WO2022128544A1 - Cosmetic composition comprising an oily dispersion of polymer particles and an aqueous dispersion of colloidal silica particles - Google Patents
Cosmetic composition comprising an oily dispersion of polymer particles and an aqueous dispersion of colloidal silica particles Download PDFInfo
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- WO2022128544A1 WO2022128544A1 PCT/EP2021/084235 EP2021084235W WO2022128544A1 WO 2022128544 A1 WO2022128544 A1 WO 2022128544A1 EP 2021084235 W EP2021084235 W EP 2021084235W WO 2022128544 A1 WO2022128544 A1 WO 2022128544A1
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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
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
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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
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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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/31—Hydrocarbons
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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
- A61K8/72—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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/025—Semi-permanent tattoos, stencils, e.g. "permanent make-up"
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/65—Characterized by the composition of the particulate/core
- A61K2800/654—The particulate/core comprising macromolecular material
Definitions
- Cosmetic composition comprising an oily dispersion of polymer particles and an aqueous dispersion of colloidal silica particles
- the present application relates to the field of making up keratin materials, in particular the skin, eyelashes and eyebrows.
- composition comprising, preferably in a physiologically acceptable medium, at least: - one oily dispersion which comprises: i) one or more particles comprising: a) one or more ethylenic copolymers of a 1 ) (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate, and of a 2 ) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a 2 ) is a (C 1 - C 4 )(alkyl)acrylic acid; and ii) one or more polymeric stabilizers chosen from: b) polymers of (C 3 -C 12 )cycloalkyl (C 1 -C 6 )(alkyl)acrylate monomers; and c) copolymers of c 1 ) (C 3 -C 12 )cycloalky
- the present invention also relates to a method for making up and/or caring for keratin materials consisting in applying to the surface of said materials at least one composition as defined previously.
- Cosmetic makeup compositions are commonly used to give keratin materials such as the skin, eyelashes and eyebrows an attractive colour, but also to enhance the beauty of uneven skin, by making it possible to hide marks and dyschromias, and to reduce the visibility of relief imperfections such as pores and wrinkles.
- They may also be used to correct and harmonize the appearance of the eyelashes or eyebrows. Many formulations have been developed to date.
- compositions which provide a good wear property of the makeup effect over time notably makeup which is resistant, in everyday life, to the test of showering or bathing in the presence of hot water and detergent surfactants, to sweat and to sebum, in order to be able to avoid having to re-apply the composition too often.
- semipermanent makeup techniques exist, such as tattooing and in particular the techniques of microblading and microshading which consist in inserting, using a needle, a coloured pigment under the surface layers of the skin.
- the application is painful, irreversible and very expensive unlike standard makeup products which are very comfortable but do not generally enable a long wear property beyond one day.
- Aqueous makeup formulations containing film-forming polymers in dispersion in water such as latices have good resistance to sebum but do not withstand the test of showering or bathing (hot water and detergent surfactants).
- anhydrous mascara formulations and eyeliner formulations are known that contain a dispersion in isododecane of particles of at least one polymer that is surface-stabilized by a stabilizer, the polymer of the particles being a polymer of C 1 -C 4 alkyl (meth)acrylate and at least one ethylenically unsaturated acid monomer or a salt thereof, or the anhydride thereof or a salt thereof; the stabilizer being an isobornyl (meth)acrylate polymer chosen from isobornyl (meth)acrylate homopolymer and statistical copolymers of isobornyl (meth)acrylate and of C 1 -C 4 alkyl (meth)acryl
- compositions in the presence of waxes have a tendency to be unstable and heterogeneous due to a recrystallization phenomenon of the waxes. They are not entirely satisfactory either for coverage in order to be able to effectively conceal or correct imperfections. They are moreover sensitive to sebum and in contact therewith have a tendency to produce a sticky and tacky deposit. [0008] There is therefore a need to find new semipermanent compositions for making up and/or caring for keratin materials without the drawbacks of the techniques and formulations known from the prior art. It is sought to obtain formulations that are stable, comfortable and have a long wear property on keratin materials and in particular that are resistant to hot water and to surfactants and to sebum.
- compositions comprising, preferably in a cosmetically acceptable medium, at least: - one oily dispersion which comprises: i) one or more particles comprising: a) one or more ethylenic copolymers of a 1 ) (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate, and of a 2 ) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a 2 ) is a (C 1 - C 4 )(alkyl)acrylic acid; and ii) one or more polymeric stabilizers chosen from: b) polymers of (C 3 -C 12 )cycloalkyl (C 1 -C 6 )(alkyl)acrylate monomers; and c) copo
- a first subject of the present invention is a composition comprising, preferably in a cosmetically acceptable medium, at least: - one oily dispersion which comprises: i) one or more particles comprising: a) one or more ethylenic copolymers of a 1 ) (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate, and of a 2 ) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a 2 ) is a (C 1 - C 4 )(alkyl)acrylic acid; and ii) one or more polymeric stabilizers chosen from: b) polymers of (C 3 -C 12 )cycloalkyl (C 1 -C 6 )(alkyl)acrylate monomers;
- a second subject of the present invention is a method for making up and/or caring for keratin materials consisting in applying to the surface of said materials at least one composition as defined previously.
- the term “keratin fibres” is understood to mean the skin, the eyelashes and the eyebrows.
- this term “keratin fibres” also extends to synthetic false eyelashes.
- physiologically acceptable means compatible with the skin and its integuments, which has a pleasant colour, odour and feel, and which does not cause any unacceptable discomfort (stinging or tautness) liable to discourage the consumer from using this composition.
- an “alkyl” radical is a linear or branched saturated C 1 -C 8 , in particular C 1 -C 6 , preferably C 1 -C 4 hydrocarbon-based group such as methyl, ethyl, n-propyl, isopropyl or i-propyl, n-butyl, isobutyl or i-butyl, and tert-butyl or t-butyl;
- - an “alkylene” radical is a linear or branched divalent saturated C 1 -C 8 , in particular C 1 -C 6 , preferably C 1 -C 4 hydrocarbon-based group such as methylene, ethylene or propylene;
- a “cycloalkyl” radical is a cyclic saturated hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 13 carbon atoms, preferably between 5 and 10 carbon atoms, and which may be substituted with one or more (C 1
- aryl-O-, radical with aryl as defined previously, preferably phenoxy;
- an “aryl(C 1 -C 4 )alkoxy” radical is an aryl-(C 1 -C 4 )alkyl-O- radical, preferably benzoxy;
- the term “insoluble monomer” thus means any monomer whose homopolymer or copolymer is not in soluble form, i.e.
- ethylenic homopolymer means a polymer derived from the polymerization of identical monomers
- ethylenic copolymer means a polymer derived from the polymerization of different monomers, in particular at least two different monomers.
- fatty substance means an organic compound that is immiscible in water at ordinary room temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably 1% and even more preferentially 0.1%). They bear in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms or a sequence of at least two siloxane groups.
- the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance ethanol, ether, liquid petroleum jelly or decamethylcyclopentasiloxane.
- fatty substances are neither polyoxyethylenated nor polyglycerolated. They are different from fatty acids, since salified fatty acids constitute soaps that are generally soluble in aqueous media; - the term “liquid” fatty substance notably refers to a fatty substance that is liquid at 25°C and 1 atmosphere; preferably, said fatty substance has a viscosity of less than or equal to 7000 centipoises at 20°C; - the term “hydrocarbon-based” fatty substance means a fatty substance which comprises at least 50% by weight, notably from 50% to 100% by weight, for example from 60% to 99% by weight, or else from 65% to 95% by weight, or even from 70% to 90% by weight, relative to the total weight of said fatty substance, of carbon-based compound, having a global solubility parameter in the Hansen solubility space of less than or equal to 20 (MPa) 1/2 , or a mixture of such compounds; - the term “oil” means a fatty substance that is liquid at
- volatile oil means an oil (or non-aqueous medium) that can evaporate on contact with keratin materials, in particular the skin, in less than one hour, at room temperature and at atmospheric pressure.
- the volatile oil is a volatile cosmetic oil, which is liquid at room temperature, notably having a non- zero vapour pressure, at room temperature and at atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40000 Pa (10 -3 to 300 mmHg), preferably ranging from 1.3 Pa to 13000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg); - the term “non-volatile oil” means an oil with a vapour pressure of less than 0.13 Pa at room temperature and at atmospheric pressure.
- the dispersions according to the invention are therefore constituted of particles, which are generally spherical, of at least one polymer i) which is surface stabilized with one or more stabilizers ii), in a non-aqueous medium.
- a polymeric statistical stabilizer ii) comprising in major amount a portion ii) that is soluble and in minor amount a portion ii) that is insoluble in the dispersion medium, i.e.
- the polymer particles i) and the stabilizer(s) ii) are preferably in the hydrocarbon-based liquid fatty substance(s) iii) in an amount of between 2% and 40% by weight, in particular between 4% and 35% by weight of soluble monomer (the one forming the stabilizer(s) ii)) and between 60% and 98% by weight, in particular from 65% to 96% by weight of insoluble monomer (the one forming the particles i)).
- the particle(s) i) of the dispersion of the process of the invention is (are) constituted of one or more ethylenic copolymers derived from the polymerization a 1 ) of at least one (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate monomer and a 2 ) of at least one ethylenic monomer comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a 2 ) is a (C 1 -C 4 )(alkyl)acrylic acid.
- the particle(s) i) is (are) constituted of an ethylenic polymeric core derived from copolymers a), as defined previously.
- ethylenic copolymer means a polymer resulting from the polymerization of two monomers: of (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate monomer a 1 ) and of ethylenic monomer a 2 ) comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl, such as phenyl, groups.
- the ethylenic compound may also be a cyclic compound, which is preferably 5- or 6-membered, and comprising an ethylenic unsaturation.
- An ethylenic monomer comprising “one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups” is understood to mean that the monomer is substituted on the one of the carbon atoms of the polymeric monomer with one or more groups, preferably a single group, chosen from carboxyl ⁇ C(O)-OH, phosphoric acid ⁇ O-P(O)(OH) 2 or ⁇ P(O)(OH) 2 , and sulfonic acid ⁇ O-S(O) 2 -OH or ⁇ S(O) 2 -OH, maleic anhydride, and aryl such as phenyl.
- the particle(s) i) comprises (comprise) a) ethylenic copolymers of a 1 ) (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate and of a 2 ) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl, such as benzyl, groups.
- a 2 is a (C 1 - C 4 )(alkyl)acrylic acid, more particularly b) is (are) copolymers of (C 1 -C 4 )alkyl (meth)acrylate and of (meth)acrylic acid.
- a 2 is chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, acrylamidopropanesulfonic acid, acrylamidoglycolic acid, and salts thereof, more preferentially a 2 ) represents maleic anhydride.
- the salts may be chosen from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminium, manganese or copper; ammonium salts of formula NH 4 +; quaternary ammonium salts; salts of organic amines, for instance salts of methylamine, diethylamine, trimethylamine, triethylamine, ethylamine, 2-hydroxyethylamine, bis(2-hydroxyethyl)amine or tris(2-hydroxyethyl)amine; lysine or arginine salts.
- alkali metals for example sodium or potassium
- salts of alkaline-earth metals for example calcium, magnesium or strontium
- metal salts for example zinc, aluminium, manganese or copper
- ammonium salts of formula NH 4 + quaternary ammonium salts
- salts of organic amines for instance salts of
- the (C 1 -C 4 )alkyl (C 1 - C 4 )(alkyl)acrylate monomer(s) a 1 ) is (are) chosen from those of formula (I): [Chem 2] in which formula (I): - R represents a hydrogen atom or a (C 1 -C 4 )alkyl group such as methyl, and - R' represents a (C 1 -C 4 )alkyl group such as methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, preferably methyl, ethyl or i-butyl, preferably (I) represents a C 1 -C 4 alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl acrylate and isobutyl methacrylate.
- the polymer constituting the particles i) is an ethylenic acrylate copolymer a) resulting from the polymerization: - a 1 ) of at least one monomer of formula (I) as defined previously, preferably a C 1 - C 4 alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl acrylate and isobutyl methacrylate; and - a 2 ) of at least one monomer chosen from (1), (2), (3) and (4) as defined previously and preferentially of formula (II) and also the salts thereof: [Chem 3] in which formula (II) R is as defined previously, in particular (II) represents acrylic acid.
- the amount of a 2 ) notably of compound (II) and in particular of acrylic acid is greater than 2.5% by weight relative to the total weight of the particle i), more particularly between 3% and 35% by weight relative to the weight of polymer of the particle i), even more particularly between 5% and 25% by weight and the polymer of the particles i), better still between 10% and 15% by weight and the polymer of the particles i).
- a) is a copolymer resulting from the copolymerization a 2 ) of acrylic acid with a 1 ) one or more C 1 -C 4 alkyl (meth)acrylate monomers, preferably at least two different C 1 -C 4 alkyl (meth)acrylate monomers, in particular chosen from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and isobutyl (meth)acrylate.
- the polymer constituting the particles i) is an ethylenic acrylate copolymer a) resulting from the polymerization: - of at least two different monomers: of formula (I) as defined previously, preferably a C 1 -C 4 alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl (meth)acrylate; and - of at least one monomer chosen from (1), (2), (3) and (4) as defined previously, preferably of formula (II) as defined previously.
- the polymer of the particles i) is a polymer derived from C 1 -C 4 alkyl (meth)acrylate monomers a 1 ).
- a linear or branched, preferably linear, C 1 -C 4 alkyl acrylate, in particular (C 1 -C 3 )alkyl acrylate, monomer is used.
- a) is chosen from methyl acrylate and ethyl acrylate.
- the monomers a 1 ) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl (meth)acrylate, more preferentially chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
- the polymer constituting the particles i) is an acrylate copolymer a) resulting: a 1 ) from at least one monomer of formula (I) as defined previously; and a 2 ) from at least one ethylenically unsaturated anhydride monomer, notably of formula (4) as defined previously.
- the polymer of the particles a) is a polymer a 1 ) of linear or branched, preferably linear, C 1 -C 4 alkyl (meth)acrylate, in particular (C 1 -C 3 )alkyl (meth)acrylate, and a 2 ) of ethylenically unsaturated anhydride monomer.
- the monomers a 1 ) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl (meth)acrylate.
- use is made of one, or two different, linear or branched, preferably linear, C 1 -C 4 alkyl acrylate, in particular (C 1 -C 3 )alkyl acrylate monomers a 1 ).
- a 1 is chosen from methyl acrylate and ethyl acrylate.
- a 1 ) is chosen from isobutyl acrylate and isobutyl methacrylate.
- the ethylenically unsaturated anhydride compound(s) a 2 ) of the invention is (are) chosen from derivatives of maleic anhydride (4a) and of itaconic anhydride (4b) as defined previously.
- the ethylenically unsaturated anhydride monomer of the invention is of formula (4a) and even more preferentially is maleic anhydride.
- the polymer of the particles may be chosen from: methyl acrylate/maleic anhydride copolymers; ethyl acrylate/maleic anhydride copolymers; and methyl acrylate/ethyl acrylate/maleic anhydride copolymers.
- the copolymer(s) of the particles i) of the oily dispersion comprises (comprise) from 80% to 95% by weight of ingredient a 1 ) and from 5% to 20% by weight of ingredient a 2 ), relative to the total weight of the copolymer(s).
- the polymer of the particles i) comprises preferably from 80% to 93% by weight of ingredient a 1 ), notably of C 1 -C 4 alkyl (meth)acrylate, and from 7% to 20% by weight of ingredient a 2 ) relative to the total weight of the polymer i).
- the polymer of the particles i) comprises preferably from 85% to 93% by weight, more particularly 87% to 92% by weight, even more preferentially from 85% to 90% by weight of ingredient a 1 ), notably of C 1 -C 4 alkyl (meth)acrylate, and from 10% to 20% by weight of ingredient a 2 ) relative to the total weight of the polymer.
- the polymer of the particles i) is a non-crosslinked polymer.
- the copolymers i) are chosen from: - copolymers of methyl acrylate/ethyl acrylate/acrylic acid and its salts; - copolymers of methyl acrylate/ethyl acrylate/maleic anhydride; - copolymers of methyl acrylate/acrylic acid and its salts; - copolymers of ethyl acrylate/acrylic acid and its salts; - copolymers of methyl acrylate/maleic anhydride; - copolymers of ethyl acrylate/maleic anhydride; - copolymers of isobutyl acrylate/acrylic acid and its salts; and - copolymers of isobutyl acrylate/isobutyl methacrylate/acrylic acid and its salts.
- the polymer of the particles i) of the dispersion preferably has a number-average molecular weight ranging from 2000 to 10000000 g/mol.
- the polymer of the particles i) may be present in the dispersion (A) in a content ranging from 20% to 60% by weight relative to the total weight of the dispersion, in particular between 21% and 58.5% by weight relative to the total weight of the dispersion, preferably ranging from 30% to 50% by weight relative to the total weight of the dispersion, more preferentially ranging from 36% to 42% by weight relative to the total weight of the dispersion (A).
- the particle(s) i) is (are) constituted of a copolymer of a 1 ) and a 2 ).
- the particles i) are constituted of copolymers resulting from the polymerization of monomers a 1 ) and a 2 ) with an a 1 ) / a 2 ) weight ratio inclusively between 4.4 and 20, more particularly between 5.5 and 19, preferably between 6.5 and 16 and even more preferentially between 6.6 and 15.6.
- the polymer particle(s) i) of the dispersion (A) preferably has (have) a number-average size ranging from 5 to 600 nm, notably ranging from 10 to 500 nm and better still ranging from 20 to 400 nm.
- the stabilizer(s) ii) [0056]
- the dispersion (A) according to the invention also comprises one or more stabilizers ii). Preferably, only one type of stabilizer ii) is used in the invention.
- the stabilizer(s) of the invention is (are) constituted of ethylenic polymers chosen from b) polymers of (C 3 -C 12 )cycloalkyl (C 1 -C 6 )(alkyl)acrylate monomers; and c) copolymers of c 1 ) (C 3 -C 12 )cycloalkyl (C 1 -C 6 )(alkyl)acrylate and c 2 ) (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate.
- the stabilizer(s) of the invention is (are) constituted of ethylenic polymers chosen from c) copolymers of c 1 ) (C 3 - C 12 )cycloalkyl (C 1 -C 6 )(alkyl)acrylate and c 2 ) (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate.
- the stabilizer(s) of the invention is (are) constituted of ethylenic polymers chosen from b) polymers of (C 3 - C 12 )cycloalkyl (C 1 -C 6 )(alkyl)acrylate monomers, particularly of formula (III) as defined previously.
- the stabilizer(s) of the invention is (are) constituted of ethylenic polymers chosen from c) copolymers of c 1 ) (C 3 -C 12 )cycloalkyl (C 1 -C 6 )(alkyl)acrylate, particularly of formula (III) as defined previously and of c 2 ) (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate, particularly of formula (I) as defined previously.
- the ingredient c 2 ) is a (C 1 - C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate monomer, notably of formula (I), more particularly chosen from methyl (meth)acrylate and ethyl (meth)acrylate, more preferentially methyl (meth)acrylate.
- the ingredient c 2 ) is a mixture of several different (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate monomers, in particular two different (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate monomers, notably formula (I), more particularly chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
- formula (I) more particularly chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
- the stabilizer ii) is chosen from b) polymers of (C 3 - C 12 )cycloalkyl (C 1 -C 6 )(alkyl)acrylate monomers; and c) statistical copolymers of c 1 ) (C 3 -C 12 )cycloalkyl (C 1 -C 6 )(alkyl)acrylate and of c 2 ) (C 1 -C 4 )alkyl (C 1 - C 4 )(alkyl)acrylate with a c 1 )/c 2 ) weight ratio of greater than 4.
- said weight ratio ranges from 4.5 to 19.
- said c 1 )/c 2 ) weight ratio ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 12.
- the stabilizer ii) is a polymer chosen from b) isobornyl (meth)acrylate homopolymer and c) statistical copolymers of c 1 ) isobornyl (meth)acrylate and of c 2 ) C 1 -C 4 alkyl (meth)acrylate preferably present in an isobornyl (meth)acrylate/C 1 -C 4 alkyl (meth)acrylate (c 1 )/c 2 )) weight ratio of greater than 4.
- said c 1 )/c 2 ) weight ratio ranges from 4.5 to 19.
- said c 1 )/c 2 ) weight ratio ranges from 5 to 15 and more preferentially said c 1 )/c 2 ) weight ratio ranges from 5.5 to 12.
- the defined weight ratio makes it possible to obtain a polymer dispersion that is stable, notably after storage for seven days at room temperature.
- the stabilizer is chosen from: b) isobornyl acrylate homopolymers, c) statistical copolymers of isobornyl acrylate/methyl acrylate, statistical copolymers of isobornyl acrylate/ethyl acrylate, and statistical copolymers of isobornyl acrylate/methyl acrylate/ethyl acrylate in the weight ratio described previously.
- the stabilizing polymer ii) preferably has a number-average molecular weight ranging from 10000 to 400000, preferably ranging from 20000 to 200000 g/mol.
- the stabilizer ii) is in contact with the surface of the polymer particles i) and thus makes it possible to stabilize these particles at the surface in order to keep these particles in dispersion in the medium of the dispersion (A).
- the stabilizer(s) ii) is (are) chosen from c) the copolymers of: c 1 ) (C 3 -C 12 )cycloalkyl (C 1 -C 6 )(alkyl)acrylate; and c 2 ) (C 1 -C 4 )alkyl (C 1 -C 4 )(alkyl)acrylate; with 80% to 95% by weight of ingredient c 1 ), notably of isobornyl (meth)acrylate, and from 5% to 20% by weight of ingredient c 2 ), notably methyl acrylate and ethyl acrylate, relative to the total weight of the stabilizer.
- the stabilizer(s) ii) comprises (comprise) from 85% to 94% by weight, more particularly 87% to 93% by weight of ingredient c 1 ), notably of isobornyl (meth)acrylate, and from 10% to 20% by weight of ingredient c 2 ), notably methyl acrylate and/or ethyl acrylate, relative to the total weight of the polymer.
- the sum of ii) stabilizer(s) + i) polymer particle(s) present in the dispersion (A) comprises from 5% to 60%, in particular comprises from 10% to 40% by weight of polymers b) or c) and from 60% to 90%, in particular from 61% to 89% by weight of polymers a), relative to the total weight of the sum of ii) stabilizer(s) + i) polymer particle(s).
- the sum of ii) stabilizer(s) + i) polymer particle(s) present in the dispersion comprises from 15% to 30% by weight of polymers b) or c) and from 70% to 85% by weight of polymers a), relative to the total weight of the sum of ii) stabilizer(s) + i) polymer particle(s).
- the stabilizer(s) ii) and the particle(s) i) have a number- average molecular weight (Mn) of between 1000 and 1000000 g/mol, notably between 5000 and 500000 g/mol and even better still between 10000 and 300 000 g/mol.
- the dispersion (A) according to the invention is finally formed from polymeric particles of relatively large diameter, i.e. preferably greater than 100 nm, and leads to glossy, film-forming deposits which are resistant to fatty substances at room temperature (25°C), which are advantageous notably for makeup applications.
- the final particle size is greater than 100 nm.
- polymeric particles have a number-average size ranging from 100 nm to 600 nm, more particularly ranging from 150 nm to 500 nm and even more particularly ranging from 160 nm to 400 nm.
- the average particle size is determined via standard methods known to those skilled in the art.
- a Malvern brand NanoZS model laser particle size analyser (which is particularly suitable for submicron dispersions) makes it possible to measure the size distribution of these samples.
- the operating principle of this type of machine is based on dynamic light scattering (DLS), also known as quasi-elastic light scattering (QELS) or photon correlation spectroscopy (PCS).
- DLS dynamic light scattering
- QELS quasi-elastic light scattering
- PCS photon correlation spectroscopy
- the results may also be expressed in the form of statistical data such as D10; D50 (median), D90 and the mode.
- Other particle size techniques make it possible to obtain this type of information, such as analysis of the individual tracking of particles (Nanoparticle Tracking Analysis, NTA), laser scattering (LS), acoustic extinction spectroscopy (AES) spatial-filter Doppler velocimetry or image analysis.
- NTA Nanoparticle Tracking Analysis
- LS laser scattering
- AES acoustic extinction spectroscopy
- Doppler velocimetry or image analysis.
- the hydrocarbon-based oil(s) iii) [0080]
- the oily medium of the polymer dispersion comprises at least one hydrocarbon-based oil iii).
- the hydrocarbon-based oil is an oil that is liquid at room temperature (25°C) and at atmospheric pressure.
- hydrocarbon-based oil means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
- the hydrocarbon-based oil may be chosen from: - hydrocarbon-based oils having from 8 to 14 carbon atoms, and especially: - branched C 8 -C 14 alkanes, for instance C 8 -C 14 isoalkanes of petroleum origin (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6- pentamethylheptane), isodecane and, for example, the oils sold under the trade names Isopar or Permethyl, - linear alkanes, for instance n-dodecane (C 12 ) and n-tetradecane (C 14 ) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, the mixtures of n-undecane (C 11 ) and of n-tridecane (C 13 ) obtained in Examples 1 and 2 of application WO 2008/155059 from the company
- the hydrocarbon-based oil(s) of the invention is (are) formed solely of carbon and hydrogen atoms.
- the oily dispersion comprises at least one hydrocarbon-based oil iii) formed solely of carbon and hydrogen atoms, preferably chosen from: - linear or branched C 8 -C 30 , in particular C 10 -C 20 and more particularly C 10 -C 16 alkanes, which are volatile or non-volatile, preferably volatile; - non-aromatic cyclic C 5 -C 12 alkanes, which are volatile or non-volatile, preferably volatile; and - mixtures thereof.
- the hydrocarbon-based oil(s) is (are) preferably chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, in particular containing from 10 to 14 carbon atoms, which are preferably volatile.
- branched C 8 -C 16 and notably C 10 -C 14 alkanes that are suitable for use as liquid hydrocarbon-based fatty substances iii) in the dispersion of the invention, mention may be made of: - isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane and, for example, the oils sold under the Isopar or Permethyl trade names, - linear alkanes, for instance n-dodecane (C 12 ) and n-tetradecane (C 14 ) sold by Sasol under the references, respectively, Parafol 12-97 and Parafol 14-97,
- the liquid hydrocarbon-based oil(s) iii) of the invention is (are) formed solely of carbon and hydrogen atoms, more particularly of isododecane.
- the hydrocarbon-based oil(s) is (are) a mixture of non-volatile oil and volatile oil; preferably, the mixture comprises isododecane as volatile oil.
- the non-volatile oil is a phenyl silicone oil, preferably chosen from pentaphenyl silicone oils.
- the liquid hydrocarbon-based oil(s) iii) is (are) present in the dispersion of the invention in an amount of between 15% and 80% by weight, more preferentially between 20% and 60% by weight, relative to the total weight of said oily dispersion.
- the weight ratio of the sum of the ingredients [i) + ii)] / iii) is less than or equal to 1, more particularly the [i) + ii)] / iii) weight ratio is between 0.5 and 1.
- the polymer particles i) of the dispersion preferably have an average size, notably a number-average size, ranging from 50 to 500 nm, notably ranging from 75 to 400 nm and better still ranging from 100 to 250 nm.
- the dispersion according to the invention may be prepared in the following manner, which is given as an example.
- Non-volatile oils [0093] According to a specific form of the invention, the composition according to the invention comprises at least one non-volatile oil.
- oil is understood to mean a water-immiscible non-aqueous compound which is liquid at ambient temperature (25°C) and atmospheric pressure (760 mmHg).
- non-volatile oil is understood to mean an oil which remains on the keratin fibre, at room temperature and atmospheric pressure, for at least several hours and which has in particular a vapour pressure of less than 10 -3 mmHg (0.13 Pa).
- oils can be hydrocarbon-based oils, silicone oils or mixtures thereof.
- hydrocarbon-based oil is intended to mean an oil mainly containing hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur or phosphorus atoms.
- sicone oil is understood to mean an oil comprising at least one silicon atom, and in particular at least one Si-O group.
- Non-volatile hydrocarbon-based oils that may in particular be mentioned include: - hydrocarbon-based oils of plant origin, such as fatty acid triesters of glycerol, the fatty acids of which may have chain lengths ranging from C 4 to C 24 , these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably wheatgerm oil, sunflower oil, grapeseed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, red kuri squash oil, pumpkin oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil or musk rose oil; or else caprylic/capric acid trig
- the non-volatile silicone oils that may be used in the composition according to the invention may be non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups, that are pendent and/or at the end of a silicone chain, the groups each containing from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates.
- PDMSs non-volatile polydimethylsiloxanes
- polydimethylsiloxanes comprising alkyl or alkoxy groups, that are pendent and/or at the end of a silicone chain, the groups each containing from 2 to 24 carbon atoms
- the non-volatile oil or oils are present in the composition in a total concentration of less than 10.0% by weight, relative to the total weight of the composition.
- Method for preparing the dispersion may be prepared in the following manner: - The polymerization is performed in dispersion in non-aqueous medium, i.e. by precipitation of the polymer being formed, with protection of the formed particles with one or more stabilizers ii), preferably only one type of stabilizer ii) chosen from b) and c) as defined previously.
- the stabilizing polymer (or stabilizer ii)) is prepared by mixing the constituent monomer(s) of the stabilizing polymer b) or c) with iv) a free-radical initiator, in a solvent known as the synthesis solvent, and by polymerizing these monomers; and then -
- the constituent monomers of the polymer of the particles i) are added to the stabilizing polymer ii) formed in the preceding step and polymerization of these added monomers is performed in the presence of the free-radical initiator.
- water and the sum of ingredients i) + ii) are stirred in the reactor before removing the dispersion.
- the polymerization may be performed in an organic solvent (synthesis solvent), followed by adding the non-volatile hydrocarbon- based oil (which should be miscible with said synthesis solvent) and selectively distilling off the synthesis solvent.
- synthesis solvent may be constituted of hydrocarbon-based oil iii) combined with an additional solvent notably chosen from linear or branched hydrocarbon-based aliphatic-chain esters containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate.
- step 1 when the synthesis solvent is a mixture, the additional solvent including the hydrocarbon-based aliphatic-chain esters as defined previously is removed via a method that is conventional to those skilled in the art, such as distillation.
- the polymers of the particles i) are found in the hydrocarbon-based oil iii).
- a synthesis solvent which is such that the monomers of the polymeric stabilizer(s) ii) and the free-radical initiator iv) are soluble therein, and the polymer particles i) obtained are insoluble therein, so that they precipitate therein during their formation, is thus chosen.
- the synthesis solvent chosen is one which is organic and volatile, preferably chosen from volatile hydrocarbon-based oils iii), notably alkanes such as heptane, cyclohexane or isododecane, preferably isododecane.
- the non-aqueous medium is a volatile hydrocarbon-based oil iii
- the polymerization may be performed directly in said oil, which thus also acts as synthesis solvent.
- the monomers should also be soluble therein, as should the free-radical initiator, and the polymer of the particles i) which is obtained should be insoluble therein.
- the monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of 15% to 45% by weight.
- the total amount of the monomers may be present in the solvent before the start of the reaction, or a portion of the monomers may be added gradually as the polymerization reaction proceeds.
- the polymerization is preferably performed in the presence iv) of one or more free-radical initiators which may be any initiator known to those skilled in the art for radical polymerization, such as peroxide or azo initiators, redox couples and photochemical initiators.
- - peroxide in particular chosen from tert-butyl peroxy-2-ethylhexanoate: Trigonox 21S; 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane: Trigonox 141; tert-butyl peroxypivalate: Trigonox 25C75 from AkzoNobel; or - azo, in particular chosen from AIBN: azobisisobutyronitrile; V50: 2,2'-azobis(2- amidinopropane) dihydrochloride.
- the polymerization is preferably performed at a temperature ranging from 70 to 110°C and at atmospheric pressure.
- the polymer particles i) are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer ii).
- the stabilization may be performed by any known means, and in particular by direct addition of the stabilizer ii), during the polymerization.
- the stabilizer ii) is preferably also present in the mixture before polymerization of the monomers of the polymer of the particles i). However, it is also possible to add it continuously, notably when the monomers of the particles i) are also added continuously.
- the dispersion of polymer particles i) advantageously comprises from 30% to 65% by weight of solids relative to the total weight of said dispersion and preferably from 40% to 60% by weight relative to the total weight of said dispersion.
- the composition according to the invention preferably comprises a solids (or active material) content of polymers of particle i) + dispersing polymers ii) ranging from 10% to 80% by weight, relative to the total weight of the composition, preferably ranging from 20% to 60% by weight, notably 30% to 50% by weight, relative to the total weight of the composition.
- the dispersion of the invention does not comprise more than 3% by weight of surfactants relative to the total weight of the dispersion, preferentially not more than 2% by weight of surfactants relative to the total weight of the dispersion, more particularly not more than 1% by weight of surfactants relative to the total weight of the dispersion; even more preferentially, the composition does not comprise more than 0.5% by weight of surfactants relative to the total weight of the dispersion, and better still the mixture does not comprise any surfactant.
- the statistical stabilizing polymer ii) is prepared in a first step.
- This stabilizing polymer is soluble in an organic solvent of alkane type, such as isododecane.
- the polymer particles i) are synthesized in the presence of the stabilizing polymer ii).
- a solution of stabilizing polymer ii) in the hydrocarbon- based oil(s) iii) is prepared for the final dispersion, and the polymerization of the monomers which form the core of the particle is performed in the presence of this stabilizer ii).
- the stabilizing polymer ii) may be prepared by radical polymerization optionally in the presence of a polymerization initiator iv) as defined previously.
- the monomers which form the core of the particle i) may be polymerized in the presence of said stabilizing polymer ii).
- This second step may be a conventional radical polymerization.
- water or an aqueous composition is added, preferably with stirring.
- the dispersions are prepared in the presence of one or more hydrocarbon-based oils iii), preferably in an organic solvent, in particular of alkane type such as isododecane, according to an industrially feasible process.
- the dispersions according to the invention are thus finally formed from polymer particles, of relatively large diameter (preferably greater than 100 nm), and give glossy film-forming deposits that are resistant to fatty substances at the observation temperature (25°C).
- the oily dispersion may comprise a plasticizer chosen from tri-n-butyl citrate, tripropylene glycol monomethyl ether (INCI name: PPG-3 Methyl Ether) and trimethyl pentaphenyl trisiloxane (sold under the name Dow Corning PH-1555 HRI Cosmetic Fluid by the company Dow Corning).
- a plasticizer chosen from tri-n-butyl citrate, tripropylene glycol monomethyl ether (INCI name: PPG-3 Methyl Ether) and trimethyl pentaphenyl trisiloxane (sold under the name Dow Corning PH-1555 HRI Cosmetic Fluid by the company Dow Corning).
- the plasticizer is preferably present in the oily dispersion in a content ranging from 5% to 50% by weight, relative to the total weight of the polymer of the particles.
- a dispersion in iii notably isododecane, of surface-stabilized polymer particles i) chosen from: - a dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (24.5/62.8/12.7) copolymer particles stabilized by an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the oily dispersion containing in total (stabilizer + particles) 10% of acrylic acid, 20% of methyl acrylate, 50% of ethyl acrylate and 20% of isobornyl acrylate; - a dispersion in is
- a dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (11.7/75.6/12.7) copolymer particles stabilized by an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the oily dispersion containing in total (stabilizer ii) + particles i)) 10% of acrylic acid, 10% of methyl acrylate, 60% of ethyl acrylate and 20% of isobornyl acrylate.
- the amount of oily dispersion of particles i) in the composition of the invention preferably varies from 20% to 40% by weight, more preferentially from 25% to 35% by weight relative to the total weight of the composition.
- Water [00133]
- the composition according to the invention preferably comprises an amount of water greater than or equal to 2% by weight and less than 50% by weight relative to the total weight of the composition, more preferentially the amount of water in the composition is between 5% and 49% by weight relative to the total weight of the composition, more particularly between 10% and 47% by weight, between 15% and 48% by weight, preferentially between 18% and 45%, more preferentially still between 20% and 40% by weight, relative to the total weight of the composition.
- compositions according to the invention comprise at least one aqueous dispersion of colloidal silica particles.
- colloidal particles is understood to mean particles having a number-average diameter of between 0.1 and 100 nm, preferably between 3 and 30 nm, better still between 10 and 15 nm.
- colloidal particles retain the abovementioned diameters in the composition containing them, without aggregating, and do not therefore have thickening properties in the sense that at a concentration greater than or equal to 15% by weight in water, the colloidal particles have a viscosity of less than 0.05 Pa.s for a shear rate equal to 10-1 s, the viscosity being measured at 25°C using a Haake RheoStress® RS150 rheometer in cone-plate configuration, the cone having a diameter of 60 mm and an angle of 2°.
- This dispersion of colloidal particles may be prepared according to the “sol-gel” process well known to those skilled in the art, from salts or alkoxides of the corresponding metals dissolved in a solvent, such as an alcohol. A hydrolysis reaction is then carried out to form an amorphous precipitate. This is then dispersed in water with an acid or a base depending on the desired pH, which leads to peptization of the precipitate and to crystallization. In this way a crystalline oxide dispersed in water is formed.
- Such colloidal aqueous suspensions may for example be prepared according to the processes described in J. Collo ⁇ d Interface Sci., 26, p.62-69, 1968 for SiO 2 , Appli.
- the precursor is hydrolysed or fluorinated then polymerized until a finished product is obtained, which is insoluble in the chosen solvent, nucleated and referred to as a colloidal suspension.
- the hydrolysis must be rigorously controlled given the very hydrophilic nature of these organometallic derivatives.
- the colloidal particles may as a variant be constituted of a mixed oxide, in particular of a silica-alumina composite filler.
- the term “particles of silica-alumina composite filler” means particles constituted of silicon oxide and the surface of which has been chemically modified so as to replace at least some of the silicon atoms with aluminium atoms forming at most one monomolecular layer of aluminium.
- They may be prepared, in particular, as described in patent US- 2,892,797, by mixing a silica sol with a sodium aluminate.
- the aqueous dispersions of colloidal silica particles according to the present invention preferably contain silica particles in concentrations ranging from 10% to 50% by weight, preferably from 25% to 40% by weight relative to the total weight of the aqueous dispersion.
- the colloidal silica particles according to the invention are preferably anionic and amorphous silica particles.
- anionic particles is understood to denote silica particles bearing at the surface anionic charges, in particular neutralized with one or more cations.
- Such particles are obtained, for example, by reacting silanol groups at the surface of silica particles with alkaline agents such as sodium hydroxide (NaOH) or ammonium hydroxide (NH 4 OH).
- alkaline agents such as sodium hydroxide (NaOH) or ammonium hydroxide (NH 4 OH).
- NaOH sodium hydroxide
- NH 4 OH ammonium hydroxide
- These particles are preferably spherical or approximately spherical.
- these particles are non-porous.
- the anionic colloidal silica particles according to the invention may be monodisperse or polydisperse.
- the term “monodisperse” means that the sizes of said particles have a narrow distribution.
- the term “polydisperse” means that the sizes of the particles have a broader distribution.
- the anionic colloidal silica particles according to the invention are monodisperse.
- the mean diameter of the anionic colloidal silica particles is generally between 3 and 100 nm, preferably between 3 and 50 nm and more preferentially between 5 and 10 nm.
- This mean diameter may be measured using a particle size distribution analyser of the Coulter N4 PLUS® type manufactured by Beckman Coulter Inc.
- the anionic colloidal silica particles are monodisperse, their mean diameter is preferably between 3 and 50 nm, in particular between 5 and 25 nm and more preferentially between 5 and 10 nm.
- the anionic colloidal silica particles are polydisperse, their mean diameter is preferably between 5 and 70 nm, in particular between 10 and 50 nm.
- the specific surface area of the anionic colloidal silica particles generally ranges from 50 to 500 m 2 /g SiO 2 .
- the specific surface area 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 (Annex D).
- the BET specific surface area corresponds to the total specific surface area of the particles under consideration.
- the sizes of the 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.
- the specific surface area of the anionic colloidal silica particles generally ranges from 100 to 500 m 2 /g SiO 2 , in particular from 130 to 450 m 2 /g SiO 2 , more preferentially from 250 to 400 m 2 /g SiO 2 , and more particularly still from 320 to 370 m 2 /g SiO 2 , in particular when they are monodisperse.
- the anionic colloidal silica particles are polydisperse, their specific surface area generally ranges from 50 to 300 m 2 /g SiO 2 , in particular from 70 to 280 m 2 /g SiO 2 .
- the anionic colloidal silica particles are silica particles neutralized by counterions of cationic nature so as to ensure the electroneutrality of the particles.
- These counterions may notably be chosen from sodium (Na + ) and ammonium ( NH 4 +).
- the cationic counterions are sodium ions (Na + ).
- the aqueous dispersions of anionic colloidal silica particles according to the invention have a pH preferably of from 8 to 10.
- dispersions of anionic colloidal silica particles mention may notably be made of those sold under the name Ludox ® by the company Grace.
- the dispersions of anionic silica particles denote the particles sold by the company Grace under the names Ludox ® AM X6021, Ludox ® FM, Ludox ® SM, Ludox ® HS-30, Ludox ® HS-40, Ludox ® LS, Ludox ® TM-40, Ludox ® TM-50, Ludox ® PX-30, Ludox ® PT-40, Ludox ® PW-50, Ludox ® SM-AS, Ludox ® AS-30 and Ludox ® AS-40.
- the particles are monodisperse, they are preferably chosen from those sold under the names Ludox ® AM X6021, Ludox ® FM, Ludox ® SM, Ludox ® HS-30, Ludox ® HS-40, Ludox ® LS, Ludox ® TM-40, Ludox ® TM-50, Ludox ® SM-AS, Ludox ® AS-30 and Ludox ® AS-40.
- the anionic colloidal silica particles denote the Ludox ® SM particles sold by the company Grace.
- the particles are polydisperse, they are preferably chosen from Ludox ® PX-30, Ludox ® PT-40 and Ludox ® PW-50 sold by the company Grace.
- aqueous dispersion of Ludox AM X6021® anionic colloidal silica particles containing 29-31% by weight of silica particles relative to the total weight of the dispersion. It also contains alumina in a content of the order of 0.2% by weight.
- the silica particles have a mean diameter of the order of 12 nm and a specific surface area of 198 ⁇ 258 m 2 /g SiO 2 .
- the aqueous dispersion is alkaline and has a pH at 25°C of from 8.5 to 9.3.
- aqueous dispersions of anionic colloidal silica particles that can be used according to the invention
- the dispersions of anionic silica particles denote the particles sold by the company Grace under the names Klebesol ® 40PA50, Klebesol ® 30N50, Klebesol ® 30N50PHN, Klebesol ® 30H50, Klebesol ® 1501-50, Klebesol ® 1508-50, Klebesol ® 1498-50.
- TEOS tetraethoxysilane
- SiO-C 2 H 5 organometallic precursors SiO-C 2 H 5 according to the Stöber synthesis method [Stöber et al. (1968), Green et al. (2003)].
- the synthesis of this silica is catalysed by the presence of aqueous ammonia in solution. It is obtained in the form of an ammoniacal aqueous dispersion of spherical monodisperse particles, with a mean diameter of the order of 50 nm and a density of the order of 2400 kg/m 3 .
- Their pH at 25°C typically varies between 10 and 11.
- the colloidal silica particles have a mean size of the order of 50 nm.
- the aqueous dispersion is alkaline and has a pH at 25°C of 10.9.
- the amount of aqueous dispersion of colloidal silica particles in the composition of the invention preferably varies from 5% to 20% by weight, more preferentially from 5% to 15% by weight relative to the total weight of the composition.
- the weight ratio of the oily dispersion of surface-stabilized polymer particles to the aqueous dispersion of colloidal silica particles varies from 2 to 6, more preferentially from 2 to 5.
- Waxes [00174]
- the composition according to the invention may in addition comprise at least one wax in an amount of less than 5.0% by weight, or less than 2.0% relative to the total weight of the composition. This wax makes it possible to obtain thick, charging textures.
- the term “wax” means a deformable or undeformable lipophilic compound, which is solid at room temperature (25°C), with a reversible solid/liquid change of state, having a melting point of greater than or equal to 40°C, which may be up to 120°C.
- the waxes that are suitable for use in the invention may have a melting point of greater than or equal to 45°C and in particular greater than or equal to 55°C.
- the term “lipophilic compound” refers to a compound having an acid number and a hydroxyl number of less than 150 mg KOH/g.
- the melting point corresponds to the temperature of the most endothermic peak observed on thermal analysis (DSC) as described in the standard ISO 11357-3; 1999.
- the melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2920 ® by the company TA Instruments.
- the measuring protocol is as follows: [00179] A sample of 5 mg of wax placed in a crucible is subjected to a first temperature rise ranging from -20°C to 100°C, at a heating rate of 10°C/minute, it is then cooled from 100°C to -20°C at a cooling rate of 10°C/minute and is finally subjected to a second temperature rise ranging from -20°C to 100°C at a heating rate of 5°C/minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the sample of wax is measured as a function of the temperature.
- the melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.
- the waxes may be hydrocarbon-based waxes, silicone waxes and/or fluoro waxes, and may be of plant, mineral, animal and/or synthetic origin.
- Use may in particular be made, as wax, of hydrocarbon waxes, such as beeswax, lanolin wax; rice wax, carnauba wax, candelilla wax, ouricury wax, Japan wax, berry wax, shellac wax and sumac wax; montan wax.
- waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C 8 -C 32 fatty chains.
- Use may also be made of the wax obtained by hydrogenation of olive oil esterified with stearyl alcohol, sold under the name Phytowax Olive 18L57 ® , or the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, sold under the names Phytowax Ricin 16L64 ® and 22L73 ® by the company Sophim.
- Such waxes are described in patent application FR-A-2792190.
- Use may also be made of a C 20 -C 40 alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture, in particular a C 20 - C 40 alkyl 12-(12'-hydroxystearyloxy)stearate of formula (I) [Chem 4] in which n is an integer ranging from 18 to 38, or a mixture of compounds of formula (I).
- a tacky wax is notably sold under the names Kester Wax K 82 P ® and Kester Wax K 80 P ® by the company Koster Keunen.
- Mention may be made of microcrystalline waxes, paraffins and ozokerite, polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers and also esters thereof; silicone waxes and fluoro waxes.
- Mention may be made of the linear fatty acid monoesters of formula (1) below: [Chem 5] R 3 -O-R 4 (1) in which R 3 and R 4 are linear and saturated and have, independently of one another, a number of carbon atoms greater than or equal to 20, with R 3 representing an acyl radical, and R 4 representing an alkyl radical.
- the fatty acid monoester according to the invention is chosen from arachidyl arachidate and behenyl behenate and more particularly behenyl behenate.
- a wax chosen from beeswax, carnauba wax, cetyl alcohol, paraffins, behenyl behenate and mixtures thereof.
- Colorant [00188]
- the composition according to the invention additionally comprises at least one colorant, in particular chosen from pulverulent colorants, water-soluble dyes and mixtures thereof.
- the pulverulent colorants can be chosen from pigments and pearlescent agents.
- the pigments can be white or coloured, inorganic and/or organic, and coated or uncoated.
- mineral pigments that may be mentioned are titanium dioxide, optionally surface-treated, zirconium oxide, zinc oxide or cerium oxide, and also iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Mention may be made, among the organic pigments, of carbon black, pigments of D & C type, and lakes based on cochineal carmine and on barium, strontium, calcium or aluminium.
- the pearlescent agents may be chosen from white pearlescent pigments such as mica coated with titanium or with bismuth oxychloride, coloured pearlescent pigments such as titanium mica with iron oxides, titanium mica especially with ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also pearlescent pigments based on bismuth oxychloride.
- the composition according to the invention comprises a pulverulent colorant, preferably of pigment type, in particular metal oxides, especially titanium dioxides, iron oxides, and mixtures thereof; and more particularly iron oxides.
- the water-soluble dyes are, for example, beetroot juice and caramel.
- the colorant(s) is (are) present in the composition (B) in a total content ranging from 2.0% to 25.0% by weight, preferably from 3.0% to 20.0% by weight, more particularly from 4.0% to 15.0% by weight, relative to the total weight of the composition.
- Non-volatile oils [00196] According to a specific form of the invention, the composition according to the invention comprises at least one non-volatile oil such as those described above.
- Additives Mention may in particular be made, as cosmetic additives which can be used in the compositions according to the invention, of antioxidants; preservatives; fragrances; organic or inorganic fillers; thickeners and gelling agents; sequestrants; chelating agents; sunscreens; vitamins, such as vitamin C or ascorbic acid and its derivatives, such as 2-O-alpha-D-glucopyranosyl-L- ascorbic acid (INCI name: Ascorbyl Glucoside), vitamin B3 or niacinamide; vitamin B8, also called vitamin H: D-biotin, vitamin E and its derivatives, such as tocopherol acetate; provitamins such as panthenol also called provitamin B5 or dexpanthenol; moisturizing agents, such as polyols, for example 1,3-propanediol, glycerol, pentylene glycol, propylene glycol, ethylene glycol, 1,3-butylene glycol, di
- the composition is in the form of a makeup and/or care product for the skin, in particular of the face, area around the eyes, and cheeks, such as a foundation.
- the composition is in the form of a makeup and/or care product such as a lipstick.
- the composition is in the form of a makeup and/or care product for the eyelashes, such as a mascara or an eyeliner.
- Packaging and applicators [00203]
- the compositions according to the invention may each be packaged in a container delimiting at least one compartment that comprises said composition, said container being closed by a closing member.
- the container may be in any suitable form. It may notably be in the form of a bottle, a tube, a jar or a case.
- the closing member may be in the form of a removable stopper, a lid or a cover, notably of the type including a body fixed to the container and a cap articulated on the body.
- the container may be combined with an applicator, notably in the form of a brush including an arrangement of bristles maintained by a twisted wire.
- an applicator notably in the form of a brush including an arrangement of bristles maintained by a twisted wire.
- a twisted brush is described notably in patent US 4887622.
- It may also be in the form of a comb including a plurality of application members, obtained notably by moulding. Such combs are described, for example, in patent FR 2796 529.
- the applicator may be in the form of a fine brush, as described, for example, in patent FR 2722380.
- the applicator may be in the form of a block of foam or of elastomer.
- the applicator may be free (sponge) or securely fastened to a rod borne by the closing member, as described, for example, in patent US 5492426.
- the applicator may be securely fastened to the container, as described, for example, in patent FR 2761959.
- the product may be contained directly in the container, or indirectly.
- the closing member may be coupled to the container by screwing. Alternatively, the coupling between the closing member and the container occurs other than by screwing, in particular via a bayonet mechanism, by click-fastening or by gripping.
- the term “click-fastening” in particular means any system involving the crossing of a bead or cord of material by elastic deformation of a portion, notably of the closing member, followed by return to the elastically unconstrained position of said portion after the bead or cord has been crossed.
- the container may be at least partially made of thermoplastic material. Examples of thermoplastic materials that may be mentioned include polypropylene and polyethylene.
- the container may have rigid or deformable walls, notably in the form of a tube or a tube bottle.
- the container may comprise means intended to bring about or facilitate the dispensing of the composition.
- the container may have deformable walls so as to cause the composition to exit in response to excess pressure inside the container, which excess pressure is brought about by the elastic (or non-elastic) squeezing of the walls of the container.
- the container may be equipped with a drainer positioned in the vicinity of the opening of the container. Such a drainer makes it possible to wipe the applicator and possibly the rod to which it may be securely fastened. Such a drainer is described, for example, in patent FR 2792618.
- the term “including a” should be understood as being synonymous with “including at least one”, unless otherwise specified.
- Example 1 of preparing an oily dispersion of polymer A dispersion of polymer particles i) in isododecane was prepared using: Step 1: 315.2 g of isobornyl acrylate, 12.5 g of methyl acrylate, 12.5 g of ethyl acrylate, 3.4 g of Trigonox 21, 540 g of isododecane, 360 g of ethyl acetate.
- Step 2 303 g of methyl acrylate, 776 g of ethyl acrylate, 157 g of acrylic acid, 11 g of Trigonox 21S, 741.6 g of isododecane and 494.4 g of ethyl acetate.
- the oily dispersion contains in total (particles i) + stabilizer ii)) 10% acrylic acid, 20% methyl acrylate, 50% ethyl acrylate and 20% isobornyl acrylate.
- Example 2 of preparing an oily dispersion of polymer [00218] A dispersion of polymer particles i) in isododecane was prepared according to the preparation method of Example 1, using: Step 1: 315.2 g of isobornyl acrylate, 12.5 g of methyl acrylate, 12.5 g of ethyl acrylate, 3.4 g of Trigonox 21, 540 g of isododecane, 360 g of ethyl acetate; followed by addition, after reaction, of 540 g of isododecane and 360 g of ethyl acetate.
- Step 2 145 g of methyl acrylate, 934 g of ethyl acrylate, 157 g of acrylic acid, 12.36 g of Trigonox 21S, 741.6 g of isododecane and 494.4 g of ethyl acetate.
- 3 litres of an isododecane/ethyl acetate mixture 60/40 weight/weight were added and total evaporation of the ethyl acetate and partial evaporation of the isododecane was performed to obtain a solids content of 44% by weight.
- the oily dispersion contains in total (particles i) + stabilizer ii)) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate.
- Example 3 of preparing an oily dispersion of polymer [00220] A dispersion of polymer particles i) in isododecane was prepared according to the preparation method of Example 1, using: Step 1: 48 g of isobornyl acrylate, 2 g of methyl acrylate, 2 g of ethyl acrylate, 0.52 g of Trigonox 21, 57.6 g of isododecane, 38.4 g of ethyl acetate; followed by addition, after reaction, of 540 g of isododecane and 360 g of ethyl acetate.
- Step 2 98 g of methyl acrylate, 73 g of ethyl acrylate, 25 g of maleic anhydride, 1.96 g of Trigonox 21S, 50.4 g of isododecane and 33.60 g of ethyl acetate.
- 1 litre of an isododecane/ethyl acetate mixture 60/40 weight/weight was added and total evaporation of the ethyl acetate and partial evaporation of the isododecane was performed to obtain a solids content of 46.2% by weight.
- the oily dispersion contains in total (particles i) + stabilizer ii)) 10% maleic anhydride, 30% methyl acrylate, 40% ethyl acrylate and 20% isobornyl acrylate.
- compositions 1 and 2 were produced by simple mixing at room temperature (25°C).
- Composition 1 according to the invention is stable and homogeneous after 48 h at room temperature (25°C) unlike composition 2 outside the invention which is unstable: the silica particles settle.
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Abstract
The present application relates to the field of making up keratin materials, in particular the skin, eyelashes and eyebrows. It relates more particularly to a composition comprising, preferably in a cosmetically acceptable medium, at least: - one oily dispersion which comprises: i) one or more particle(s) comprising: a) one or more ethylenic copolymers of a1) (C1-C4)alkyl (C1-C4)(alkyl)acrylate, and of a2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a2) is a (C1-C4)(alkyl)acrylic acid; and ii) one or more polymeric stabilizers chosen from: b) polymers of (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate monomers; and c) copolymers of c1) (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate and of c2) (C1-C4)alkyl (C1-C4)(alkyl)acrylate; and iii) one or more hydrocarbon-based oils; and - an aqueous dispersion of colloidal silica particles. The present invention also relates to a method for making up and/or caring for keratin materials consisting in applying to the surface of said materials at least one composition as defined previously.
Description
Description Title of the invention: Cosmetic composition comprising an oily dispersion of polymer particles and an aqueous dispersion of colloidal silica particles [0001] The present application relates to the field of making up keratin materials, in particular the skin, eyelashes and eyebrows. It relates more particularly to a composition comprising, preferably in a physiologically acceptable medium, at least: - one oily dispersion which comprises: i) one or more particles comprising: a) one or more ethylenic copolymers of a1) (C1-C4)alkyl (C1-C4)(alkyl)acrylate, and of a2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a2) is a (C1- C4)(alkyl)acrylic acid; and ii) one or more polymeric stabilizers chosen from: b) polymers of (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate monomers; and c) copolymers of c1) (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate and of c2) (C1- C4)alkyl (C1-C4)(alkyl)acrylate; and iii) one or more hydrocarbon-based oils; and - an aqueous dispersion of colloidal silica particles. [0002] The present invention also relates to a method for making up and/or caring for keratin materials consisting in applying to the surface of said materials at least one composition as defined previously. [0003] Cosmetic makeup compositions are commonly used to give keratin materials such as the skin, eyelashes and eyebrows an attractive colour, but also to enhance the beauty of uneven skin, by making it possible to hide marks and dyschromias, and to reduce the visibility of relief imperfections such as pores and wrinkles. [0004] They may also be used to correct and harmonize the appearance of the eyelashes or eyebrows. Many formulations have been developed to date. For several years, consumers have been searching for compositions which provide a good wear property of the makeup effect over time, notably makeup which is resistant, in everyday life, to the test of showering or bathing in the presence of
hot water and detergent surfactants, to sweat and to sebum, in order to be able to avoid having to re-apply the composition too often. [0005] Several semipermanent makeup techniques exist, such as tattooing and in particular the techniques of microblading and microshading which consist in inserting, using a needle, a coloured pigment under the surface layers of the skin. The application is painful, irreversible and very expensive unlike standard makeup products which are very comfortable but do not generally enable a long wear property beyond one day. [0006] Aqueous makeup formulations containing film-forming polymers in dispersion in water such as latices have good resistance to sebum but do not withstand the test of showering or bathing (hot water and detergent surfactants). [0007] From applications FR3030260 and EP3233193 anhydrous mascara formulations and eyeliner formulations are known that contain a dispersion in isododecane of particles of at least one polymer that is surface-stabilized by a stabilizer, the polymer of the particles being a polymer of C1-C4 alkyl (meth)acrylate and at least one ethylenically unsaturated acid monomer or a salt thereof, or the anhydride thereof or a salt thereof; the stabilizer being an isobornyl (meth)acrylate polymer chosen from isobornyl (meth)acrylate homopolymer and statistical copolymers of isobornyl (meth)acrylate and of C1-C4 alkyl (meth)acrylate present in an isobornyl (meth)acrylate/C1-C4 alkyl (meth)acrylate weight ratio of greater than 4 and which may contain waxes. However, these compositions in the presence of waxes have a tendency to be unstable and heterogeneous due to a recrystallization phenomenon of the waxes. They are not entirely satisfactory either for coverage in order to be able to effectively conceal or correct imperfections. They are moreover sensitive to sebum and in contact therewith have a tendency to produce a sticky and tacky deposit. [0008] There is therefore a need to find new semipermanent compositions for making up and/or caring for keratin materials without the drawbacks of the techniques and formulations known from the prior art. It is sought to obtain formulations that are stable, comfortable and have a long wear property on keratin materials and in particular that are resistant to hot water and to surfactants and to sebum.
[0009] Unexpectedly, the applicant has found in the course of its research that it is possible to achieve this objective with a composition comprising, preferably in a cosmetically acceptable medium, at least: - one oily dispersion which comprises: i) one or more particles comprising: a) one or more ethylenic copolymers of a1) (C1-C4)alkyl (C1-C4)(alkyl)acrylate, and of a2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a2) is a (C1- C4)(alkyl)acrylic acid; and ii) one or more polymeric stabilizers chosen from: b) polymers of (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate monomers; and c) copolymers of c1) (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate and of c2) (C1- C4)alkyl (C1-C4)(alkyl)acrylate; and iii) one or more hydrocarbon-based oils; and - an aqueous dispersion of colloidal silica particles. [0010] This discovery forms the basis of the invention. Subjects of the invention [0011] Thus, a first subject of the present invention is a composition comprising, preferably in a cosmetically acceptable medium, at least: - one oily dispersion which comprises: i) one or more particles comprising: a) one or more ethylenic copolymers of a1) (C1-C4)alkyl (C1-C4)(alkyl)acrylate, and of a2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a2) is a (C1- C4)(alkyl)acrylic acid; and ii) one or more polymeric stabilizers chosen from: b) polymers of (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate monomers; and c) copolymers of c1) (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate and of c2) (C1- C4)alkyl (C1-C4)(alkyl)acrylate; and iii) one or more hydrocarbon-based oils; and - an aqueous dispersion of colloidal silica particles.
[0012] A second subject of the present invention is a method for making up and/or caring for keratin materials consisting in applying to the surface of said materials at least one composition as defined previously. Definitions [0013] In the context of the present invention, the term “keratin fibres” is understood to mean the skin, the eyelashes and the eyebrows. For the purposes of the present invention, this term “keratin fibres” also extends to synthetic false eyelashes. [0014] The term “physiologically acceptable” means compatible with the skin and its integuments, which has a pleasant colour, odour and feel, and which does not cause any unacceptable discomfort (stinging or tautness) liable to discourage the consumer from using this composition.
- an “alkyl” radical is a linear or branched saturated C1-C8, in particular C1-C6, preferably C1-C4 hydrocarbon-based group such as methyl, ethyl, n-propyl, isopropyl or i-propyl, n-butyl, isobutyl or i-butyl, and tert-butyl or t-butyl; - an “alkylene” radical is a linear or branched divalent saturated C1-C8, in particular C1-C6, preferably C1-C4 hydrocarbon-based group such as methylene, ethylene or propylene; - a “cycloalkyl” radical is a cyclic saturated hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 13 carbon atoms, preferably between 5 and 10 carbon atoms, and which may be substituted with one or more (C1-C4)alkyl groups such as methyl, for instance cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl; preferably, the cycloalkyl radical is an isobornyl group; - a “cyclic” radical is a cyclic saturated or unsaturated, aromatic or non-aromatic hydrocarbon-based group comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms, such as cyclohexyl or phenyl;
- an “aryl” radical is a monocyclic or fused or non-fused bicyclic, unsaturated cyclic aromatic radical comprising from 6 to 12 carbon atoms; preferably, the aryl group comprises 1 ring and contains 6 carbon atoms, such as phenyl; - an “aryloxy” radical is an aryl-oxy, i.e. aryl-O-, radical, with aryl as defined previously, preferably phenoxy; - an “aryl(C1-C4)alkoxy” radical is an aryl-(C1-C4)alkyl-O- radical, preferably benzoxy; - the term “insoluble monomer” thus means any monomer whose homopolymer or copolymer is not in soluble form, i.e. not fully dissolved at a concentration of greater than 5% by weight at room temperature (20°C) in said medium; - the term “ethylenic homopolymer” means a polymer derived from the polymerization of identical monomers; - the term “ethylenic copolymer” means a polymer derived from the polymerization of different monomers, in particular at least two different monomers. Preferably, the ethylenic copolymer of the invention is derived from two or three different monomers; - the term “ethylenic monomer” means an organic compound including one or more conjugated or non-conjugated unsaturations of >C=C< type, which is capable of polymerizing; - the term “soluble monomer” means any monomer whose homopolymer or copolymer, preferably homopolymer, is soluble to at least 5% by weight, at 20°C, in the hydrocarbon-based liquid fatty substance(s) iii) of the dispersion. The homopolymer is completely dissolved in the carbon-based liquid(s) iii), visually at 20°C, i.e. there is no visible sign of any deposit, or precipitate, or agglomerate, or insoluble sediment; - the term “fatty substance” means an organic compound that is immiscible in water at ordinary room temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably 1% and even more preferentially 0.1%). They bear in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance ethanol, ether, liquid petroleum jelly or decamethylcyclopentasiloxane. These fatty substances are neither polyoxyethylenated nor polyglycerolated. They are different from fatty
acids, since salified fatty acids constitute soaps that are generally soluble in aqueous media; - the term “liquid” fatty substance notably refers to a fatty substance that is liquid at 25°C and 1 atmosphere; preferably, said fatty substance has a viscosity of less than or equal to 7000 centipoises at 20°C; - the term “hydrocarbon-based” fatty substance means a fatty substance which comprises at least 50% by weight, notably from 50% to 100% by weight, for example from 60% to 99% by weight, or else from 65% to 95% by weight, or even from 70% to 90% by weight, relative to the total weight of said fatty substance, of carbon-based compound, having a global solubility parameter in the Hansen solubility space of less than or equal to 20 (MPa)1/2 , or a mixture of such compounds; - the term “oil” means a fatty substance that is liquid at room temperature (25°C) and at atmospheric pressure; - the term “hydrocarbon-based oil” means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain hydroxyl, ester, ether, carboxylic acid, amine and/or amide groups; - the term “volatile oil” means an oil (or non-aqueous medium) that can evaporate on contact with keratin materials, in particular the skin, in less than one hour, at room temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil, which is liquid at room temperature, notably having a non- zero vapour pressure, at room temperature and at atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40000 Pa (10-3 to 300 mmHg), preferably ranging from 1.3 Pa to 13000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg); - the term “non-volatile oil” means an oil with a vapour pressure of less than 0.13 Pa at room temperature and at atmospheric pressure. Oily dispersion of solid polymer particles [0015] The dispersions according to the invention are therefore constituted of particles, which are generally spherical, of at least one polymer i) which is surface stabilized with one or more stabilizers ii), in a non-aqueous medium. [0016] In order to obtain the dispersion, it is proposed to polymerize particular monomers that are capable of forming the polymeric core i) in the presence of a
polymeric statistical stabilizer ii) comprising in major amount a portion ii) that is soluble and in minor amount a portion ii) that is insoluble in the dispersion medium, i.e. in the hydrocarbon-based liquid fatty substance(s) iii) optionally containing iv) water. [0017] Preferably, said particles i) are not or are sparingly crosslinked. [0018] The polymer particles i) and the stabilizer(s) ii) are preferably in the hydrocarbon-based liquid fatty substance(s) iii) in an amount of between 2% and 40% by weight, in particular between 4% and 35% by weight of soluble monomer (the one forming the stabilizer(s) ii)) and between 60% and 98% by weight, in particular from 65% to 96% by weight of insoluble monomer (the one forming the particles i)). Polymer particles i) [0019] The particle(s) i) of the dispersion of the process of the invention is (are) constituted of one or more ethylenic copolymers derived from the polymerization a1) of at least one (C1-C4)alkyl (C1-C4)(alkyl)acrylate monomer and a2) of at least one ethylenic monomer comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a2) is a (C1-C4)(alkyl)acrylic acid. [0020] Preferably, the particle(s) i) is (are) constituted of an ethylenic polymeric core derived from copolymers a), as defined previously. [0021] The term “ethylenic copolymer” means a polymer resulting from the polymerization of two monomers: of (C1-C4)alkyl (C1-C4)(alkyl)acrylate monomer a1) and of ethylenic monomer a2) comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl, such as phenyl, groups. [0022] The term “ethylenic monomer” means a compound comprising at least one ethylenic unsaturation ‒(Ra)C=C(Rb)‒, ‒C(Ra)=C(Rb)‒Rc or >C=C(Ra)‒Rb, with Ra, Rb, and Rc, which may be identical or different, representing a hydrogen atom or a (C1-C4)alkyl group such as methyl, preferably hydrogen. [0023] The ethylenic compound may also be a cyclic compound, which is preferably 5- or 6-membered, and comprising an ethylenic unsaturation. [0024] An ethylenic monomer comprising “one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups” is understood to mean that the monomer is substituted on the one of the carbon atoms of the polymeric
monomer with one or more groups, preferably a single group, chosen from carboxyl ‒C(O)-OH, phosphoric acid ‒O-P(O)(OH)2 or ‒P(O)(OH)2, and sulfonic acid ‒O-S(O)2-OH or ‒S(O)2-OH, maleic anhydride, and aryl such as phenyl. [0025] According to one embodiment of the invention, the particle(s) i) comprises (comprise) a) ethylenic copolymers of a1) (C1-C4)alkyl (C1-C4)(alkyl)acrylate and of a2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl, such as benzyl, groups. [0026] More particularly, the ethylenic monomers a2) comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups are chosen from (1), (2), (3), and (4): (1) R1(R2)C=C(R3)-Acid with R1, R2 and R3 representing a hydrogen atom or a CO2H, H2PO4 or SO3H group, and Acid representing a carboxyl, phosphoric acid or sulfonic acid group, preferably carboxyl group, preferably (1) represents (5) H2C=C(R)- C(O)-O-H with R representing a hydrogen atom or a (C1-C4)alkyl group such as methyl; (2) H2C=C(R)-C(O)-N(R')-Alk-Acid with R and R', which may be identical or different, representing a hydrogen atom or a (C1-C4)alkyl group; Alk represents a (C1-C6)alkylene group optionally substituted with at least one group chosen from Acid as defined previously and hydroxyl; and Acid is as defined previously, preferably carboxyl or sulfonic acid; (3) Ar-(Ra)C=C(Rb)-Rc with Ra, Rb and Rc, which may be identical or different, representing a hydrogen atom or a (C1-C4)alkyl group, and Ar representing an aryl group, preferably benzyl, optionally substituted with at least one acid group CO2H, H2PO4 or SO3H, preferably substituted with a CO2H or SO3H group; (4) maleic anhydride of formula (4a) and itaconic anhydride of formula (4b): [Chem.3]
in which formulae (4a) and (4b): Ra, Rb and Rc, which may be identical or different, represent a hydrogen atom or a (C1-C4)alkyl group; preferably, Ra, Rb and Rc represent a hydrogen atom; Preferentially, the ethylenically unsaturated anhydride monomer of the invention is of formula (4a) and more preferentially is maleic anhydride; and more particularly a2) is chosen from (1) and (4), in particular (4). [0027] According to one particular variant of the invention, a2) is a (C1- C4)(alkyl)acrylic acid, more particularly b) is (are) copolymers of (C1-C4)alkyl (meth)acrylate and of (meth)acrylic acid. [0028] According to another variant of the invention, a2) is chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, acrylamidopropanesulfonic acid, acrylamidoglycolic acid, and salts thereof, more preferentially a2) represents maleic anhydride. [0029] The salts may be chosen from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminium, manganese or copper; ammonium salts of formula NH4+; quaternary ammonium salts; salts of organic amines, for instance salts of methylamine, diethylamine, trimethylamine, triethylamine, ethylamine, 2-hydroxyethylamine, bis(2-hydroxyethyl)amine or tris(2-hydroxyethyl)amine; lysine or arginine salts. According to one preferred embodiment of the invention, the (C1-C4)alkyl (C1- C4)(alkyl)acrylate monomer(s) a1) is (are) chosen from those of formula (I): [Chem 2]
in which formula (I): - R represents a hydrogen atom or a (C1-C4)alkyl group such as methyl, and
- R' represents a (C1-C4)alkyl group such as methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, preferably methyl, ethyl or i-butyl, preferably (I) represents a C1-C4 alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl acrylate and isobutyl methacrylate. [0030] According to a particular embodiment of the invention, the polymer constituting the particles i) is an ethylenic acrylate copolymer a) resulting from the polymerization: - a1) of at least one monomer of formula (I) as defined previously, preferably a C1- C4 alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl acrylate and isobutyl methacrylate; and - a2) of at least one monomer chosen from (1), (2), (3) and (4) as defined previously and preferentially of formula (II) and also the salts thereof: [Chem 3]
in which formula (II) R is as defined previously, in particular (II) represents acrylic acid. [0031] According to one preferred embodiment of the invention, the amount of a2) notably of compound (II) and in particular of acrylic acid is greater than 2.5% by weight relative to the total weight of the particle i), more particularly between 3% and 35% by weight relative to the weight of polymer of the particle i), even more particularly between 5% and 25% by weight and the polymer of the particles i), better still between 10% and 15% by weight and the polymer of the particles i). [0032] In particular a) is a copolymer resulting from the copolymerization a2) of acrylic acid with a1) one or more C1-C4 alkyl (meth)acrylate monomers, preferably at least two different C1-C4 alkyl (meth)acrylate monomers, in particular chosen from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and isobutyl (meth)acrylate. [0033] According to another preferred embodiment of the invention, the polymer constituting the particles i) is an ethylenic acrylate copolymer a) resulting from the polymerization: - of at least two different monomers: of formula (I) as defined previously, preferably a C1-C4 alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl (meth)acrylate; and
- of at least one monomer chosen from (1), (2), (3) and (4) as defined previously, preferably of formula (II) as defined previously. [0036] According to a particular embodiment of the invention, the polymer of the particles i) is a polymer derived from C1-C4 alkyl (meth)acrylate monomers a1). [0037] Advantageously, a linear or branched, preferably linear, C1-C4 alkyl acrylate, in particular (C1-C3)alkyl acrylate, monomer is used. Preferentially, a) is chosen from methyl acrylate and ethyl acrylate. [0038] The monomers a1) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl (meth)acrylate, more preferentially chosen from methyl (meth)acrylate and ethyl (meth)acrylate. [0039] According to another particular embodiment of the invention, the polymer constituting the particles i) is an acrylate copolymer a) resulting: a1) from at least one monomer of formula (I) as defined previously; and a2) from at least one ethylenically unsaturated anhydride monomer, notably of formula (4) as defined previously. [0040] Particularly, the polymer of the particles a) is a polymer a1) of linear or branched, preferably linear, C1-C4 alkyl (meth)acrylate, in particular (C1-C3)alkyl (meth)acrylate, and a2) of ethylenically unsaturated anhydride monomer. [0041] The monomers a1) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl (meth)acrylate. [0042] Advantageously, use is made of one, or two different, linear or branched, preferably linear, C1-C4 alkyl acrylate, in particular (C1-C3)alkyl acrylate monomers a1). Preferentially, a1) is chosen from methyl acrylate and ethyl acrylate. [0043] According to a particular embodiment, use is made of one, or two different, branched (C3-C4)alkyl (meth)acrylate monomers. Preferentially, a1) is chosen from isobutyl acrylate and isobutyl methacrylate. [0044] According to a specific form of the invention, the ethylenically unsaturated anhydride compound(s) a2) of the invention is (are) chosen from derivatives of maleic anhydride (4a) and of itaconic anhydride (4b) as defined previously. [0045] More preferentially, the ethylenically unsaturated anhydride monomer of the invention is of formula (4a) and even more preferentially is maleic anhydride.
[0046] The polymer of the particles may be chosen from: methyl acrylate/maleic anhydride copolymers; ethyl acrylate/maleic anhydride copolymers; and methyl acrylate/ethyl acrylate/maleic anhydride copolymers. [0047] According to a preferred embodiment of the invention, the copolymer(s) of the particles i) of the oily dispersion comprises (comprise) from 80% to 95% by weight of ingredient a1) and from 5% to 20% by weight of ingredient a2), relative to the total weight of the copolymer(s). [0048] More particularly, the polymer of the particles i) comprises preferably from 80% to 93% by weight of ingredient a1), notably of C1-C4 alkyl (meth)acrylate, and from 7% to 20% by weight of ingredient a2) relative to the total weight of the polymer i). More preferentially, the polymer of the particles i) comprises preferably from 85% to 93% by weight, more particularly 87% to 92% by weight, even more preferentially from 85% to 90% by weight of ingredient a1), notably of C1-C4 alkyl (meth)acrylate, and from 10% to 20% by weight of ingredient a2) relative to the total weight of the polymer. [0049] Advantageously, the polymer of the particles i) is a non-crosslinked polymer. [0050] According to one embodiment of the invention, the copolymers i) are chosen from: - copolymers of methyl acrylate/ethyl acrylate/acrylic acid and its salts; - copolymers of methyl acrylate/ethyl acrylate/maleic anhydride; - copolymers of methyl acrylate/acrylic acid and its salts; - copolymers of ethyl acrylate/acrylic acid and its salts; - copolymers of methyl acrylate/maleic anhydride; - copolymers of ethyl acrylate/maleic anhydride; - copolymers of isobutyl acrylate/acrylic acid and its salts; and - copolymers of isobutyl acrylate/isobutyl methacrylate/acrylic acid and its salts. [0051] The polymer of the particles i) of the dispersion preferably has a number-average molecular weight ranging from 2000 to 10000000 g/mol. [0052] The polymer of the particles i) may be present in the dispersion (A) in a content ranging from 20% to 60% by weight relative to the total weight of the dispersion, in particular between 21% and 58.5% by weight relative to the total weight of the dispersion, preferably ranging from 30% to 50% by weight relative to
the total weight of the dispersion, more preferentially ranging from 36% to 42% by weight relative to the total weight of the dispersion (A). [0053] Preferably, the particle(s) i) is (are) constituted of a copolymer of a1) and a2). [0054] According to a particular embodiment of the invention, the particles i) are constituted of copolymers resulting from the polymerization of monomers a1) and a2) with an a1) / a2) weight ratio inclusively between 4.4 and 20, more particularly between 5.5 and 19, preferably between 6.5 and 16 and even more preferentially between 6.6 and 15.6. [0055] The polymer particle(s) i) of the dispersion (A) preferably has (have) a number-average size ranging from 5 to 600 nm, notably ranging from 10 to 500 nm and better still ranging from 20 to 400 nm. The stabilizer(s) ii) [0056] The dispersion (A) according to the invention also comprises one or more stabilizers ii). Preferably, only one type of stabilizer ii) is used in the invention. [0057] The stabilizer(s) of the invention is (are) constituted of ethylenic polymers chosen from b) polymers of (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate monomers; and c) copolymers of c1) (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate and c2) (C1-C4)alkyl (C1-C4)(alkyl)acrylate. Preferably, the stabilizer(s) of the invention is (are) constituted of ethylenic polymers chosen from c) copolymers of c1) (C3- C12)cycloalkyl (C1-C6)(alkyl)acrylate and c2) (C1-C4)alkyl (C1-C4)(alkyl)acrylate. [0058] According to a preferred embodiment of the invention, the stabilizer(s) ii) is (are) constituted of ethylenic polymers chosen from: b) polymers of monomers of formula H2C=C(R)-C(O)-O-R'' (III) with R representing a hydrogen atom or (C1-C4)alkyl group such as methyl, and R'' representing a (C5-C10)cycloalkyl group such as norbornyl or isobornyl, preferably isobornyl; and c) the copolymers of c1) H2C=C(R)-C(O)-O-R'' (III) in which R and R'' have the same meanings indicated previously in b) and of c2) H2C=C(R)-C(O)-O-R' (I) in which R has the same meaning as that in formula (III) and R' represents a (C1-C4)alkyl group. [0059] According to a particular embodiment, the stabilizer(s) of the invention is (are) constituted of ethylenic polymers chosen from b) polymers of (C3-
C12)cycloalkyl (C1-C6)(alkyl)acrylate monomers, particularly of formula (III) as defined previously. [0060] According to another particular embodiment of the invention, the stabilizer(s) of the invention is (are) constituted of ethylenic polymers chosen from c) copolymers of c1) (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate, particularly of formula (III) as defined previously and of c2) (C1-C4)alkyl (C1-C4)(alkyl)acrylate, particularly of formula (I) as defined previously. [0061] According to a specific form of the invention, the ingredient c2) is a (C1- C4)alkyl (C1-C4)(alkyl)acrylate monomer, notably of formula (I), more particularly chosen from methyl (meth)acrylate and ethyl (meth)acrylate, more preferentially methyl (meth)acrylate. [0062] According to another particular form of the invention, the ingredient c2) is a mixture of several different (C1-C4)alkyl (C1-C4)(alkyl)acrylate monomers, in particular two different (C1-C4)alkyl (C1-C4)(alkyl)acrylate monomers, notably formula (I), more particularly chosen from methyl (meth)acrylate and ethyl (meth)acrylate. [0063] Particularly, the stabilizer ii) is chosen from b) polymers of (C3- C12)cycloalkyl (C1-C6)(alkyl)acrylate monomers; and c) statistical copolymers of c1) (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate and of c2) (C1-C4)alkyl (C1- C4)(alkyl)acrylate with a c1)/c2) weight ratio of greater than 4. Advantageously, said weight ratio ranges from 4.5 to 19. More advantageously, said c1)/c2) weight ratio ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 12. [0064] More particularly, the stabilizer ii) is a polymer chosen from b) isobornyl (meth)acrylate homopolymer and c) statistical copolymers of c1) isobornyl (meth)acrylate and of c2) C1-C4 alkyl (meth)acrylate preferably present in an isobornyl (meth)acrylate/C1-C4 alkyl (meth)acrylate (c1)/c2)) weight ratio of greater than 4. Advantageously, said c1)/c2) weight ratio ranges from 4.5 to 19. Advantageously, said c1)/c2) weight ratio ranges from 5 to 15 and more preferentially said c1)/c2) weight ratio ranges from 5.5 to 12. [0065] For these statistical copolymers, the defined weight ratio makes it possible to obtain a polymer dispersion that is stable, notably after storage for seven days at room temperature.
[0066] Advantageously, the stabilizer is chosen from: b) isobornyl acrylate homopolymers, c) statistical copolymers of isobornyl acrylate/methyl acrylate, statistical copolymers of isobornyl acrylate/ethyl acrylate, and statistical copolymers of isobornyl acrylate/methyl acrylate/ethyl acrylate in the weight ratio described previously. [0067] The stabilizing polymer ii) preferably has a number-average molecular weight ranging from 10000 to 400000, preferably ranging from 20000 to 200000 g/mol. [0068] The stabilizer ii) is in contact with the surface of the polymer particles i) and thus makes it possible to stabilize these particles at the surface in order to keep these particles in dispersion in the medium of the dispersion (A). [0069] More particularly, the stabilizer(s) ii) is (are) chosen from c) the copolymers of: c1) (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate; and c2) (C1-C4)alkyl (C1-C4)(alkyl)acrylate; with 80% to 95% by weight of ingredient c1), notably of isobornyl (meth)acrylate, and from 5% to 20% by weight of ingredient c2), notably methyl acrylate and ethyl acrylate, relative to the total weight of the stabilizer. [0070] More preferentially, the stabilizer(s) ii) comprises (comprise) from 85% to 94% by weight, more particularly 87% to 93% by weight of ingredient c1), notably of isobornyl (meth)acrylate, and from 10% to 20% by weight of ingredient c2), notably methyl acrylate and/or ethyl acrylate, relative to the total weight of the polymer. [0071] Advantageously, the sum of ii) stabilizer(s) + i) polymer particle(s) present in the dispersion (A) comprises from 5% to 60%, in particular comprises from 10% to 40% by weight of polymers b) or c) and from 60% to 90%, in particular from 61% to 89% by weight of polymers a), relative to the total weight of the sum of ii) stabilizer(s) + i) polymer particle(s). [0072] Preferentially, the sum of ii) stabilizer(s) + i) polymer particle(s) present in the dispersion comprises from 15% to 30% by weight of polymers b) or c) and from 70% to 85% by weight of polymers a), relative to the total weight of the sum of ii) stabilizer(s) + i) polymer particle(s). [0073] Preferably, the stabilizer(s) ii) and the particle(s) i) have a number- average molecular weight (Mn) of between 1000 and 1000000 g/mol, notably
between 5000 and 500000 g/mol and even better still between 10000 and 300 000 g/mol. [0074] The dispersion (A) according to the invention is finally formed from polymeric particles of relatively large diameter, i.e. preferably greater than 100 nm, and leads to glossy, film-forming deposits which are resistant to fatty substances at room temperature (25°C), which are advantageous notably for makeup applications. [0075] The final particle size is greater than 100 nm. In particular, polymeric particles have a number-average size ranging from 100 nm to 600 nm, more particularly ranging from 150 nm to 500 nm and even more particularly ranging from 160 nm to 400 nm. [0076] The average particle size is determined via standard methods known to those skilled in the art. A Malvern brand NanoZS model laser particle size analyser (which is particularly suitable for submicron dispersions) makes it possible to measure the size distribution of these samples. The operating principle of this type of machine is based on dynamic light scattering (DLS), also known as quasi-elastic light scattering (QELS) or photon correlation spectroscopy (PCS). [0077] The sample is pipetted into a disposable plastic cuvette (four transparent sides, side length of 1 cm and capacity of 4 mL) placed in the measuring cell. The data are analysed on the basis of a method of cumulants which leads to a unimodal particle size distribution characterized by an intensity- average diameter d (nm) and a size polydispersity factor Q. The results may also be expressed in the form of statistical data such as D10; D50 (median), D90 and the mode. [0078] Other particle size techniques make it possible to obtain this type of information, such as analysis of the individual tracking of particles (Nanoparticle Tracking Analysis, NTA), laser scattering (LS), acoustic extinction spectroscopy (AES) spatial-filter Doppler velocimetry or image analysis. [0079] The hydrocarbon-based oil(s) iii) [0080] The oily medium of the polymer dispersion comprises at least one hydrocarbon-based oil iii).
[0081] The hydrocarbon-based oil is an oil that is liquid at room temperature (25°C) and at atmospheric pressure. [0082] The term “hydrocarbon-based oil” means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups. [0083] The hydrocarbon-based oil may be chosen from: - hydrocarbon-based oils having from 8 to 14 carbon atoms, and especially: - branched C8-C14 alkanes, for instance C8-C14 isoalkanes of petroleum origin (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6- pentamethylheptane), isodecane and, for example, the oils sold under the trade names Isopar or Permethyl, - linear alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, the mixtures of n-undecane (C11) and of n-tridecane (C13) obtained in Examples 1 and 2 of application WO 2008/155059 from the company Cognis, and mixtures thereof, - hydrocarbon-based oils of plant origin such as triglycerides constituted of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C4 to C24, these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides, or alternatively wheatgerm oil, sunflower oil, grapeseed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, red kuri squash oil, pumpkin oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil or musk rose oil; shea butter; or else caprylic/capric acid triglycerides, for instance those sold by the company Stéarinerie Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel, - synthetic ethers containing from 10 to 40 carbon atoms, - linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane and liquid paraffins, and mixtures thereof,
- synthetic esters such as oils of formula R1COOR2 in which R1 represents a linear or branched fatty acid residue including from 1 to 40 carbon atoms and R2 represents a, notably branched, hydrocarbon-based chain containing from 1 to 40 carbon atoms, on condition that R1 + R2 ≥ 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12 to C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2- octyldodecyl myristate, alcohol or polyalcohol heptanoates, octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, diisostearyl malate and 2-octyldodecyl lactate; polyol esters and pentaerythritol esters, - fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2- butyloctanol and 2-undecylpentadecanol. [0084] Advantageously, the hydrocarbon-based oil(s) of the invention is (are) formed solely of carbon and hydrogen atoms. [0085] Preferably, the oily dispersion comprises at least one hydrocarbon-based oil iii) formed solely of carbon and hydrogen atoms, preferably chosen from: - linear or branched C8-C30, in particular C10-C20 and more particularly C10-C16 alkanes, which are volatile or non-volatile, preferably volatile; - non-aromatic cyclic C5-C12 alkanes, which are volatile or non-volatile, preferably volatile; and - mixtures thereof. [0086] The hydrocarbon-based oil(s) is (are) preferably chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, in particular containing from 10 to 14 carbon atoms, which are preferably volatile. [0087] Among the branched C8-C16 and notably C10-C14 alkanes that are suitable for use as liquid hydrocarbon-based fatty substances iii) in the dispersion of the invention, mention may be made of: - isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane and, for example, the oils sold under the Isopar or Permethyl trade names,
- linear alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references, respectively, Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, mixtures of n-undecane (C11) and of n-tridecane (C13) from the company Cognis, and mixtures thereof. [0088] Preferentially, the liquid hydrocarbon-based oil(s) iii) of the invention is (are) formed solely of carbon and hydrogen atoms, more particularly of isododecane. [0089] According to another advantageous embodiment of the invention, the hydrocarbon-based oil(s) is (are) a mixture of non-volatile oil and volatile oil; preferably, the mixture comprises isododecane as volatile oil. In particular, in the mixture, the non-volatile oil is a phenyl silicone oil, preferably chosen from pentaphenyl silicone oils. [0090] Preferably, the liquid hydrocarbon-based oil(s) iii) is (are) present in the dispersion of the invention in an amount of between 15% and 80% by weight, more preferentially between 20% and 60% by weight, relative to the total weight of said oily dispersion. According to a particular embodiment of the invention, the weight ratio of the sum of the ingredients [i) + ii)] / iii) is less than or equal to 1, more particularly the [i) + ii)] / iii) weight ratio is between 0.5 and 1. [0091] The polymer particles i) of the dispersion preferably have an average size, notably a number-average size, ranging from 50 to 500 nm, notably ranging from 75 to 400 nm and better still ranging from 100 to 250 nm. [0092] In general, the dispersion according to the invention may be prepared in the following manner, which is given as an example. Non-volatile oils [0093] According to a specific form of the invention, the composition according to the invention comprises at least one non-volatile oil. [0094] The term “oil” is understood to mean a water-immiscible non-aqueous compound which is liquid at ambient temperature (25°C) and atmospheric pressure (760 mmHg). [0095] The term “non-volatile oil” is understood to mean an oil which remains on the keratin fibre, at room temperature and atmospheric pressure, for at least several hours and which has in particular a vapour pressure of less than 10-3 mmHg (0.13 Pa).
[0096] These oils can be hydrocarbon-based oils, silicone oils or mixtures thereof. [0097] The term “hydrocarbon-based oil” is intended to mean an oil mainly containing hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur or phosphorus atoms. [0098] Within the meaning of the present invention, the term “silicone oil” is understood to mean an oil comprising at least one silicon atom, and in particular at least one Si-O group. [0099] Non-volatile hydrocarbon-based oils that may in particular be mentioned include: - hydrocarbon-based oils of plant origin, such as fatty acid triesters of glycerol, the fatty acids of which may have chain lengths ranging from C4 to C24, these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably wheatgerm oil, sunflower oil, grapeseed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, red kuri squash oil, pumpkin oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil or musk rose oil; or else caprylic/capric acid triglycerides, for instance those sold by the company Stéarinerie Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel; - linear or branched hydrocarbons of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, polydecenes, polybutenes, hydrogenated polyisobutene such as Parleam, or squalane; - synthetic ethers containing from 10 to 40 carbon atoms; - synthetic esters such as oils of formula R1COOR2 in which R1 represents a linear or branched fatty acid residue including from 1 to 40 carbon atoms and R2 represents a, notably branched, hydrocarbon-based chain containing from 1 to 40 carbon atoms, on condition that R1 + R2 ≥ 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12 to C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, alcohol or polyalcohol octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate and diisostearyl malate; and pentaerythritol esters;
- fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2- butyloctanol and 2-undecylpentadecanol; - higher fatty acids such as oleic acid, linoleic acid or linolenic acid; and mixtures thereof. [00100] The non-volatile silicone oils that may be used in the composition according to the invention may be non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups, that are pendent and/or at the end of a silicone chain, the groups each containing from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates. [00101] According to a preferential form of the invention, the non-volatile oil or oils are present in the composition in a total concentration of less than 10.0% by weight, relative to the total weight of the composition. Method for preparing the dispersion [00102] Without this being limiting, in general, the dispersion according to the invention may be prepared in the following manner: - The polymerization is performed in dispersion in non-aqueous medium, i.e. by precipitation of the polymer being formed, with protection of the formed particles with one or more stabilizers ii), preferably only one type of stabilizer ii) chosen from b) and c) as defined previously. - In a first step, the stabilizing polymer (or stabilizer ii)) is prepared by mixing the constituent monomer(s) of the stabilizing polymer b) or c) with iv) a free-radical initiator, in a solvent known as the synthesis solvent, and by polymerizing these monomers; and then - In a second step, the constituent monomers of the polymer of the particles i) are added to the stabilizing polymer ii) formed in the preceding step and polymerization of these added monomers is performed in the presence of the free-radical initiator. - In a third step, water and the sum of ingredients i) + ii) are stirred in the reactor before removing the dispersion. When the non-aqueous medium is a non-volatile hydrocarbon-based oil iii), the polymerization may be performed in an organic
solvent (synthesis solvent), followed by adding the non-volatile hydrocarbon- based oil (which should be miscible with said synthesis solvent) and selectively distilling off the synthesis solvent. [00103] The synthesis solvent may be constituted of hydrocarbon-based oil iii) combined with an additional solvent notably chosen from linear or branched hydrocarbon-based aliphatic-chain esters containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate. [00104] At the end of step 1, when the synthesis solvent is a mixture, the additional solvent including the hydrocarbon-based aliphatic-chain esters as defined previously is removed via a method that is conventional to those skilled in the art, such as distillation. The polymers of the particles i) are found in the hydrocarbon-based oil iii). [00105] A synthesis solvent which is such that the monomers of the polymeric stabilizer(s) ii) and the free-radical initiator iv) are soluble therein, and the polymer particles i) obtained are insoluble therein, so that they precipitate therein during their formation, is thus chosen. [00106] In particular, the synthesis solvent chosen is one which is organic and volatile, preferably chosen from volatile hydrocarbon-based oils iii), notably alkanes such as heptane, cyclohexane or isododecane, preferably isododecane. [00107] When the non-aqueous medium is a volatile hydrocarbon-based oil iii), the polymerization may be performed directly in said oil, which thus also acts as synthesis solvent. The monomers should also be soluble therein, as should the free-radical initiator, and the polymer of the particles i) which is obtained should be insoluble therein. [00108] The monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of 15% to 45% by weight. The total amount of the monomers may be present in the solvent before the start of the reaction, or a portion of the monomers may be added gradually as the polymerization reaction proceeds. [00109] The polymerization is preferably performed in the presence iv) of one or more free-radical initiators which may be any initiator known to those skilled in the art for radical polymerization, such as peroxide or azo initiators, redox couples and photochemical initiators. [00110] Mention may notably be made of those of the following types:
- peroxide, in particular chosen from tert-butyl peroxy-2-ethylhexanoate: Trigonox 21S; 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane: Trigonox 141; tert-butyl peroxypivalate: Trigonox 25C75 from AkzoNobel; or - azo, in particular chosen from AIBN: azobisisobutyronitrile; V50: 2,2'-azobis(2- amidinopropane) dihydrochloride. [00111] The polymerization is preferably performed at a temperature ranging from 70 to 110°C and at atmospheric pressure. [00112] The polymer particles i) are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer ii). [00113] The stabilization may be performed by any known means, and in particular by direct addition of the stabilizer ii), during the polymerization. [00114] The stabilizer ii) is preferably also present in the mixture before polymerization of the monomers of the polymer of the particles i). However, it is also possible to add it continuously, notably when the monomers of the particles i) are also added continuously. [00115] From 2% to 40% by weight, particularly from 3% to 30% by weight and more particularly from 4% to 25% by weight of the stabilizer(s) ii) may be used relative to the total weight of monomers used (stabilizers ii) + polymer particles i)), and preferably from 4.5% to 20% by weight. [00116] The dispersion of polymer particles i) advantageously comprises from 30% to 65% by weight of solids relative to the total weight of said dispersion and preferably from 40% to 60% by weight relative to the total weight of said dispersion. [00117] The composition according to the invention preferably comprises a solids (or active material) content of polymers of particle i) + dispersing polymers ii) ranging from 10% to 80% by weight, relative to the total weight of the composition, preferably ranging from 20% to 60% by weight, notably 30% to 50% by weight, relative to the total weight of the composition. [00118] According to a preferred embodiment of the invention, the dispersion of the invention does not comprise more than 3% by weight of surfactants relative to the total weight of the dispersion, preferentially not more than 2% by weight of surfactants relative to the total weight of the dispersion, more particularly not more than 1% by weight of surfactants relative to the total weight of the dispersion; even more preferentially, the composition does not comprise more
than 0.5% by weight of surfactants relative to the total weight of the dispersion, and better still the mixture does not comprise any surfactant. [00119] In one particular preparation method, the statistical stabilizing polymer ii) is prepared in a first step. This stabilizing polymer is soluble in an organic solvent of alkane type, such as isododecane. [00120] Next, in a second step, the polymer particles i) are synthesized in the presence of the stabilizing polymer ii). [00121] Preferentially, a solution of stabilizing polymer ii) in the hydrocarbon- based oil(s) iii) is prepared for the final dispersion, and the polymerization of the monomers which form the core of the particle is performed in the presence of this stabilizer ii). [00122] The stabilizing polymer ii) may be prepared by radical polymerization optionally in the presence of a polymerization initiator iv) as defined previously. [00123] In a second step, the monomers which form the core of the particle i) may be polymerized in the presence of said stabilizing polymer ii). This second step may be a conventional radical polymerization. [00124] Next, water or an aqueous composition is added, preferably with stirring. [00125] The dispersions are prepared in the presence of one or more hydrocarbon-based oils iii), preferably in an organic solvent, in particular of alkane type such as isododecane, according to an industrially feasible process. [00126] The dispersions according to the invention are thus finally formed from polymer particles, of relatively large diameter (preferably greater than 100 nm), and give glossy film-forming deposits that are resistant to fatty substances at the observation temperature (25°C). [00127] Furthermore, since said dispersion is in oily medium with the presence of water, it becomes easy to formulate it in cosmetic compositions based on oily medium commonly used in cosmetics, in particular anhydrous media or in the fatty phases of emulsions, but also in aqueous media to enable the dissolution of water-soluble active agents. [00128] Advantageously, the oily dispersion may comprise a plasticizer chosen from tri-n-butyl citrate, tripropylene glycol monomethyl ether (INCI name: PPG-3 Methyl Ether) and trimethyl pentaphenyl trisiloxane (sold under the name Dow Corning PH-1555 HRI Cosmetic Fluid by the company Dow Corning). These
plasticizers make it possible to improve the mechanical strength of the polymer film. [00129] The plasticizer is preferably present in the oily dispersion in a content ranging from 5% to 50% by weight, relative to the total weight of the polymer of the particles. [00130] Preferentially, use will be made of a dispersion in iii), notably isododecane, of surface-stabilized polymer particles i) chosen from: - a dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (24.5/62.8/12.7) copolymer particles stabilized by an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the oily dispersion containing in total (stabilizer + particles) 10% of acrylic acid, 20% of methyl acrylate, 50% of ethyl acrylate and 20% of isobornyl acrylate; - a dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (11.7/75.6/12.7) copolymer particles stabilized by an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the oily dispersion containing in total (stabilizer + particles) 10% of acrylic acid, 10% of methyl acrylate, 60% of ethyl acrylate and 20% of isobornyl acrylate; - a dispersion in isododecane of methyl acrylate/ethyl acrylate/maleic anhydride (50/37.2/12.8) copolymer particles stabilized by an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the oily dispersion containing in total (stabilizer ii) + particles i)) 10% of maleic anhydride, 30% of methyl acrylate, 40% of ethyl acrylate and 20% of isobornyl acrylate. [00131] More preferentially, use will be made of a dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (11.7/75.6/12.7) copolymer particles stabilized by an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the oily dispersion containing in total (stabilizer ii) + particles i)) 10% of acrylic acid, 10% of methyl acrylate, 60% of ethyl acrylate and 20% of isobornyl acrylate. [00132] The amount of oily dispersion of particles i) in the composition of the invention preferably varies from 20% to 40% by weight, more preferentially from 25% to 35% by weight relative to the total weight of the composition. Water
[00133] The composition according to the invention preferably comprises an amount of water greater than or equal to 2% by weight and less than 50% by weight relative to the total weight of the composition, more preferentially the amount of water in the composition is between 5% and 49% by weight relative to the total weight of the composition, more particularly between 10% and 47% by weight, between 15% and 48% by weight, preferentially between 18% and 45%, more preferentially still between 20% and 40% by weight, relative to the total weight of the composition. Aqueous dispersion of colloidal particles [00134] The compositions according to the invention comprise at least one aqueous dispersion of colloidal silica particles. [00135] Within the meaning of the present invention, the term “colloidal particles” is understood to mean particles having a number-average diameter of between 0.1 and 100 nm, preferably between 3 and 30 nm, better still between 10 and 15 nm. These particles retain the abovementioned diameters in the composition containing them, without aggregating, and do not therefore have thickening properties in the sense that at a concentration greater than or equal to 15% by weight in water, the colloidal particles have a viscosity of less than 0.05 Pa.s for a shear rate equal to 10-1 s, the viscosity being measured at 25°C using a Haake RheoStress® RS150 rheometer in cone-plate configuration, the cone having a diameter of 60 mm and an angle of 2°. [00136] This dispersion of colloidal particles may be prepared according to the “sol-gel” process well known to those skilled in the art, from salts or alkoxides of the corresponding metals dissolved in a solvent, such as an alcohol. A hydrolysis reaction is then carried out to form an amorphous precipitate. This is then dispersed in water with an acid or a base depending on the desired pH, which leads to peptization of the precipitate and to crystallization. In this way a crystalline oxide dispersed in water is formed. [00137] Such colloidal aqueous suspensions may for example be prepared according to the processes described in J. Colloïd Interface Sci., 26, p.62-69, 1968 for SiO2, Appli. Opt.26, 4688, 1987 for TiO2, Inorg. Chem., 3, 146, 1964 for ZrO2, Appl. Opt., 27, 3356, 1988 for CaF2 and MgF2.
[00138] These suspensions are prepared using ionic precursors chosen most often from chlorides, oxychlorides, perchlorates, nitrates, oxynitrates or else acetates, or molecular precursors preferably chosen from alkoxides, of molecular formula M(OR)n (M representing a metal, OR an alkoxy radical with from 1 to 6 carbon atoms and n representing the valency of the metal). In the methods described above, the precursor is hydrolysed or fluorinated then polymerized until a finished product is obtained, which is insoluble in the chosen solvent, nucleated and referred to as a colloidal suspension. In the case of alkoxides, the hydrolysis must be rigorously controlled given the very hydrophilic nature of these organometallic derivatives. [00139] Another process for preparing such products is described in J. LIVAGE et al., “SOL-GEL SYNTHESIS OF METAL OXIDE CLUSTERS AND COLLOIDS” (MAT. RES. SOC. SYNT. PROC., volume 272, pages 3 to 14). [00140] The colloidal particles may as a variant be constituted of a mixed oxide, in particular of a silica-alumina composite filler. [00141] Within the meaning of the present invention, the term “particles of silica-alumina composite filler” means particles constituted of silicon oxide and the surface of which has been chemically modified so as to replace at least some of the silicon atoms with aluminium atoms forming at most one monomolecular layer of aluminium. [00142] They may be prepared, in particular, as described in patent US- 2,892,797, by mixing a silica sol with a sodium aluminate. [00143] The aqueous dispersions of colloidal silica particles according to the present invention preferably contain silica particles in concentrations ranging from 10% to 50% by weight, preferably from 25% to 40% by weight relative to the total weight of the aqueous dispersion. [00144] The colloidal silica particles according to the invention are preferably anionic and amorphous silica particles. [00145] Within the meaning of the present invention, the term “anionic particles” is understood to denote silica particles bearing at the surface anionic charges, in particular neutralized with one or more cations.
[00146] Such particles are obtained, for example, by reacting silanol groups at the surface of silica particles with alkaline agents such as sodium hydroxide (NaOH) or ammonium hydroxide (NH4OH). [00147] These particles are preferably spherical or approximately spherical. [00148] According to a specific form of the invention, these particles are non-porous. [00149] The anionic colloidal silica particles according to the invention may be monodisperse or polydisperse. [00150] Within the meaning of the present invention, the term “monodisperse” means that the sizes of said particles have a narrow distribution. Conversely, within the meaning of the present invention, the term “polydisperse” means that the sizes of the particles have a broader distribution. [00151] Preferably, the anionic colloidal silica particles according to the invention are monodisperse. [00152] The mean diameter of the anionic colloidal silica particles is generally between 3 and 100 nm, preferably between 3 and 50 nm and more preferentially between 5 and 10 nm. [00153] This mean diameter may be measured using a particle size distribution analyser of the Coulter N4 PLUS® type manufactured by Beckman Coulter Inc. [00154] When the anionic colloidal silica particles are monodisperse, their mean diameter is preferably between 3 and 50 nm, in particular between 5 and 25 nm and more preferentially between 5 and 10 nm. [00155] When the anionic colloidal silica particles are polydisperse, their mean diameter is preferably between 5 and 70 nm, in particular between 10 and 50 nm. [00156] The specific surface area of the anionic colloidal silica particles generally ranges from 50 to 500 m2/g SiO2. [00157] The specific surface area 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 (Annex D). The BET specific surface area corresponds to the total specific surface area of the particles under consideration. The sizes of the 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 notably described in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957. [00158] The specific surface area of the anionic colloidal silica particles generally ranges from 100 to 500 m2/g SiO2, in particular from 130 to 450 m2/g SiO2, more preferentially from 250 to 400 m2/g SiO2, and more particularly still from 320 to 370 m2/g SiO2, in particular when they are monodisperse. [00159] When the anionic colloidal silica particles are polydisperse, their specific surface area generally ranges from 50 to 300 m2/g SiO2, in particular from 70 to 280 m2/g SiO2. [00160] Advantageously, the anionic colloidal silica particles are silica particles neutralized by counterions of cationic nature so as to ensure the electroneutrality of the particles. [00161] These counterions may notably be chosen from sodium (Na+) and ammonium ( NH4+). [00162] According to a specific form of the invention, the cationic counterions are sodium ions (Na+). [00163] The aqueous dispersions of anionic colloidal silica particles according to the invention have a pH preferably of from 8 to 10. [00164] Among the dispersions of anionic colloidal silica particles, mention may notably be made of those sold under the name Ludox® by the company Grace. In particular, the dispersions of anionic silica particles denote the particles sold by the company Grace under the names Ludox® AM X6021, Ludox® FM, Ludox® SM, Ludox® HS-30, Ludox® HS-40, Ludox® LS, Ludox® TM-40, Ludox®
TM-50, Ludox® PX-30, Ludox® PT-40, Ludox® PW-50, Ludox® SM-AS, Ludox® AS-30 and Ludox® AS-40. [00165] When the particles are monodisperse, they are preferably chosen from those sold under the names Ludox® AM X6021, Ludox® FM, Ludox® SM, Ludox® HS-30, Ludox® HS-40, Ludox® LS, Ludox® TM-40, Ludox® TM-50, Ludox® SM-AS, Ludox® AS-30 and Ludox® AS-40. In particular, the anionic colloidal silica particles denote the Ludox® SM particles sold by the company Grace. [00166] When the particles are polydisperse, they are preferably chosen from Ludox® PX-30, Ludox® PT-40 and Ludox® PW-50 sold by the company Grace. [00167] They are synthesised in the aqueous phase by precipitation of sodium silicate SiONa+ by nitric acid HNO3. It is obtained in the form of an alkaline aqueous dispersion of spherical and relatively monodisperse particles, with a mean diameter of between 10 and 15 nm and a density of the order of 2200 kg/m3. Their pH at 25°C typically varies between 8 and 10. The aqueous dispersions of Ludox colloidal silica particles contain from 20% to 40% by weight of silica particles relative to the total weight of the dispersion. [00168] Use will in particular be made of the aqueous dispersion of Ludox AM X6021® anionic colloidal silica particles containing 29-31% by weight of silica particles relative to the total weight of the dispersion. It also contains alumina in a content of the order of 0.2% by weight. The silica particles have a mean diameter of the order of 12 nm and a specific surface area of 198 ‒ 258 m2/g SiO2. The aqueous dispersion is alkaline and has a pH at 25°C of from 8.5 to 9.3. [00169] Among the aqueous dispersions of anionic colloidal silica particles that can be used according to the invention, mention may also be made of the aqueous dispersions of silica available commercially from the company MERCK under the commercial references Klebesol®. In particular, the dispersions of anionic silica particles denote the particles sold by the company Grace under the names Klebesol® 40PA50, Klebesol® 30N50, Klebesol® 30N50PHN, Klebesol® 30H50, Klebesol® 1501-50, Klebesol® 1508-50, Klebesol® 1498-50.
[00170] They are obtained in an alkaline aqueous phase by hydrolysis of tetraethoxysilane (TEOS) containing organometallic precursors SiO-C2H5 according to the Stöber synthesis method [Stöber et al. (1968), Green et al. (2003)]. The synthesis of this silica is catalysed by the presence of aqueous ammonia in solution. It is obtained in the form of an ammoniacal aqueous dispersion of spherical monodisperse particles, with a mean diameter of the order of 50 nm and a density of the order of 2400 kg/m3. Their pH at 25°C typically varies between 10 and 11. [00171] Use will in particular be made of the aqueous dispersion of anionic colloidal silica particles of commercial reference Klebesol 30N50PHN® containing 30% by weight of silica particles relative to the total weight of the dispersion. The colloidal silica particles have a mean size of the order of 50 nm. The aqueous dispersion is alkaline and has a pH at 25°C of 10.9. [00172] The amount of aqueous dispersion of colloidal silica particles in the composition of the invention preferably varies from 5% to 20% by weight, more preferentially from 5% to 15% by weight relative to the total weight of the composition. [00173] In one preferred embodiment, the weight ratio of the oily dispersion of surface-stabilized polymer particles to the aqueous dispersion of colloidal silica particles varies from 2 to 6, more preferentially from 2 to 5. Waxes [00174] The composition according to the invention may in addition comprise at least one wax in an amount of less than 5.0% by weight, or less than 2.0% relative to the total weight of the composition. This wax makes it possible to obtain thick, charging textures. [00175] The term “wax” means a deformable or undeformable lipophilic compound, which is solid at room temperature (25°C), with a reversible solid/liquid change of state, having a melting point of greater than or equal to 40°C, which may be up to 120°C. In particular, the waxes that are suitable for use in the invention may have a melting point of greater than or equal to 45°C and in particular greater than or equal to 55°C.
[00176] The term “lipophilic compound” refers to a compound having an acid number and a hydroxyl number of less than 150 mg KOH/g. [00177] For the purposes of the invention, the melting point corresponds to the temperature of the most endothermic peak observed on thermal analysis (DSC) as described in the standard ISO 11357-3; 1999. The melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2920® by the company TA Instruments. [00178] The measuring protocol is as follows: [00179] A sample of 5 mg of wax placed in a crucible is subjected to a first temperature rise ranging from -20°C to 100°C, at a heating rate of 10°C/minute, it is then cooled from 100°C to -20°C at a cooling rate of 10°C/minute and is finally subjected to a second temperature rise ranging from -20°C to 100°C at a heating rate of 5°C/minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the sample of wax is measured as a function of the temperature. The melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature. [00180] The waxes may be hydrocarbon-based waxes, silicone waxes and/or fluoro waxes, and may be of plant, mineral, animal and/or synthetic origin. [00181] Use may in particular be made, as wax, of hydrocarbon waxes, such as beeswax, lanolin wax; rice wax, carnauba wax, candelilla wax, ouricury wax, Japan wax, berry wax, shellac wax and sumac wax; montan wax. [00182] Mention may also be made of waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C8-C32 fatty chains. [00183] Among these waxes, mention may notably be made of hydrogenated jojoba oil, hydrogenated palm oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut kernel oil, hydrogenated lanolin oil and bis(1,1,1- trimethylolpropane) tetrastearate sold under the name Hest 2T-4S® by the
company Heterene, and bis(1,1,1-trimethylolpropane) tetrabehenate sold under the name Hest 2T-4B® by the company Heterene. [00184] Use may also be made of the wax obtained by hydrogenation of olive oil esterified with stearyl alcohol, sold under the name Phytowax Olive 18L57®, or the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, sold under the names Phytowax Ricin 16L64® and 22L73® by the company Sophim. Such waxes are described in patent application FR-A-2792190. Use may also be made of a C20-C40 alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture, in particular a C20- C40 alkyl 12-(12'-hydroxystearyloxy)stearate of formula (I) [Chem 4]
in which n is an integer ranging from 18 to 38, or a mixture of compounds of formula (I). Such a tacky wax is notably sold under the names Kester Wax K 82 P® and Kester Wax K 80 P® by the company Koster Keunen. [00185] Mention may be made of microcrystalline waxes, paraffins and ozokerite, polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers and also esters thereof; silicone waxes and fluoro waxes. Mention may be made of the linear fatty acid monoesters of formula (1) below: [Chem 5] R3-O-R4 (1) in which R3 and R4 are linear and saturated and have, independently of one another, a number of carbon atoms greater than or equal to 20, with R3 representing an acyl radical, and R4 representing an alkyl radical. [00186] In particular, the fatty acid monoester according to the invention is chosen from arachidyl arachidate and behenyl behenate and more particularly behenyl behenate.
[00187] According to a preferred embodiment, use will be made of a wax chosen from beeswax, carnauba wax, cetyl alcohol, paraffins, behenyl behenate and mixtures thereof. Colorant [00188] According to a specific form of the invention, the composition according to the invention additionally comprises at least one colorant, in particular chosen from pulverulent colorants, water-soluble dyes and mixtures thereof. [00189] The pulverulent colorants can be chosen from pigments and pearlescent agents. [00190] The pigments can be white or coloured, inorganic and/or organic, and coated or uncoated. Among the mineral pigments that may be mentioned are titanium dioxide, optionally surface-treated, zirconium oxide, zinc oxide or cerium oxide, and also iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Mention may be made, among the organic pigments, of carbon black, pigments of D & C type, and lakes based on cochineal carmine and on barium, strontium, calcium or aluminium. [00191] The pearlescent agents may be chosen from white pearlescent pigments such as mica coated with titanium or with bismuth oxychloride, coloured pearlescent pigments such as titanium mica with iron oxides, titanium mica especially with ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also pearlescent pigments based on bismuth oxychloride. [00192] Preferably, the composition according to the invention comprises a pulverulent colorant, preferably of pigment type, in particular metal oxides, especially titanium dioxides, iron oxides, and mixtures thereof; and more particularly iron oxides. [00193] As water-soluble dyes that are suitable for use in the invention, mention may be made especially of synthetic or natural water-soluble dyes, for instance FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanin (beetroot), carmine, copper chlorophyllin, methylene blue, anthocyanins (enocyanin, black carrot, hibiscus and elder), caramel and riboflavin.
[00194] The water-soluble dyes are, for example, beetroot juice and caramel. [00195] Preferably, the colorant(s) is (are) present in the composition (B) in a total content ranging from 2.0% to 25.0% by weight, preferably from 3.0% to 20.0% by weight, more particularly from 4.0% to 15.0% by weight, relative to the total weight of the composition. Non-volatile oils [00196] According to a specific form of the invention, the composition according to the invention comprises at least one non-volatile oil such as those described above. Additives [00197] Mention may in particular be made, as cosmetic additives which can be used in the compositions according to the invention, of antioxidants; preservatives; fragrances; organic or inorganic fillers; thickeners and gelling agents; sequestrants; chelating agents; sunscreens; vitamins, such as vitamin C or ascorbic acid and its derivatives, such as 2-O-alpha-D-glucopyranosyl-L- ascorbic acid (INCI name: Ascorbyl Glucoside), vitamin B3 or niacinamide; vitamin B8, also called vitamin H: D-biotin, vitamin E and its derivatives, such as tocopherol acetate; provitamins such as panthenol also called provitamin B5 or dexpanthenol; moisturizing agents, such as polyols, for example 1,3-propanediol, glycerol, pentylene glycol, propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol and mixtures thereof, C1-C5 monoalcohols such as ethanol, isopropanol, and mixtures thereof. [00198] These additives can be present in the composition in a content ranging from 0.01% to 15.0% of the total weight of the composition. [00199] Needless to say, those skilled in the art will take care to select the optional additional additives and/or the amount thereof such that the advantageous properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition. [00200] According to a specific form of the invention, the composition is in the form of a makeup and/or care product for the skin, in particular of the face, area around the eyes, and cheeks, such as a foundation.
[00201] According to a specific form of the invention, the composition is in the form of a makeup and/or care product such as a lipstick. [00202] According to a specific form of the invention, the composition is in the form of a makeup and/or care product for the eyelashes, such as a mascara or an eyeliner. Packaging and applicators [00203] The compositions according to the invention may each be packaged in a container delimiting at least one compartment that comprises said composition, said container being closed by a closing member. [00204] The container may be in any suitable form. It may notably be in the form of a bottle, a tube, a jar or a case. [00205] The closing member may be in the form of a removable stopper, a lid or a cover, notably of the type including a body fixed to the container and a cap articulated on the body. It may also be in the form of a member for selectively closing the container, notably a pump, a valve or a flap valve. [00206] The container may be combined with an applicator, notably in the form of a brush including an arrangement of bristles maintained by a twisted wire. Such a twisted brush is described notably in patent US 4887622. It may also be in the form of a comb including a plurality of application members, obtained notably by moulding. Such combs are described, for example, in patent FR 2796 529. The applicator may be in the form of a fine brush, as described, for example, in patent FR 2722380. The applicator may be in the form of a block of foam or of elastomer. The applicator may be free (sponge) or securely fastened to a rod borne by the closing member, as described, for example, in patent US 5492426. The applicator may be securely fastened to the container, as described, for example, in patent FR 2761959. [00207] The product may be contained directly in the container, or indirectly. [00208] The closing member may be coupled to the container by screwing. Alternatively, the coupling between the closing member and the container occurs other than by screwing, in particular via a bayonet mechanism, by click-fastening or by gripping. The term “click-fastening” in particular means any system involving the crossing of a bead or cord of material by elastic deformation of a
portion, notably of the closing member, followed by return to the elastically unconstrained position of said portion after the bead or cord has been crossed. [00209] The container may be at least partially made of thermoplastic material. Examples of thermoplastic materials that may be mentioned include polypropylene and polyethylene. [00210] The container may have rigid or deformable walls, notably in the form of a tube or a tube bottle. [00211] The container may comprise means intended to bring about or facilitate the dispensing of the composition. By way of example, the container may have deformable walls so as to cause the composition to exit in response to excess pressure inside the container, which excess pressure is brought about by the elastic (or non-elastic) squeezing of the walls of the container. [00212] The container may be equipped with a drainer positioned in the vicinity of the opening of the container. Such a drainer makes it possible to wipe the applicator and possibly the rod to which it may be securely fastened. Such a drainer is described, for example, in patent FR 2792618. [00213] Throughout the description, including the claims, the term “including a” should be understood as being synonymous with “including at least one”, unless otherwise specified. [00214] The expressions “between ... and ...”, and “ranging from ... to ...” should be understood as meaning limits included, unless otherwise specified. [00215] The invention is illustrated in greater detail by the examples and figures presented below. Unless otherwise indicated, the amounts shown are expressed as weight percentages. Example 1 of preparing an oily dispersion of polymer [00216] A dispersion of polymer particles i) in isododecane was prepared using: Step 1: 315.2 g of isobornyl acrylate, 12.5 g of methyl acrylate, 12.5 g of ethyl acrylate, 3.4 g of Trigonox 21, 540 g of isododecane, 360 g of ethyl acetate. After 2 hours of reaction, 540 g of isododecane and 360 g of ethyl acetate were added to the reactor feedstock and the mixture was heated to 90°C.
Step 2: 303 g of methyl acrylate, 776 g of ethyl acrylate, 157 g of acrylic acid, 11 g of Trigonox 21S, 741.6 g of isododecane and 494.4 g of ethyl acetate. After reaction, 3 litres of an isododecane/ethyl acetate mixture (60/40 weight/weight) were added and total evaporation of the ethyl acetate and partial evaporation of the isododecane was performed to obtain a solids content of 44% by weight. [00217] A dispersion in isododecane of particles i) of methyl acrylate/ethyl acrylate/acrylic acid (24.5/62.8/12.7) copolymer a) which are stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer ii) was obtained. The oily dispersion contains in total (particles i) + stabilizer ii)) 10% acrylic acid, 20% methyl acrylate, 50% ethyl acrylate and 20% isobornyl acrylate. Example 2 of preparing an oily dispersion of polymer [00218] A dispersion of polymer particles i) in isododecane was prepared according to the preparation method of Example 1, using: Step 1: 315.2 g of isobornyl acrylate, 12.5 g of methyl acrylate, 12.5 g of ethyl acrylate, 3.4 g of Trigonox 21, 540 g of isododecane, 360 g of ethyl acetate; followed by addition, after reaction, of 540 g of isododecane and 360 g of ethyl acetate. Step 2: 145 g of methyl acrylate, 934 g of ethyl acrylate, 157 g of acrylic acid, 12.36 g of Trigonox 21S, 741.6 g of isododecane and 494.4 g of ethyl acetate. After reaction, 3 litres of an isododecane/ethyl acetate mixture (60/40 weight/weight) were added and total evaporation of the ethyl acetate and partial evaporation of the isododecane was performed to obtain a solids content of 44% by weight. [00219] A dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (11.7/75.6/12.7) copolymer particles i) stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer ii) was obtained. The oily dispersion contains in total (particles i) + stabilizer ii)) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate. Example 3 of preparing an oily dispersion of polymer [00220] A dispersion of polymer particles i) in isododecane was prepared according to the preparation method of Example 1, using:
Step 1: 48 g of isobornyl acrylate, 2 g of methyl acrylate, 2 g of ethyl acrylate, 0.52 g of Trigonox 21, 57.6 g of isododecane, 38.4 g of ethyl acetate; followed by addition, after reaction, of 540 g of isododecane and 360 g of ethyl acetate. Step 2: 98 g of methyl acrylate, 73 g of ethyl acrylate, 25 g of maleic anhydride, 1.96 g of Trigonox 21S, 50.4 g of isododecane and 33.60 g of ethyl acetate. After reaction, 1 litre of an isododecane/ethyl acetate mixture (60/40 weight/weight) was added and total evaporation of the ethyl acetate and partial evaporation of the isododecane was performed to obtain a solids content of 46.2% by weight. [00221] A dispersion in isododecane of methyl acrylate/ethyl acrylate/maleic anhydride (50/37.2/12.8) copolymer particles i) stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer ii) was obtained. The oily dispersion contains in total (particles i) + stabilizer ii)) 10% maleic anhydride, 30% methyl acrylate, 40% ethyl acrylate and 20% isobornyl acrylate. Examples 1 and 2 [00222] [Table 1]
Preparation protocol [00223] Compositions 1 and 2 were produced by simple mixing at room temperature (25°C). [00224] Composition 1 according to the invention is stable and homogeneous after 48 h at room temperature (25°C) unlike composition 2 outside the invention which is unstable: the silica particles settle.
Claims
Claims [Claim 1] Composition comprising, preferably in a cosmetically acceptable medium, at least: - one oily dispersion which comprises: i) one or more particle(s) comprising: a) one or more ethylenic copolymers of a1) (C1-C4)alkyl (C1- C4)(alkyl)acrylate, and of a2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl, such as benzyl, groups; in particular, a2) is a (C1-C4)(alkyl)acrylic acid, more particularly copolymers of (C1-C4)alkyl (meth)acrylate and of (meth)acrylic acid; and ii) one or more polymeric stabilizers chosen from: b) polymers of (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate monomers such as isobornyl (meth)acrylates; and c) copolymers of c1) (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylates such as isobornyl (meth)acrylates, and of c2) (C1-C4)alkyl (C1--C4)(alkyl)acrylates such as (C1-C4)alkyl (meth)acrylates; and iii) one or more hydrocarbon-based oils; - an aqueous dispersion of colloidal silica particles. [Claim 2] Composition according to the preceding claim, in which the oily dispersion is such that the particle(s) i) is (are) constituted of an ethylenic polymeric core obtained from copolymers a) as defined in the preceding claim, and ii) of one or more polymeric surface stabilizers obtained from polymer b) or from copolymers c) as defined in the preceding claim. [Claim 3] Composition according to either one of the preceding claims, in which the oily dispersion is such that the a1) (C1-C4)alkyl (C1- C4)(alkyl)acrylate monomer(s) is (are) chosen from those of formula (I): in which R represents a hydrogen atom or a (C1-C4)alkyl group such as methyl, and - R' representing a (C1-C4)alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, preferably methyl, ethyl or i-butyl; particularly methyl, ethyl or isobutyl, preferably (I) is chosen from methyl (meth)acrylate, ethyl
(meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate; and more preferentially chosen from methyl (meth)acrylate, ethyl (meth)acrylate and isobutyl (meth)acrylate; more preferentially (I) represents methyl acrylate, ethyl acrylate, isobutyl acrylate and isobutyl methacrylate. [Claim 4] Composition according to any one of the preceding claims, in which the oily dispersion is such that the a2) ethylenic monomer(s) comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl, such as benzyl, groups is (are) chosen from (1), (2), (3), and (4): (1) R1(R2)C=C(R3)-Acid with R1, R2 and R3 representing a hydrogen atom or a CO2H, H2PO4 or SO3H group, and Acid representing a carboxyl, phosphoric acid or sulfonic acid group, preferably carboxyl group, preferably (1) represents (5) H2C=C(R)-C(O)-O-H with R representing a hydrogen atom or a (C1-C4)alkyl group such as methyl; (2) H2C=C(R)-C(O)-N(R')-Alk-Acid with R and R', which may be identical or different, representing a hydrogen atom or a (C1-C4)alkyl group; Alk represents a (C1-C6)alkylene group optionally substituted with at least one group chosen from Acid as defined previously and hydroxyl; and Acid is as defined previously, preferably carboxyl or sulfonic acid; (3) Ar-(Ra)C=C(Rb)-Rc with Ra, Rb and Rc, which may be identical or different, representing a hydrogen atom or a (C1-C4)alkyl group, and Ar representing an aryl group, preferably benzyl, optionally substituted with at least one acid group CO2H, H2PO4 or SO3H, preferably substituted with a CO2H or SO3H group, (4) maleic anhydride of formula (4a) and itaconic anhydride of formula (4b):
in which Ra, Rb and Rc, which may be identical or different, represent a hydrogen atom or a (C1-C4)alkyl group; preferably, Ra, Rb and Rc represent a hydrogen atom; preferentially, the ethylenically unsaturated anhydride monomer of the invention is of formula (4a) and more preferentially is maleic anhydride; more particularly a2) is chosen from (1) and (4), preferably (5). [Claim 5] Composition according to any one of the preceding claims, in which the oily dispersion is such that the a2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups is (are) chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid, acrylamidoglycolic acid, acrylic acid and salts thereof, more preferentially still a2) represents acrylic acid and salts thereof or maleic anhydride. [Claim 6] Composition according to any one of the preceding claims, in which the oily dispersion is such that the stabilizer(s) ii) is (are) constituted of ethylenic polymers chosen from: b) polymers of monomers of formula H2C=C(R)-C(O)-O-R'' (III) with R representing a hydrogen atom or (C1-C4)alkyl group such as methyl, and R'' representing a (C5-C10)cycloalkyl group such as norbornyl or isobornyl, preferably isobornyl; and c) the copolymers of c1) H2C=C(R)-C(O)-O-R'' (III) in which R and R'' have the same meanings indicated previously in b) and of c2) H2C=C(R)-C(O)-O-R' (I) in which R has the same meaning as that in formula (III) and R' represents a (C1-C4)alkyl group; more particularly, the stabilizer ii) is chosen from: isobornyl acrylate homopolymers, isobornyl acrylate/methyl acrylate statistical copolymers, isobornyl acrylate/ethyl acrylate statistical copolymers, and isobornyl acrylate/methyl acrylate/ethyl acrylate statistical copolymers. [Claim 7] Composition according to any one of Claims 1 to 5, in which the oily dispersion is such that the stabilizer(s) ii) is (are) chosen from polymers of
(C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate monomers; and c) statistical copolymers of c1) (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate and c2) (C1- C4)alkyl (C1-C4)(alkyl)acrylate with a c1/c2 weight ratio greater than 4, advantageously said weight ratio ranges from 4.5 to 19, preferentially said polymeric particles ranges from 5.5 to 12. [Claim 8] Composition according to any one of the preceding claims, in which the oily dispersion is such that the polymer of the particles i) comprises from 80% to 93% by weight of ingredient a1) notably C1-C4 alkyl (meth)acrylate and from 7% to 20% by weight of ingredient a2) relative to the total weight of the polymer i); more preferentially, the polymer of the particles i) comprises preferably from 85% to 93% by weight, more particularly 87% to 92% by weight, more preferentially still from 85% to 90% by weight, of ingredient a1) notably C1-C4 alkyl (meth)acrylate and from 10% to 20% by weight of ingredient a2) relative to the total weight of the polymer i). [Claim 9] Composition according to Claims 1 to 5, in which the oily dispersion is such that the stabilizer(s) ii) is (are) chosen from c) the copolymers of c1) (C3-C12)cycloalkyl (C1-C6)(alkyl)acrylate and c2) (C1- C4)alkyl (C1-C4)(alkyl)acrylate with from 85% to 94% by weight of ingredient c1) notably isobornyl (meth)acrylate and from 5% to 20% by weight of ingredient c2) relative to the total weight of the stabilizer; more preferentially, the stabilizer(s) ii) comprises (comprise) from 85% to 98% by weight, more particularly 87% to 94% by weight of ingredient c1) notably isobornyl (meth)acrylate and from 10% to 20% by weight of ingredient c2) relative to the total weight of the stabilizer. [Claim 10] Composition according to any one of the preceding claims, where the polymer of the particles i) is present in the dispersion in a content ranging from 21% to 58.5% by weight, preferably ranging from 30% to 50% by weight relative to the total weight of the composition. [Claim 11] Composition according to any one of the preceding claims, in which the hydrocarbon-based oil(s) is (are) formed solely of carbon and hydrogen atoms; preferably chosen from: - linear or branched C8-C30, in particular C10-C20 and more particularly C10- C16 alkanes, which are volatile or non-volatile, preferably volatile;
- non-aromatic cyclic C5-C12 alkanes, which are volatile or non-volatile, preferably volatile; and - mixtures thereof; more preferentially chosen from the hydrocarbon-based oils having from 8 to 16 carbon atoms, in particular having from 10 to 14 carbon atoms, which are preferably volatile, more particularly: - isoalkanes of petroleum origin (isoparaffins); - linear alkanes; more preferentially still, the liquid hydrocarbon-based oil iii) is isododecane. [Claim 12] Composition according to any one of the preceding claims, in which the hydrocarbon-based oil(s) iii) is (are) in the oily dispersion in an amount of between 15% by weight and 80% by weight, more preferentially between 20% and 60% by weight relative to the total weight of said oily dispersion, more particularly still the weight ratio of the sum of the ingredients [i) + ii)] / iii) is less than or equal to 1, more particularly the [i) + ii)] / iii) weight ratio is between 0.5 and 1. [Claim 13] Composition according to any one of the preceding claims, where the polymer particles of the dispersion have an average size, in particular a number-average size, ranging from 50 to 500 nm, notably ranging from 75 to 400 nm and better still ranging from 100 to 250 nm. [Claim 14] Composition according to any one of the preceding claims, where the dispersion of particles i) is chosen from: - a dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (24.5/62.8/12.7) copolymer particles stabilized by an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the oily dispersion containing in total (stabilizer ii) + particles i)) 10% of acrylic acid, 20% of methyl acrylate, 50% of ethyl acrylate and 20% of isobornyl acrylate; - a dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (11.7/75.6/12.7) copolymer particles stabilized by an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the oily dispersion containing in total (stabilizer ii) + particles i)) 10% of acrylic acid, 10% of methyl acrylate, 60% of ethyl acrylate and 20% of isobornyl acrylate;
- a dispersion in isododecane of methyl acrylate/ethyl acrylate/maleic anhydride (50/37.2/12.8) copolymer particles stabilized by an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the oily dispersion containing in total (stabilizer ii) + particles i)) 10% of maleic anhydride, 30% of methyl acrylate, 40% of ethyl acrylate and 20% of isobornyl acrylate. [Claim 15] Composition according to any one of the preceding claims, where the amount of oily dispersion of particles i) varies from 20% to 40% by weight, more preferentially from 25% to 35% by weight relative to the total weight of the composition. [Claim 16] Composition according to any one of the preceding claims, where the amount of water is greater than or equal to 2% by weight and less than 50% by weight relative to the total weight of the composition, more particularly the amount of water in the composition is between 5% and 49% by weight relative to the total weight of the composition, more particularly between 10% and 47% by weight, between 15% and 48% by weight, preferentially between 18% and 45%, more preferentially still between 20% and 40% by weight, relative to the total weight of the composition. [Claim 17] Composition according to any one of the preceding claims, where the colloidal silica particles are anionic and amorphous. [Claim 18] Composition according to Claim 13, where the anionic colloidal silica particles are monodisperse. [Claim 19] Composition according to Claim 13 or 14, where the colloidal silica particles have an average diameter of between 3 and 100 nm, preferably between 3 and 50 nm and more preferentially between 5 and 10 nm. [Claim 20] Composition according to any one of Claims 13 to 15, where the specific surface area of the anionic colloidal silica particles varies in general from 50 to 500 m2/g SiO2. [Claim 21] Composition according to any one of the preceding claims, where the amount of aqueous dispersion of colloidal silica particles varies
from 5% to 20% by weight, more preferentially from 5% to 15% by weight relative to the total weight of the composition. [Claim 22] Composition according to any one of the preceding claims, where the weight ratio of the oily dispersion of polymer particles i) to the aqueous dispersion of colloidal silica particles varies from 2 to 6, more preferentially from 2 to 5. [Claim 23] Composition according to any one of the preceding claims, comprising one or more waxes in an amount of less than 5.0% by weight relative to the total weight of the composition. [Claim 24] Composition according to any one of the preceding claims, comprising at least one colorant, in particular chosen from pulverulent colorants, water-soluble dyes and mixtures thereof. [Claim 25] Composition according to Claim 18, where the colorant(s) is (are) present in a total content ranging from 2.0% to 25.0% by weight, preferably from 3.0% to 20.0% by weight, more particularly from 4.0% to 15.0% by weight, relative to the total weight of the composition. [Claim 26] Composition according to any one of the preceding claims, comprising one or more non-volatile oils, preferably in a total concentration of less than 10.0% by weight relative to the total weight of the composition. [Claim 27] Method for making up and/or caring for keratin materials consisting in applying to the surface of said materials at least one composition as defined in any one of the preceding claims.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FRFR2013679 | 2020-12-18 | ||
| FR2013679A FR3117793A1 (en) | 2020-12-18 | 2020-12-18 | Cosmetic composition comprising an oily dispersion of polymer particles and an aqueous dispersion of colloidal silica particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022128544A1 true WO2022128544A1 (en) | 2022-06-23 |
Family
ID=75339859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2021/084235 Ceased WO2022128544A1 (en) | 2020-12-18 | 2021-12-03 | Cosmetic composition comprising an oily dispersion of polymer particles and an aqueous dispersion of colloidal silica particles |
Country Status (2)
| Country | Link |
|---|---|
| FR (1) | FR3117793A1 (en) |
| WO (1) | WO2022128544A1 (en) |
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|---|---|
| FR3117793A1 (en) | 2022-06-24 |
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