples of emulsifiers that may be mentioned include nonionic surfactants, and especially esters of polyols and of fatty acids with a saturated or unsaturated chain containing, for example, from 8 to 24 carbon atoms and better still from 12 to 22 carbon atoms, and the oxyalkylenated derivatives thereof, i.e. derivatives containing oxyethylenated and/or oxypropylenated units, such as the glyceryl esters of C8-C24 fatty acids, and the oxyalkylenated derivatives thereof; the polyethylene glycol esters of C8- C24 fatty acids, and the oxyalkylenated derivatives thereof; the sorbitol esters of C8-C24 fatty acids, and the oxyalkylenated derivatives thereof; fatty alcohol ethers; the sugar ethers of C8-C24 fatty alcohols, and mixtures thereof.
Glyceryl esters of fatty acids that may especially be mentioned include glyceryl stearate (glyceryl monostearate, distearate and/or tristearate) (CTFA name: glyceryl stearate) or glyceryl ricinoleate, and mixtures thereof.
Polyethylene glycol esters of fatty acids that may especially be mentioned include polyethylene glycol stearate (polyethylene glycol monostearate, distearate and/or tristearate) and more especially polyethylene glycol 50 OE monostearate (CTFA name: PEG-50 stearate) and polyethylene glycol 100 OE monostearate (CTFA name: PEG-100 stearate), and mixtures thereof.
Mixtures of these surfactants may also be used, for instance the product containing glyceryl stearate and PEG-100 stearate, sold under the name Arlacel 165 by the company Uniqema, and the product containing glyceryl stearate (glyceryl mono- distearate) and potassium stearate, sold under the name Tegin by the company Goldschmidt (CTFA name: glyceryl stearate SE).
Examples of fatty alcohol ethers that may be mentioned include polyethylene glycol ethers of fatty alcohols containing from 8 to 30 carbon atoms and especially from 10 to 22 carbon atoms, such as polyethylene glycol ethers of cetyl alcohol, of stearyl alcohol or of cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol). Examples that may be mentioned include ethers comprising from 1 to 200 and preferably from 2 to 100 oxyethylene groups, such as those of CTFA name Ceteareth-20 and Ceteareth-30, and mixtures thereof.
Mention may also be made of lipoamino acids and salts thereof, such as monosodium and disodium acylglutamates, for instance the monosodium stearoyl glutamate sold under the name Amisoft HS-1 1 PF and the disodium stearoyl glutamate sold under the name Amisoft HS-21 P by the company Ajinomoto. In a known manner, all the compositions of the invention may contain one or more adjuvants that are common in cosmetics and dermatology: hydrophilic or lipophilic gelling agents and/or thickeners; moisturizers; emollients; hydrophilic or lipophilic active agents; free-radical scavengers; sequestrants; antioxidants; preserving agents; acidifying or basifying agents; fragrances; film-forming agents; fillers; and mixtures thereof. The amounts of these various adjuvants are those conventionally used in the fields under consideration. In particular, the amounts of active agents vary according to the desired objective and are those conventionally used in the fields under consideration, and for example from 0.1 % to 20%, and preferably from 0.5% to 10% by weight of the total weight of the composition.
Active agents
Non-limiting examples of active agents that may be mentioned include ascorbic acid and derivatives thereof such as 5,6-di-O-dimethylsilyl ascorbate (sold by the company Exsymol under the reference Pro-AA), D,L-otocopheryl-21 -ascorbyl phosphate potassium salt (sold by the company Senju Pharmaceutical under the reference Sepivital EPC), magnesium ascorbyl phosphate, sodium ascorbyl phosphate (sold by the company Roche under the reference Stay-C 50); phloroglucinol; enzymes; and mixtures thereof. According to one preferred embodiment of the invention, ascorbic acid is used among the oxidation-sensitive hydrophilic active agents. The ascorbic acid may be of any nature. Thus, it may be of natural origin in powder form or in the form of orange juice, preferably orange juice concentrate. It may also be of synthetic origin, preferably in powder form.
As other active agents that may be used in the composition of the invention, examples that may be mentioned include moisturizing agents, such as protein hydrolysates and polyols, for instance glycerol, glycols, for instance polyethylene glycols; natural extracts; anti-inflammatory agents; oligomeric proanthocyanidins; vitamins such as vitamin A
(retinol), vitamin E (tocopherol), vitamin B5 (panthenol), vitamin B3 (niacinamide), derivatives of these vitamins (in particular esters) and mixtures thereof; urea; caffeine; depigmenting agents such as kojic acid, hydroquinone and caffeic acid; salicylic acid and derivatives thereof; ohydroxy acids, such as lactic acid and glycolic acid and derivatives thereof; retinoids, such as carotenoids and vitamin A derivatives; hydrocortisone; melatonin; extracts of algae, of fungi, of plants, of yeasts, of bacteria; steroids; antibacterial active agents, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether (or triclosan), 3,4,4'-trichlorocarbanilide (or triclocarban) and the acids indicated above, and in particular salicylic acid and derivatives thereof; matting agents, for instance fibres; tensioning agents; UV-screening agents; and mixtures thereof.
Needless to say, a person skilled in the art will take care to select the optional adjuvant(s) added to the composition according to the invention such that the advantageous properties intrinsically associated with the composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition.
The examples that follow will allow the invention to be understood more clearly, without, however, being limiting in nature. The amounts indicated are given as weight percentages of active material, unless otherwise mentioned. The names of the compounds are indicated as INCI names.
EXAMPLES
For each of the compositions, the "aqueous sensation" is evaluated according to the following protocols.
The aqueous sensation on application is evaluated, monadically, by a panel of experts trained in the description of care products. The sensory evaluation of the care products by this panel is performed as follows: The products are conditioned in standard 15 ml_ transparent jars that are coded. Within the same session, the samples are presented in random order to each panellist. 15 descriptors are evaluated in four steps: appearance of the product in the jar (after smoothing the product), uptake, during application to the hand (onto a hand that has been cleaned beforehand with water and liquid soap and wiped with a paper handkerchief). 0.05 ml of product is applied to the top half of the hand (5 passes with the index and the middle finger). The product is evaluated during the five passes, and 2 minutes after application. Each descriptor is evaluated on a non- linear scale, at five levels: poor, sparingly, moderately, quite, very.
The descriptor "aqueous sensation on application" is more particularly of interest here, and is defined as being the visualizations of droplets, drops or liquid pools at the surface of the skin (independently of the colour and of the texture). Procedure (application action): The droplets are evaluated visually, on application of 0.05 ml of the product to half of the back of the hand, by massaging this area over five passes. The droplets are evaluated visually during the spreading of the product.
Comparative example Cream-gel SPF15
A * B C* D
Water qs 100 100 100 100
A Preserving agent(s) 1 1 1 1
Glycerol 3 3 3 3
Ammonium
B polyacryldimethyltauramide 0.5 0.5 - - (Hostacerin AMPS® from Clariant)
Sodium polyacrylate
- - 0.5 0.5 (Cosmedia SP from Cognis)
Isononyl isononanoate 8 8 8 8
C1
UV screening agent(s) 15 15 15 15 Silica silylate
C2 1 .3 - 1 .3 -
(Aerogel VM2270 from Dow Corning)
Inulin lauryl carbamate
C3 (Inutec SP1 from Beneo Bio Based 1 1 1 1
Chemicals)
* Composition according to the invention
Manufacturing process:
- Heat the aqueous phase A to 85°C with magnetic stirring - Cool to 75°C.
- While mixing with a Rayneri blender, add phase B to phase A and leave to swell.
- Heat the oily phase C1 to 85°C with magnetic stirring.
- While mixing with a Rayneri blender, add phase C2 to phase C1 , and then phase C3 to phase C2 + C1 .
- While mixing with a Rayneri blender, add the oily phase C1 +C2+C3 to the aqueous phase A + B at 75°C. Cool to room temperature.
Results of the evaluation:
Figure imgf000033_0001
* composition according to the invention
Compositions A and C according to the invention are more aqueous on application than the equivalent compositions (B and D, respectively), but which do not contain any aerogel.
Comparative example Cream-gel for greasy skin
E* F
Water 66.5 67.5
A Propanediol 5 5
Tetrasodium EDTA 0.1 0.1 Sodium polyacrylate (Cosmedia SP from
0.4 0.4
Cognis)
Glycerol 7 7
Sodium acrylates crosspolymer-2 (and) water
(and) silica (Aquakeep 10SH-NFC from 0.8 0.8
Sumitomo Seika)
Dimethicone 5 cSt 5 5
Isopropyl lauroyl sarcosinate 5 5
B Preserving agent(s) 0.7 0.7
Inulin lauryl carbamate
0.2 0.2
(Inutec SP1 from Beneo Bio Based Chemicals)
Silica silylate
C 1 -
(Aerogel VM2270 from Dow Corning)
Perlite
D 1 1
(Optimat 2550 OR from World Minerals)
Denatured alcohol 7 7
E
Fragrance 0.25 0.25
Water 0.04995 0.04995
F
CI 42090 0.00005 0.00005
* Composition according to the invention
Manufacturing process:
- While mixing with a Rayneri blender, leave phase A to swell.
- While mixing with a Rayneri blender, add the oily phase B to the aqueous phase A.
- While mixing with a Rayneri blender, disperse phase C, and then add phases D, E and F.
Results of the evaluation:
Figure imgf000034_0001
* composition according to the invention Composition E according to the invention is more opalescent (in the sense that it is more transparent) and more aqueous on application than the equivalent composition F not containing any aerogel.
Composition according to the invention: Moisturizing cream-gel
Figure imgf000035_0001
* Composition according to the invention Composition G affords an aqueous sensation on application.
Comparative example Cream-gel for greasy skin
H* I
Silica 1 .5 1 .5
Silica silylate
(Aerogel VM2270 from Dow Corning) 1
Preserving agent(s) 0.4 0.4
Isohexadecane 9 9
Fragrance 0.1 0.1
Ammonium acryloyldimethyltaurate/Steareth-25 0.7 0.7 methacrylate crosspolymer
(Aristoflex HMS from Clariant)
Denatured alcohol 5 5
Water qs 100 qs 100
Glycerol 5 5
* Composition according to the invention
Results of the evaluation:
Figure imgf000036_0001
* composition according to the invention
Composition H according to the invention is more opalescent (in the sense that it is more transparent) and more aqueous on application than the equivalent composition I not containing any aerogel.
Composition according to the invention: Moisturizing cream-gel
Figure imgf000036_0002
* Composition according to the invention Composition J according to the invention affords an aqueous sensation on application.

Claims

1 . Composition for topical application comprising at least 5% by weight, relative to the total weight of the composition, of a fatty phase dispersed in an aqueous phase; hydrophobic silica aerogel particles with a specific surface area per unit of mass (SM) ranging from 500 to 1500 m2/g, preferably from 600 to 1200 m2/g and better still from 600 to 800 m2/g, and a size expressed as the mean volume diameter (D[0.5]) ranging from 1 to 1500 μηη, better still from 1 to 1000 μηη, even more preferentially from 1 to 100 μηη, in particular from 1 to 30 μηη, more preferably from 5 to 25 μηη, better still from 5 to 20 μηη and even better still from 5 to 15 μηη;
and at least one hydrophilic acrylic homopolymer or copolymer;
with the exception of the following compositions:
Composition A
Phase INCI name
A Water qs 100
Glycerol 5.00
Disodium EDTA 0.05
Propylene glycol 6.60
B Caprylyl glycol 0.15
Isohexadecane 3.50
1.00
Polysorbate 80 (Tween 80-LQ-(WL) from Croda)
Dimethicone (and) Ceteth-10 (and) Laureth-4 (Dow 1.50
Corning 7-3099 Dimethicone HIP Emulsion)
Dimethicone 350 cSt 0.3
Dimethicone 10 cSt 4.25
Dimethicone 5 cSt 4.75
C Isohexadecane 2.00
Carbomer (Carbopol 981 from Lubrizol) 0.15
D Sodium Hydroxide 0.06
Water 0.54
Ammonium polyacryloyldimethyl taurate (Hostacerin AMPS®
1.80
from Clariant)
E Nylon-12 (Orgasol 2002 EXD NAT COS from Arkema) 0.50 Ethanol 5.00
Hydrophobic silica aerogel particles (VM-2270 from Dow
0.7
Corning)
Composition B
Phase INCI name
A1 Water qs 100
Butylene glycol 5.00
Glycerol 5.00
Tetrasodium EDTA 0.20
Phenoxyethanol 0.70
Glyceryl stearate (and) PEG-100 stearate (Arlacel 165-FL
B 2.00 from Croda)
Cetyl alcohol 0.50
Methylparaben 0.25
PEG-20 stearate (Myrj S20-PA-(WL) from Croda) 0.80
Stearyl alcohol 0.50
Stearic acid 3.00
Capryloylsalicylic acid (Mexoryl SAB from Chimex) 0.05
Ammonium polyacryloyldimethyl taurate (Hostacerin AMPS® 1.60 from Clariant)
Dimethicone 350 cSt 0.15
Dimethicone 10 cSt 3.64
Dimethicone 5 cSt 3.64
B2 Triethanolamine 0.30
Hydrophobic silica aerogel particles (VM-2270 from Dow
B3 0.56 Corning)
Composition C
Phase INCI name
A Water qs 100
Glycerol 5.00
Disodium EDTA 0.05 Propylene glycol 6.60
B Caprylyl glycol 0.15
Isohexadecane 9.06
Polysorbate 80 (Tween 80-LQ-(WL) from Croda) 1 .00
Dimethicone (and) Ceteth-10 (and) Laureth-4 (Dow 1 .50
Corning 7-3099 Dimethicone HIP Emulsion)
Pentaerythrityl tetraoctanoate 3.68
C Isohexadecane 1 .00
Carbomer (Carbopol 981 from Lubrizol) 0.15
D Sodium hydroxide 0.06
Water 0.54
Ammonium polyacryloyldimethyl taurate (Hostacerin AMPS®
1 .80 from Clariant)
E Nylon-12 (Orgasol 2002 EXD NAT COS from Arkema) 0.50
Ethanol 5.00
Hydrophobic silica aerogel particles (VM-2270 from Dow
G 0.8 Corning)
Composition D
Phase INCI name
A1 Water qs 100
Butylene glycol 5.00
Glycerol 5.00
Tetrasodium EDTA 0.20
Phenoxyethanol 0.70
Glyceryl stearate (and) PEG-100 stearate (Arlacel 165-FL
B 2.00 from Croda)
Cetyl alcohol 0.50
Methylparaben 0.25
PEG-20 stearate (Myrj S20-PA-(WL) from Croda) 0.80
Stearyl alcohol 0.50
Stearic acid 3.00
Capryloylsalicylic acid (Mexoryl SAB from Chimex) 0.05 Ammonium polyacryloyldimethyl taurate (Hostacerin 1 .60
AMPS® from Clariant)
Isohexadecane 4.41
Parleam 2.94
B2 Triethanolamine 0.30
Hydrophobic silica aerogel particles (VM-2270 from
B3 0.64
Dow Corning)
2. Composition according to Claim 1 , in which the hydrophilic acrylic homopolymer(s) or copolymer(s) are chosen from non-superabsorbent and at least partially neutralized acrylic acid homopolymers or copolymers and homopolymers or copolymers comprising at least one monomer bearing a sulfonic group.
3. Composition for topical application comprising at least 5% by weight, relative to the total weight of the composition, of a fatty phase dispersed in an aqueous phase; hydrophobic silica aerogel particles with a specific surface area per unit of mass (SM) ranging from 500 to 1500 m2/g, preferably from 600 to 1200 m2/g and better still from 600 to 800 m2/g, and a size expressed as the mean volume diameter (D[0.5]) ranging from 1 to 1500 μηη, better still from 1 to 1000 μηη, even more preferentially from 1 to 100 μηη, in particular from 1 to 30 μηη, more preferably from 5 to 25 μηη, better still from 5 to 20 μηη and even better still from 5 to 15 μηη; and at least one hydrophilic acrylic homopolymer or copolymer chosen from non-superabsorbent and at least partially neutralized acrylic acid homopolymers or copolymers and copolymers comprising at least one monomer bearing a sulfonic group.
4. Composition according to any one of Claims 1 to 3, in which the non-superabsorbent acrylic acid homopolymers or copolymers are in a particulate form, their mean size in the hydrated state preferably being less than or equal to 10 μηη and even more preferentially less than or equal to 5 μηη, and their mean size in the dry and unhydrated state preferably being less than or equal to 2 μηη and even more preferentially less than or equal to 1 μηι.
5. Composition according to Claim 4, in which the non-superabsorbent acrylic acid homopolymers or copolymers are chosen from at least partially neutralized acrylic acid homopolymers.
6. Composition according to one of Claims 1 to 5, in which the monomer bearing a sulfonic group is 2-acrylamido-2-methylpropanesulfonic acid.
7. Composition according to any one of Claims 1 to 6, in which the polymer comprising at least one monomer bearing a sulfonic group is chosen from copolymers of (meth)acrylic acid or of (meth)acrylate and of 2-acrylamido-2-methylpropanesulfonic acid, in particular the optionally salified copolymers of 2-acrylamido-2- methylpropanesulfonic acid and of a hydroxylated, optionally salified C2-C4 alkyl (meth)acrylate.
8. Composition according to any one of Claims 1 to 7, in which the polymer comprising at least one monomer bearing a sulfonic group is a copolymer of 2-acrylamido-2- methylpropanesulfonic acid and of 2-hydroxyethyl acrylate.
9. Composition according to one of Claims 1 to 8, in which the polymer comprising at least one monomer bearing a sulfonic group is chosen from hydrophobic-modified polymers obtained by polymerization of 2-acrylamido-2-methylpropanesulfonic acid or a sodium or ammonium salt thereof with a (meth)acrylic acid ester and
- of a C -C alcohol oxyethylenated with 8 mol of ethylene oxide,
- of a On oxo alcohol oxyethylenated with 8 mol of ethylene oxide,
- of a On oxo alcohol oxyethylenated with 7 mol of ethylene oxide,
- of a C-I2-C-U alcohol oxyethylenated with 7 mol of ethylene oxide,
- of a C-I2-C-U alcohol oxyethylenated with 9 mol of ethylene oxide,
- of a C-I2-C-U alcohol oxyethylenated with 1 1 mol of ethylene oxide,
- of a C16-C18 alcohol oxyethylenated with 8 mol of ethylene oxide,
- of a C16-C18 alcohol oxyethylenated with 15 mol of ethylene oxide,
- of a C16-C18 alcohol oxyethylenated with 1 1 mol of ethylene oxide,
- of a C16-C18 alcohol oxyethylenated with 20 mol of ethylene oxide,
- of a C16-C18 alcohol oxyethylenated with 25 mol of ethylene oxide,
- of a C18-C22 alcohol oxyethylenated with 25 mol of ethylene oxide and/or of a Ci6-Ci8 iso alcohol oxyethylenated with 25 mol of ethylene oxide,
and mixtures thereof.
10. Composition according to any one of Claims 1 to 9, in which the hydrophilic acrylic homopolymer(s) or copolymer(s) are present in an active material content ranging, for example, from 0.02% to 5% by weight, preferably from 0.05% to 3% by weight and better still from 0.05% to 2% by weight, relative to the total weight of the composition.
1 1 . Composition according to any one of Claims 1 to 10, in which the hydrophobic silica aerogel particles have a specific surface area per unit of volume Sv ranging from 5 to 60 m2/cm3, preferably from 10 to 50 m2/cm3 and better still from 15 to 40 m2/cm3 and/or have an oil-absorbing capacity measured at the wet point ranging from 5 to 18 ml/g of particles, preferably from 6 to 15 ml/g and better still from 8 to 12 ml/g.
12. Composition according to any one of Claims 1 to 1 1 , in which the hydrophobic silica aerogel particles are trimethylsiloxyl silica particles.
13. Composition according to any one of Claims 1 to 12, in which the hydrophobic silica aerogel particles may be present in the composition according to the invention in a content ranging from 0.05% to 15% by weight, preferably from 0.1 % to 10% by weight, better still from 0.5% to 5% by weight and more preferably from 0.5% to 2% by weight relative to the total weight of the composition.
14. Cosmetic treatment process for a keratin material, in which a cosmetic composition as defined in any one of Claims 1 to 13 is applied to the keratin material.
15. Use of a cosmetic composition as defined in any one of claims 1 to 13, in the cosmetic or dermatological field, and in particular for caring for, protecting and/or making up bodily or facial skin, or for haircare.
PCT/EP2012/075776 2011-12-16 2012-12-17 Composition comprising silica aerogel particles and a hydrophilic acrylic homopolymer or copolymer WO2013087927A1 (en)

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FR1161791A FR2984133B1 (en) 2011-12-16 2011-12-16 COMPOSITION COMPRISING SILICA AEROGEL PARTICLES AND A HYDROPHILIC ACRYLIC HOMO- OR COPOLYMER
FR1161791 2011-12-16
US201161578186P 2011-12-20 2011-12-20
US61/578,186 2011-12-20

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WO2013190238A3 (en) * 2012-06-21 2014-12-04 L'oreal Cosmetic composition of hydrophobic silica aerogel particles and an acrylic thickening polymer
US10398631B2 (en) 2013-02-25 2019-09-03 L'oreal Gel-type cosmetic composition
US10238584B2 (en) 2013-02-25 2019-03-26 L'oreal Gel-type cosmetic composition
KR101573574B1 (en) 2013-09-05 2015-12-01 주식회사 엘지생활건강 Cosmetic composition comprising film forming agents for skin
US9517188B2 (en) * 2014-03-21 2016-12-13 L'oreal Water-based gel cosmetic compositions containing emulsifier
US20150265504A1 (en) * 2014-03-21 2015-09-24 L'oreal Water-based gel cosmetic compositions containing emulsifier
WO2016030838A1 (en) * 2014-08-28 2016-03-03 L'oreal Gel-gel comprising at lease two fillers with a soft-focus effect
FR3025094A1 (en) * 2014-08-28 2016-03-04 Oreal GEL / GEL COMPOSITION COMPRISING A UV FILTER AND A HYDROPHOBIC SILICA AEROGEL
FR3025097A1 (en) * 2014-08-28 2016-03-04 Oreal GEL / GEL COMPRISING AT LEAST TWO LOOSE EFFECTS
FR3025095A1 (en) * 2014-08-28 2016-03-04 Oreal GEL / GEL COMPOSITION COMPRISING A UV FILTER AND AN ORGANOPOLYSILOXANE ELASTOMER
FR3025103A1 (en) * 2014-08-28 2016-03-04 Oreal GEL / GEL COMPOSITION COMPRISING A UV FILTER
WO2016030839A1 (en) * 2014-08-28 2016-03-03 L'oreal Gel composition and gel comprising a uv filter
US11311465B2 (en) 2014-08-28 2022-04-26 L'oreal Gel-type cosmetic composition with improved staying power
US20190231663A1 (en) * 2018-01-31 2019-08-01 L'oreal Cooling gel composition
JP2019151594A (en) * 2018-03-05 2019-09-12 株式会社トクヤマ Aqueous cosmetic
JP7019460B2 (en) 2018-03-05 2022-02-15 株式会社トクヤマ Water-based cosmetics

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