WO2017167667A1 - Aqueous emulsion comprising a silicone-based dendritic polymer, a silicone gum and a semi-crystalline polymer or a wax and treatment of the lips - Google Patents

Aqueous emulsion comprising a silicone-based dendritic polymer, a silicone gum and a semi-crystalline polymer or a wax and treatment of the lips Download PDF

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Publication number
WO2017167667A1
WO2017167667A1 PCT/EP2017/057122 EP2017057122W WO2017167667A1 WO 2017167667 A1 WO2017167667 A1 WO 2017167667A1 EP 2017057122 W EP2017057122 W EP 2017057122W WO 2017167667 A1 WO2017167667 A1 WO 2017167667A1
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chosen
weight
alkyl
carbon atoms
composition
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PCT/EP2017/057122
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French (fr)
Inventor
Florence Lahousse
Pascaline Cordelette
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L'oreal
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Priority claimed from FR1652846A external-priority patent/FR3049458B1/en
Priority claimed from FR1652845A external-priority patent/FR3049457B1/en
Application filed by L'oreal filed Critical L'oreal
Publication of WO2017167667A1 publication Critical patent/WO2017167667A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/04Preparations containing skin colorants, e.g. pigments for lips
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0295Liquid crystals
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/064Water-in-oil emulsions, e.g. Water-in-silicone emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/91Graft copolymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/001Preparations for care of the lips
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/544Dendrimers, Hyperbranched polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/548Associative polymers

Definitions

  • the present invention relates to a cosmetic composition for making up and/or caring for in particular the lips, in the form of an emulsion comprising an aqueous phase, at least one silicone-based dendritic film-forming polymer, at least one non-volatile oil, at least one silicone gum and at least one semi-crystalline polymer or at least one wax.
  • the present invention also relates to a makeup and/or care process, preferably for the lips, which consists in applying said composition, and also to a device suitable for the composition.
  • compositions for making up and/or caring for the lips in particular fluid compositions such as liquid lipsticks, which are stable and endowed with satisfactory properties in terms of application (glidance on application, ease of spreading and fineness of the deposit), but also in terms of the makeup effect of the deposit on the lips, for instance the absence of migration of the deposit, preferably without becoming tacky, is an ongoing objective.
  • lip glosses are anhydrous formulations whose relatively viscous texture is usually applied by means of a brush dipping into the composition.
  • the deposit is relatively thick, which gives it a more or less tacky nature, especially induced by the use of ingredients, in particular nonvolatile oils or polymers that provide gloss.
  • This tacky nature may be reflected by adhesion of the made-up lips to each other, resulting in a sensation of discomfort to the user.
  • the coverage of the deposit is variable and it has rather limited persistence.
  • compositions As examples of such compositions, mention may be made especially of those described in patent applications WO 2014/154700 and WO 2014/154701 , which are thus in emulsion form, comprising water, non-volatile and volatile oils and an acrylic film-forming polymer bearing silicone dendrimer-based units. These compositions make it possible to obtain an extremely thin deposit, which is virtually imperceptible on the lips, highly coloured and covering, non-tacky, non-migrating and with a matte result due to the large amounts of volatile species initially present in the composition.
  • the invention also relates to a make-up and/or care composition, in particular for the lips, comprising:
  • the invention also relates to a process for making up and/or caring for the lips, which consists in applying said composition, and also to a device comprising the composition and suitable for using same.
  • the compositions according to the invention are very fluid, homogeneous and stable over time, without sedimentation, for example of the pigments or fillers present, or exudation, in particular of the oil(s) present.
  • the deposited film has the advantage of always being very thin, homogeneous, allowing a precise contour to be defined on the lips.
  • the deposit obtained is comfortable, not only in the sense that it is flexible on the lips and does not cause any sensation of dryness thereon, but also because it remains mobile and modulable once applied, without degradation of the other performance qualities, especially the absence of migration and the persistence.
  • the cosmetic composition for making up and/or caring for the lips according to the invention is in the form of an emulsion, especially a water-in-oil (inverse) or oil-in-water (direct) emulsion, preferably in the form of an (inverse) water-in-oil emulsion.
  • composition according to the invention is in the form of a liquid emulsion.
  • liquid means a fluid texture, the viscosity of which at 25°C is more particularly between 0.005 and 12 Pa.s, preferably between 0.01 and 10 Pa.s and even more advantageously between 0.05 and 8 Pa.s.
  • the viscosity at 25°C of a composition according to the invention is between 0.1 and 6 Pa.s.
  • the viscosity measurement is generally performed at 25°C, using a Rheomat RM180 viscometer equipped with a No. 2 or 3 spindle, the measurement being performed after 10 minutes of rotation of the spindle in the composition, at a shear rate of 200 rpm.
  • composition according to the invention comprises at least one film-forming polymer chosen from vinyl polymers comprising at least one carbosiloxane dendrimer-based unit.
  • film-forming polymer is intended to mean a polymer that is capable of forming, by itself or in the presence of an auxiliary film-forming agent, a continuous deposit on a support, in particular on keratin materials.
  • the vinyl polymer(s) have a backbone and at least one side chain, which comprises a carbosiloxane dendrimer-based unit having a carbosiloxane dendrimer structure.
  • carbosiloxane dendrimer structure in the context of the present invention represents a molecular structure bearing branched groups of high molecular masses, said structure having high regularity in the radial direction starting from the bond to the backbone.
  • Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer in Japanese patent application JP 9-171 154.
  • a vinyl polymer according to the invention may contain carbosiloxane dendrimer-based units that may be represented by the general formula (I) below:
  • R j1 represents an aryl group containing from 5 to 10 carbon atoms or an alkyl group containing from 1 to 10 carbon atoms;
  • R 1 is as defined above in formula (I),
  • R 2 represents an alkylene radical containing from 2 to 10 carbon atoms
  • R 3 represents an alkyl group containing from 1 to 10 carbon atoms
  • . i is an integer from 1 to 10 which represents the generation of said silylalkyi group, and . a' is an integer from 0 to 3;
  • - Y represents a radical-polymerizable organic group chosen from:
  • organic groups containing a methacrylic group or an acrylic group said organic groups being represented by the formulae:
  • R 4 represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms
  • R 5 represents an alkylene group containing from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, methylene and propylene groups being preferred;
  • R 6 represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, the methyl group being preferred;
  • R 7 represents an alkyl group containing from 1 to 10 carbon atoms
  • R represents an alkylene group containing from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, the ethylene group being preferred
  • * b is an integer from 0 to 4.
  • * c is 0 or 1 , such that, if c is 0, -(R 8 ) c - represents a bond.
  • R 1 may represent an aryl group containing from 5 to 10 carbon atoms or an alkyi group containing from 1 to 10 carbon atoms.
  • the alkyi group may preferably be represented by a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group or a cyclohexyl group.
  • the aryl group may preferably be represented by a phenyl group and a naphthyl group. The methyl and phenyl groups are more particularly preferred, and the methyl group is preferred among all.
  • R 2 represents an alkylene group containing from 2 to 10 carbon atoms, in particular a linear alkylene group, such as an ethylene, propylene, butylene or hexylene group; or a branched alkylene group, such as a methylmethylene, methylethylene, 1 -methylpentylene or 1 ,4-dimethylbutylene group.
  • a linear alkylene group such as an ethylene, propylene, butylene or hexylene group
  • a branched alkylene group such as a methylmethylene, methylethylene, 1 -methylpentylene or 1 ,4-dimethylbutylene group.
  • the ethylene, methylethylene, hexylene, 1 -methylpentylene and 1 ,4-dimethylbutylene groups are preferred among all.
  • R 3 is chosen from methyl, ethyl, propyl, butyl and isopropyl groups.
  • i indicates the number of generations and thus corresponds to the number of repeats of the silylalkyl group.
  • the carbosiloxane dendrimer may be represented by the general formula shown below, in which Y, R 1 , R 2 and R 3 are as defined above, R 12 represents a hydrogen atom or is identical to R 1 ; a 1 is identical to a'.
  • the total average number of groups OR 3 in a molecule is within the range from 0 to 7.
  • the carbosiloxane dendrimer may be represented by the general formula below, in which Y, R 1 , R 2 , R 3 and R 12 are the same as defined above; a 1 and a 2 represent the a' of the indicated generation.
  • the total average number of groups OR 3 in a molecule is within the range from 0 to 25.
  • the carbosiloxane dendrimer is represented by the general formula below, in which Y, R 1 , R 2 , R 3 and R 12 are the same as defined above; a 1 , a 2 and a 3 represent the a' of the indicated generation.
  • the total average number of groups OR 3 in a molecule is within the range from 0 to 79.
  • a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit has a molecular side chain containing a carbosiloxane dendrimer structure, and may be derived from the polymerization of:
  • the monomer of vinyl type that is the component (A) in the vinyl polymer bearing at least one carbosiloxane dendrimer-based unit is a monomer of vinyl type that contains a radical-polymerizable vinyl group.
  • this monomer of vinyl type methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate or a methacrylate of lower alkyl analogue; glycidyl methacrylate; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate or a higher methacrylate analogue; vinyl acetate, vinyl propionate or a vinyl ester of a lower fatty acid
  • Multifunctional monomers of vinyl type may also be used.
  • the following represent examples of such compounds: trimethylolpropane tnmethacrylate, pentaerythrityl tnmethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1 ,4-butanediol dimethacrylate, 1 ,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl methacrylate, tris(2-hydroxyethyl)isocyanurate dimethacrylate, tris(2-hydroxyethyl)isocyanurate tnmethacrylate, polydimethylsiloxane capped with styryl groups containing divinylbenzene groups on both ends, or similar silicone compounds containing unsaturated groups.
  • a carbosiloxane dendrimer which is the component (B), may be represented by formula (I) as defined above.
  • group Y of formula (I) an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3- methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4-(2- propenyl)phenyl group, a 3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a 2-(3- vinylphenyl)ethyl group, a vinyl group, an allyl group, a methallyl group and a 5-hexenyl group.
  • a carbosiloxane dendrimer according to the present invention may be represented by the formulae having the average structures below:
  • the carbosiloxane dendrimer of the composition according to the present invention is represented by the following formula:
  • Y, R 1 , R 2 and R 3 are as defined in formulae (I) and (II) above;
  • a 1 , a 2 and a 3 correspond to the definition of a' according to formula (II);
  • R 12 is H, an aryl group containing from 5 to 10 carbon atoms or an alkyl group containing from 1 to 10 carbon atoms.
  • the carbosiloxane dendrimer of the composition according to the present invention is represented by one of the following formulae:
  • the vinyl polymer comprising the carbosiloxane dendrimer according to the invention may be manufactured according to the process for manufacturing a branched silalkylene siloxane described in Japanese patent application Hei 9-171 154.
  • the number- average molecular weight of the vinyl polymer bearing a carbosiloxane dendrimer may be chosen within the range between 3000 and 2 000 000 g/mol and preferably between 5000 and 800 000 g/mol. It may be a liquid, a gum, a paste, a solid, a powder, or any other form.
  • the preferred forms are solutions consisting of the dilution of a dispersion or of a powder in solvents.
  • the vinyl polymer may be a dispersion of a polymer of vinyl type bearing a carbosiloxane dendrimer structure in its side molecular chain, in a liquid such as a silicone oil, an organic oil, an alcohol or water.
  • the silicone oil may be a dimethylpolysiloxane having the two molecular ends capped with trimethylsiloxy groups, a copolymer of methylphenylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, a copolymer of methyl- 3,3,3-trifluoropropylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, or similar unreactive linear silicone oils, and also hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane or a similar cyclic compound.
  • modified polysiloxanes containing functional groups such as silanol groups, amino groups and polyether groups on the ends or within the molecular side chains may be used.
  • the organic oils may be isododecane, liquid paraffin, isoparaffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum oil, sunflower oil, soybean oil, camelia oil, squalane, castor oil, cottonseed oil, coconut oil, egg yolk oil, polypropylene glycol monooleate, neopentyl glycol 2-ethylhexanoate or
  • the alcohol may be any type that is suitable for use in combination with a cosmetic product starting material.
  • it may be methanol, ethanol, butanol, isopropanol or similar lower alcohols.
  • a solution or a dispersion of the alcohol should have a viscosity within the range from 10 to 10 9 mPa at 25°C. To improve the sensory use properties in a cosmetic product, the viscosity should be within the range from 100 to 5 ⁇ 10 8 mPa.s.
  • the solutions and dispersions may be readily prepared by mixing a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit with a silicone oil, an organic oil, an alcohol or water.
  • the liquids may be present in the polymerization step.
  • the unreacted residual vinyl monomer should be completely removed by heat treatment of the solution or dispersion under atmospheric pressure or reduced pressure.
  • the dispersity of the polymer of vinyl type may be improved by adding a surfactant.
  • Such an agent may be hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid or anionic surfactants of the sodium salts of these acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow-trimethylammonium hydroxide, coconut oil-trimethylammonium hydroxide, or a similar cationic surfactant; a polyoxyalkylene alkyl ether, a
  • a mean particle diameter of the polymer of vinyl type may be within a range of between 0.001 and 100 microns and preferably between 0.01 and 50 microns. The reason for this is that, outside the recommended range, a cosmetic product mixed with the emulsion will not have a nice enough feel on the lips or to the touch, nor sufficient spreading properties nor a pleasant feel.
  • a vinyl polymer contained in the dispersion or the solution may have a concentration within a range of between 0.1% and 95% by weight and preferably between 5% and 85% by weight. However, to facilitate the handling and the preparation of the mixture, the range should preferably be between 10% and 75% by weight.
  • a vinyl polymer that is suitable for use in the invention may also be one of the polymers described in the examples of patent application EP 0 963 751.
  • a vinyl polymer grafted with a carbosiloxane dendrimer may be the product of polymerization of:
  • (A1 ) from 0 to 99.9 part by weight of one or more acrylate or methacrylate monomers; and (B1 ) from 100 to 0.1 part by weight of an acrylate or methacrylate monomer of a tris[tri(trimethylsiloxy)silylethyldimethylsiloxy]silylpropyl carbosiloxane dendrimer.
  • the monomers (A1 ) and (B1 ) correspond respectively to specific monomers (A) and
  • a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit may comprise a tris[tri(trimethylsiloxy)silylethyldimethylsiloxy]silylpropyl carbosiloxane dendrimer-based unit corresponding to one of the formulae:
  • a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit used in the invention comprises at least one butyl acrylate monomer.
  • a vinyl polymer may also comprise at least one fluoro organic group.
  • polymerized vinyl units constitute the backbone and carbosiloxane dendritic structures and also fluoro organic groups are attached to side chains are particularly preferred.
  • the fluoro organic groups may be obtained by replacing with fluorine atoms all or some of the hydrogen atoms of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl groups and other alkyl groups of 1 to 20 carbon atoms, and also alkyloxyalkylene groups of 6 to 22 carbon atoms.
  • the groups represented by the formula -(CH 2 )x-(CF 2 ) y -R 13 are suggested as examples of fluoroalkyl groups obtained by substituting fluorine atoms for hydrogen atoms of alkyl groups.
  • the index "x" is 0, 1 , 2 or 3
  • "y" is an integer from 1 to 20.
  • R 13 is an atom or a group chosen from a hydrogen atom, a fluorine atom, -CH(CF 3 ) 2 - or CF(CF 3 ) 2 .
  • Such fluorine-substituted alkyl groups are exemplified by linear or branched polyfluoroalkyi or perfluoroalkyl groups represented by the formulae shown below:
  • the groups represented by -CH 2 CH 2 -(CF 2 ) m -CFR 14 -[OCF 2 CF(CF 3 )] n -OC 3 F 7 are suggested as fluoroalkyloxyfluoroalkylene groups obtained by substituting fluorine atoms for hydrogen atoms of alkyloxyalkylene groups.
  • the index "m” is 0 or 1
  • "n" is 0, 1 , 2, 3, 4 or 5
  • R 14 is a fluorine atom or CF 3 .
  • fluoroalkyloxyfluoroalkylene groups are exemplified by the perfluoroalkyloxyfluoroalkylene groups represented by the formulae shown below: -CH 2 CH 2 CF(CF 3 )-[OCF 2 CF(CF 3 )] n -OC 3 F 7 , -CH 2 CH 2 CF 2 CF 2 -[OCF 2 CF(CF 3 )] n - OC 3 F 7 .
  • the number-average molecular weight of the vinyl polymer used in the present invention may be between 3000 and 2 000 000 g/mol and more preferably between 5000 and 800 000 g/mol.
  • This type of fluorinated vinyl polymer may be obtained by addition:
  • a composition of the invention may comprise a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit and being derived from the copolymerization of a vinyl monomer (M1 ) as defined above, optionally of a vinyl monomer (M2) as defined above, and of a carbosiloxane dendrimer (B) as defined above, said vinyl polymer having a copolymerization ratio between the monomer (M1 ) and the monomer (M2) of from 0.1% to 100%/99.9% to 0% by weight, and a copolymerization ratio between the sum of the monomers (M1 ) and (M2) and the monomer (B) of from 0.1 % to 99.9%/99.9% to 0.1 % by weight.
  • the vinyl monomers (M1 ) containing fluoro organic groups in the molecule are preferably monomers represented by the general formula:
  • R 15 is a hydrogen atom or a methyl group and R f is a fluoro organic group exemplified by the fluoroalkyl and fluoroalkyloxyfluoroalkylene groups described above.
  • the compounds represented by the formulae presented below are suggested as specific examples of the component (M1 ). In the formulae present below, "z" is an integer from 1 to 4.
  • CH 2 CCH 3 COO-CF 3
  • CH 2 CCH 3 COO-C 2 F 5
  • CH 2 CCH3COO-nC 3 F 7 ,
  • CH 2 CCH 3 COO-CF(CF 3 ) 2
  • CH 2 CCH 3 COO-nC 4 F 9
  • CH 2 CCH 3 COO-CF(CF 3 ) 2
  • CH 2 CCH 3 COO-nC 5 Fn
  • CH 2 CCH 3 COO-nC 6 F 13
  • CH 2 CCH 3 COO-nC 8 F 17
  • CH 2 CCH 3 COO-CH 2 CF 3
  • CH 2 CCH 3 COO-CH(CF 3 ) 2
  • CH 2 CCH 3 COO-CH 2 CH(CF 3 ) 2
  • CH 2 CCH 3 COO-CH 2 (CF 2 ) 2 F
  • CH 2 CCH 3 COO-CH 2 (CF 2 ) 2 F
  • CH 2 CCH 3 COO-CH 2 (CF 2 ) 4 F
  • CH 2 CCH 3 COO-CH 2 (CF 2 ) 6 F
  • CH 2 CCH 3 COO-CH 2 (CF 2 ) 8 F
  • CH 2 CCH 3 COO-CH 2 CH 2 CF 3
  • CH 2 CCH 3 COO-CH 2 CH 2 (CF 2 ) 2 F
  • CH 2 CCH 3 COO-CH 2 CH 2 (CF 2 ) 3 F
  • CH 2 CCH 3 COO-CH 2 CH 2 (CF 2 ) 4 F
  • CH 2 CCH 3 COO-CH 2 CH 2 (CF 2 ) 6 F
  • CH 2 CCH 3 COO-CH 2 CH 2 (CF 2 ) 8 F
  • CH 2 CCH 3 COO-CH 2 CH 2 (CF 2 ) 10 F
  • CH 2 CCH 3 COO-CH 2 -CH 2 -(CF 2 ) 16 F
  • CH 2 CCH 3 COO-CH 2 CH 2 CH 2 CF 3
  • CH 2 CCH 3 COO-CH 2 CH 2 CH 2 (CF 2 ) 2 F
  • CH 2 CCH 3 COO-CH 2 CH 2 CH 2 (CF 2 ) 2 H
  • CH 2 CCH 3 COO-CH 2 (CF 2 ) 4 H
  • CH 2 CCH 3 COO-(CF2)3H
  • CH 2 CCH 3 COO-CH 2 CH2CF(CF3)-[OCF 2 -CF(CF3)]z-OC3F 7 ,
  • CH 2 CCH 3 COO-CH 2 CH 2 CF 2 CF 2 -[OCF 2 -CF(CF 3 )]z-OC 3 F 7 ,
  • CH 2 CHCOO-CF 3
  • CH2 CHCOO-C 2 F 5
  • CH 2 CHCOO-nC 3 F 7 ,
  • CH 2 CHCOO-CF(CF 3 ) 2
  • CH 2 CHCOO-nC 4 F 9
  • CH 2 CHCOO-CF 2 CF(CF 3 ) 2
  • CH 2 CHCOO-nC 5 F 11
  • CH 2 CHCOO-nC 6 F 13
  • CH 2 CHCOO-nC 8 F 17
  • CH 2 CHCOO-CH 2 CF 3
  • CH 2 CHCOO-CH(CF 3 ) 2
  • CH 2 CHCOO-CH 2 CH(CF 3 ) 2
  • CH 2 CHCOO-CH 2 (CF 2 ) 2 F
  • CH 2 CHCOO-CH 2 (CF 2 ) 3 F
  • CH 2 CHCOO-CH 2 (CF 2 ) 4 F
  • CH 2 CHCOO-CH 2 (CF 2 ) 6 F
  • CH 2 CHCOO-CH 2 (CF 2 ) 8 F
  • CH 2 CHCOO-CH 2 CH 2 CF 3
  • CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 2 F
  • CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 3 F
  • CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 4 F
  • CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 6 F
  • CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 8 F
  • CH 2 HCOO-CH 2 CH 2 (CF 2 ) 10 F
  • CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 16 F
  • CH 2 CHCOO-CH 2 CH 2 CH 2 CF 3
  • CH 2 CHCOO-CH 2 CH 2 CH 2 (CF 2 ) 2 F
  • CH 2 CHCOO-CH 2 CH 2 CH 2 (CF) 2 H
  • CH 2 CHCOO-CH 2 (CF 2 ) 4 H
  • CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 3 H
  • CH 2 CHCOO-CH 2 CH 2 CF(CF 3 )-, [OCF 2 -CF(CF 3 )] z -OC 3 F 7 ,
  • CH 2 CHCOO-CH 2 CH 2 CF 2 CF 2 (CF 3 )-[OCF 2 -CF(CF 3 )] 2 -OC 3 F 7 .
  • vinyl polymers represented below are preferred:
  • CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 6 F
  • CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 8 F
  • CH 2 CCH 3 COO-CH 2 CH 2 (CF 2 ) 6 F
  • CH 2 CCH 3 COO-CH 2 CH 2 (CF 2 ) 8 F
  • CH 2 CHCOO-CH 2 CF 3
  • CH 2 CCH 3 COO-CH 2 CF 3 .
  • CH 2 CCHCOO-CH 2 CF 3 .
  • the vinyl monomers (M2) not containing any fluoro organic groups in the molecule may be any monomers containing radical-polymerizable vinyl groups which are exemplified, for example, by methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and other lower alkyl acrylates or methacrylates; glycidyl acrylate, glycidyl methacrylate; n-butyl acrylate, n- butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl acrylate,
  • vinyl monomers (M2) the polyfunctional vinyl monomers illustrated, for example, by trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythrityl triacrylate, pentaerythrityl trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1 ,4- butanediol diacrylate, 1 ,4-butanediol dimethacrylate, 1 ,6-hexanediol diacrylate, 1 ,6- hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl acrylate, tri
  • Y can be chosen, for example, from organic groups containing acrylic or methacrylic groups, organic groups containing an alkenylaryl group, or alkenyl groups containing from 2 to 10 carbon atoms.
  • organic groups containing acrylic or methacrylic groups and the alkenylaryl groups are as defined above.
  • H 2 C CH-Si- -o— Si- -C 2 H 4 - -Si- -o- -Si-CH
  • the carbosiloxane dendrimers (B) may be prepared using the process for preparing siloxane/silalkylene branched copolymers described in document EP 1 055 674.
  • they may be prepared by subjecting organic alkenyl silicone compounds and silicone compounds comprising hydrogen atoms bonded to the silicon, represented by formula (IV) as defined above, to a hydrosilylation reaction.
  • the copolymerization ratio (by weight) between the monomer (B) and the monomers (M1 ) and (M2) is preferably within the range of 1 :99 to 99:1 and even more preferably within the range of 5:95 to 95:5.
  • Amino groups may be introduced into the side chains of the vinyl polymer by using, included in component (M2), vinyl monomers containing amino groups, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, followed by performing a modification with potassium acetate monochloride, ammonium acetate monochloride, the aminomethylpropanol salt of monochloroacetic acid, the triethanolamine salt of monobromoacetic acid, sodium monochloropropionate, and other alkali metal salts of halogenated fatty acids.
  • component (M2) vinyl monomers containing amino groups, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, followed by performing a modification
  • carboxylic acid groups may be introduced into the side chains of the vinyl polymer by using, included in component (M2), vinyl monomers containing carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid, and the like, followed by neutralizing the product with triethylamine, diethylamine, triethanolamine and other amines.
  • carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid, and the like
  • a fluorinated vinyl polymer may be one of the polymers described in the examples of patent application WO 03/045 337.
  • a vinyl polymer grafted in the sense of the present invention may be conveyed in an oil or a mixture of oils, which is/are preferably volatile, chosen in particular from silicone oils and hydrocarbon-based oils, and mixtures thereof.
  • a silicone oil that is suitable for use in the invention may be cyclopentasiloxane.
  • a hydrocarbon-based oil that is suitable for use in the invention may be isododecane.
  • Vinyl polymers grafted with at least one carbosiloxane dendrimer-based unit that may be particularly suitable for use in the present invention are the polymers whose I NCI name is Acrylates/polytrimethylsiloxy methacrylate copolymer, and especially sold under the names FA 4002 ID Silicone Acrylate, FA 4001 CM Silicone Acrylate by the company Dow Corning.
  • the composition according to the present invention comprises at least one vinyl polymer bearing at least one carbosiloxane dendrimer-based unit in an active material content ranging from 0.5% to 20% by weight, in particular from 1 % to 15% by weight, more particularly from 1 .5% to 10% by weight and preferably from 3% to 5% by weight, relative to the total weight of the composition.
  • composition according to the invention also comprises at least one non-volatile oil.
  • oil means a water-immiscible non-aqueous compound, which is liquid at 25°C and atmospheric pressure (1.013x10 5 Pa).
  • the term "immiscible" means that the mixture of the same amount of water and of oil, after stirring, does not lead to a stable solution comprising only one phase, under the above- mentioned temperature and pressure conditions.
  • the observation is made by eye or using a phase-contrast microscope, if necessary, on 100 g of mixture obtained after sufficient stirring using a ayneri blender to create a vortex in the mixture (as a guide, 200 to 1000 rpm); the resulting mixture being left to stand, in a closed bottle, for 24 hours at room temperature before observation.
  • non-volatile oil means an oil whose vapour pressure at 25°C is non-zero and is less than 10 ⁇ 3 mmHg (0.13 Pa) ("closed cup”).
  • the composition comprises at least one non-volatile oil in a content of at least 5% by weight, preferably ranging from 5% to 30% by weight, more particularly from 10% to 20% by weight relative to the total weight of the composition.
  • the composition comprises at least one non-volatile oil in a content varying from 25% to 60% by weight and preferably from 30% to 50% by weight relative to the total weight of volatile and non-volatile oil(s) present in said composition.
  • At least one of the nonvolatile oils is compatible with the film-forming polymer, if appropriate conveyed in an oil or a mixture of oils, which are preferably volatile, used in the composition according to the invention.
  • an oil or a mixture of oils which are preferably volatile, used in the composition according to the invention.
  • several mixtures of the non-volatile oil to be tested were made with the film-forming polymer, where appropriate conveyed in at least one oil, preferably a volatile oil: 30/70; 50/50; 70/30 (the ratios being expressed as weight, each mixture representing 10 g).
  • Each mixture is prepared at 25°C with stirring (magnetic bar) for one hour.
  • Non-volatile oils that are compatible in all the tested mixtures are more particularly suitable for use. Use may also be made of non-volatile oils that are compatible for some of the tested mixtures, if these oils are used in the composition in a content in which they are compatible. If necessary, on the basis of the results obtained previously, one or more tests may be repeated to check the compatibility at the envisaged content.
  • the non-volatile oil(s) may be chosen from polar or apolar hydrocarbon-based oils, silicone oils and fluoro oils, and mixtures thereof.
  • Polar non-volatile hydrocarbon-based oils may be chosen from polar or apolar hydrocarbon-based oils, silicone oils and fluoro oils, and mixtures thereof.
  • hydrocarbon-based oi! means an oil formed essentially from, or even consisting of, carbon and hydrogen atoms, and possibly 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 in addition to being free of silicon and fluorine, is free of heteroatoms such as nitrogen, sulfur and phosphorus.
  • the hydrocarbon-based oil is therefore different from a silicone oil and from a fluoro oil.
  • the polar non-volatile hydrocarbon-based oil comprises at least one oxygen atom.
  • this non-volatile hydrocarbon-based oil comprises at least one alcohol function (it is then an “alcohol oil”) and/or at least one ester function (it is then an “ester oil”).
  • the ester oils that may be used in the compositions according to the invention may in particular be hydroxylated.
  • the composition may comprise one or more non-volatile hydrocarbon-based oils, in particular chosen from:
  • the Ci 0 -C 2 6 alcohols are saturated or unsaturated, and branched or unbranched, and comprise from 10 to 26 carbon atoms.
  • the C 1 0-C26 alcohols are fatty alcohols, which are preferably branched when they comprise at least 16 carbon atoms.
  • fatty alcohols that may be used according to the invention, mention may be made of linear or branched fatty alcohols, of synthetic origin or alternatively of natural origin, for instance alcohols derived from plant material (coconut, palm kernel, palm, etc.) or animal material (tallow, etc.).
  • alcohols of natural origin for instance coconut (C 12 to Ci 6 ) or tallow (Ci S to Ci 8 ) or compounds of diol or cholesterol type.
  • Use is preferably made of a fatty alcohol comprising from 10 to 24 carbon atoms and more preferentially from 12 to 22 carbon atoms.
  • fatty alcohols that may preferably be used, mention may be made especially of lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2-butyloctanol, 2- undecylpentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol and octyldodecanol, and mixtures thereof.
  • the alcohol is chosen from octyldodecanol.
  • hydroxylated triesters of a C 2 -C 8 tricarboxylic acid and of a C 2 -C 8 alcohol such as citric acid esters, such as trioctyl citrate, triethyl citrate, acetyl tributyl citrate, tributyl citrate or acetyl tributyl citrate;
  • esters of a C?-C 8 polyol and of one or more C?-C 8 carboxylic acids such as glycol diesters of monoacids, such as neopentyl glycol diheptanoate, or glycol triesters of monoacids, such as triacetin;
  • Examples that may be mentioned include monoesters, diesters or triesters.
  • the ester oils may be hydroxylated or non-hydroxylated.
  • the non-volatile ester oil may for example be chosen from:
  • monoesters comprising between 18 and 40 carbon atoms in total, in particular the monoesters of formula RiCOOR 2 in which represents a saturated or unsaturated, linear or branched or aromatic fatty acid residue comprising from 4 to 40 carbon atoms and R 2 represents a hydrocarbon-based chain, which is in particular branched, containing from 4 to 40 carbon atoms, on condition that R-i + R 2 > 18, for instance Purcellin oil (cetostearyl octanoate), isononyl isononanoate, Ci 2 to Ci 5 alkyl benzoate, 2-ethylhexyl palmitate, octyldodecyl neopentanoate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, 2-octyldodecyl benzoate, alcohol or polyalcohol octanoates, de
  • esters of formula RiCOOR 2 in which R-i represents a linear or branched fatty acid residue containing from 4 to 40 carbon atoms and R 2 represents a hydrocarbon-based chain that is in particular branched, containing from 4 to 40 carbon atoms, Ri and R 2 being such that Ri + R 2 > 18.
  • the ester comprises between 18 and 40 carbon atoms in total.
  • Preferred monoesters that may be mentioned include isononyl isononanoate, oleyl erucate and/or 2-octyldodecyl neopentanoate.
  • monoesters of a fatty acid in particular of 18 to 22 carbon atoms, and in particular of lanolic acid, oleic acid, lauric acid or stearic acid, and of diols, for instance propylene glycol monoisostearate;
  • diesters in particular comprising between 18 and 60 carbon atoms in total and in particular between 18 and 50 carbon atoms in total.
  • Use may be made especially of diesters of a dicarboxylic acid and of monoalcohols, preferably such as diisostearyl malate, or glycol diesters of monocarboxylic acids, such as neopentyl glycol diheptanoate, propylene glycol dioctanoate, diethylene glycol diisononanoate or polyglyceryl-2 diisostearate (in particular such as the compound sold under the commercial reference Dermol DGDIS by the company Alzo);
  • hydroxylated monoesters and diesters preferably with a total carbon number ranging from 18 to 70, for instance polyglyceryl-3 diisostearate, isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate or glyceryl stearate;
  • triesters in particular comprising between 35 and 70 carbon atoms in total, in particular such as triesters of a tricarboxylic acid, such as triisostearyl citrate, or tridecyl trimellitate, or glycol triesters of monocarboxylic acids such as polyglyceryl-2 tri isostearate;
  • a tricarboxylic acid such as triisostearyl citrate, or tridecyl trimellitate
  • glycol triesters of monocarboxylic acids such as polyglyceryl-2 tri isostearate
  • tetraesters in particular with a total carbon number ranging from 35 to 70, such as pentaerythritol or polyglycerol tetraesters of a monocarboxylic acid, for instance pentaerythrityl tetrapelargonate, pentaerythrityl tetraisostearate, pentaerythrityl tetraisononanoate, glyceryl tris(2-decyl)tetradecanoate, polyglyceryl-2 tetraisostearate or pentaerythrityl tetrakis(2-decyl)tetradecanoate;
  • pentaerythritol or polyglycerol tetraesters of a monocarboxylic acid for instance pentaerythrityl tetrapelargonate, pentaerythrityl tetraisostearate, pentaerythrityl tetr
  • polyesters obtained by condensation of an unsaturated fatty acid dimer and/or trimer and of diol such as those described in patent application FR 0 853 634, in particular such as dilinoleic acid and 1 ,4-butanediol.
  • an unsaturated fatty acid dimer and/or trimer and of diol such as those described in patent application FR 0 853 634, in particular such as dilinoleic acid and 1 ,4-butanediol.
  • Viscoplast 14436H INCI name: dilinoleic acid/butanediol copolymer
  • copolymers of polyols and of diacid dimers, and esters thereof, such as Hailucent ISDA such as Hailucent ISDA
  • esters and polyesters of diol dimer and of monocarboxylic or dicarboxylic acid such as esters of diol dimer and of fatty acid and esters of diol dimer and of dicarboxylic acid dimer, in particular which may be obtained from a dicarboxylic acid dimer derived in particular from the dimerization of an unsaturated fatty acid especially of C 8 to C 34 , especially of C- 12 to C 22 , in particular of Ci 6 to C 2 o and more particularly of Ci 8 , such as esters of dilinoleic diacids and of dilinoleic diol dimers, for instance those sold by the company Nippon Fine Chemical under the trade names Lusplan DD-DA5 ® and DD-DA7 ® ;
  • hydrocarbon-based plant oils such as fatty acid triglycerides (which are liquid at room temperature), especially of fatty acids containing from 7 to 40 carbon atoms, such as heptanoic or octanoic acid triglycerides or jojoba oil; mention may be made in particular of saturated triglycerides such as caprylic/capric triglyceride and mixtures thereof, for example such as the product sold under the reference Myritol 318 from Cognis, glyceryl triheptanoate, glyceryl trioctanoate, and Ci 8 -36 acid triglycerides such as those sold under the reference Dub TGI 24 by Stearineries Dubois, and unsaturated triglycerides such as castor oil, olive oil, ximenia oil or pracaxi oil;
  • saturated triglycerides such as caprylic/capric triglyceride and mixtures thereof, for example such as the product sold under the reference
  • Ci?-C?fi fatty acids preferably C 12 -C 22 fatty acids, which are preferably unsaturated, such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof;
  • dialkyl carbonates the 2 alkyl chains possibly being identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC ® by Cognis;
  • composition according to the invention may also comprise at least one apolar nonvolatile hydrocarbon-based oil.
  • oils may be of plant, mineral or synthetic origin.
  • apolar hydrocarbon-based oil means an oil comprising only carbon and hydrogen atoms in its structure.
  • non-volatile apolar hydrocarbon-based oils are chosen from linear or branched hydrocarbons of mineral or synthetic origin, such as: liquid paraffin or derivatives thereof (mineral oil),
  • polyisobutenes hydrogenated polyisobutenes such as especially Parleam ® s sold by the company Nippon Oil Fats, Panalane H-300 E sold by the company Amoco, Viseal 20000 sold by the company Synteal and Rewopal PIB 1000 sold by the company Witco, or alternatively Parleam Lite sold by NOF Corporation,
  • polydecenes and hydrogenated polydecenes such as especially: Puresyn 10 and Puresyn 150, or alternatively Puresyn 6 sold by the company ExxonMobil Chemicals, - and mixtures thereof.
  • silicon o/T means an oil containing at least one silicon atom, and in particular containing Si-0 groups.
  • non-volatile silicone oils examples that may be mentioned include non-volatile non-phenyl silicone oils and nonvolatile phenyl silicone oils.
  • the silicone oils that may be used for the purposes of the invention advantageously have a molecular mass of less than or equal to 150 000 g/mol, preferably less than or equal to 100 000 g/mol and better still less than or equal to 10 000 g/mol.
  • Non-volatile non-phenyl silicone oils are non-volatile non-phenyl silicone oils
  • non-phenyl silicone oil denotes a silicone oil not comprising any phenyl substituents.
  • non-volatile non-phenyl silicone oils which may be mentioned include polydimethylsiloxanes; alkyl dimethicones; vinylmethyl methicones; and also silicones modified with aliphatic groups and/or with functional groups such as hydroxyl, thiol and/or amine groups, preferably hydroxyl groups.
  • dimethylsiloxane (INCI name) corresponds to a polydimethylsiloxane (chemical name).
  • oils can be chosen from the following non-volatile oils:
  • PDMS polydimethylsiloxanes
  • alkyl dimethicones comprising aliphatic groups, in particular alkyl or alkoxy groups, which are pendent and/or at the end of the silicone chain, these groups each comprising from 2 to 24 carbon atoms.
  • cetyl dimethicone sold under the commercial reference Abil Wax 9801 from Evonik Goldschmidt, PDMSs comprising functional groups such as hydroxyl, thiol and/or amine groups, preferably hydroxyl groups,
  • polydimethylsiloxanes substituted with aliphatic groups, in particular C2-C24 alkyl groups, pendent and/or at the end of the silicone chain, and functional groups such as hydroxyl, thiol and/or amine groups, preferably hydroxyl groups,
  • these non-volatile non-phenyl silicone oils are chosen from polydimethylsiloxanes; alkyl dimethicones and also polydimethylsiloxanes substituted with aliphatic groups, in particular C2-C24 alkyl groups, and functional groups such as hydroxyl groups.
  • the non-volatile non-phenyl silicone oil may be chosen in particular from silicones of formula (I):
  • Ri , R 2 , R5 and R 6 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms,
  • R 3 and R 4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms or a hydroxyl radical,
  • X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical, n and p are integers chosen so as to have a fluid compound, in particular whose viscosity at 25°C is between 8 centistokes (cSt) (8 x 10 "6 m 2 /s) and 800 000 cSt, advantageously less than 100 000 cSt, and advantageously a weight-average molecular mass of less than or equal to 150 000 g/mol, preferably less than or equal to 100 000 g/mol and better still less than or equal to 10 000 g/mol.
  • cSt centistokes
  • non-volatile non-phenyl silicone oils that may be used according to the invention, mention may be made of those for which:
  • the substituents Ri to R6 and X represent a methyl group, and p and n are such that the viscosity is 60 000 cSt, for example the product sold under the name Dow Corning 200 Fluid
  • phenyl silicone oil denotes a silicone oil bearing at least one phenyl substituent.
  • non-volatile phenyl silicone oils may be chosen from those also bearing at least one dimethicone fragment, or from those not bearing one.
  • dimethicone fragment denotes a divalent siloxane group whose silicon atom bears two methyl radicals, this group not being at the ends of the molecule. It may be represented by the following formula: -(Si(CH 3 ) 2 -0)-.
  • the non-volatile phenyl silicone oil may thus be chosen from:
  • phenyl silicone oils optionally bearing a dimethicone fragment corresponding to formula (I) below:
  • the groups R which are monovalent or divalent, represent, independently of each other, a methyl, methylene, phenyl or phenylene, with the proviso that at least one group R represents a phenyl.
  • the phenyl silicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six.
  • phenyl silicone oils optionally bearing a dimethicone fragment corresponding to formula (II) below:
  • groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl.
  • the compound of formula (II) comprises at least three, for example at least four or at least five, phenyl groups.
  • Examples that may be mentioned include mixtures of triphenyl-, tetraphenyl- or pentaphenyl-organopolysiloxanes.
  • phenyl silicone oils not bearing any dimethicone fragments, corresponding to formula (II) in which at least 4 or at least 5 radicals R represent a phenyl radical, the remaining radicals representing methyls.
  • non-volatile phenyl silicone oils are preferably trimethylpentaphenyltrisiloxane or tetramethyltetraphenyltrisiloxane. They are in particular sold by Dow Corning under the reference PH-1555 HRI or Dow Corning 555 Cosmetic Fluid (chemical name: 1 ,3,5-trimethyl-
  • phenyl silicone oils bearing at least one dimethicone fragment corresponding to formula (IV) below:
  • n, p and q are, independently of each other, integers between 0 and 900, with the proviso that the sum m+n+q is other than 0.
  • the sum m+n+q is between 1 and 100.
  • the sum m+n+p+q is between 1 and 900 and preferably between 1 and 800.
  • q is equal to 0.
  • R 0 independently of each other, represent a saturated or unsaturated, preferably saturated, linear or branched Ci-C 30 hydrocarbon-based radical, and in particular a preferably saturated, C C 2 o, in particular C Ci 8 , hydrocarbon-based radical, or a monocyclic or polycyclic C 6 -Ci 4 , and in particular C10-C13, aryl radical, or an aralkyl radical, the alkyl part of which is preferably C1-C3 alkyl.
  • Ri to R 10 may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical.
  • Ri to R10 may in particular be identical, and in addition may be a methyl radical.
  • o phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding
  • ⁇ Ri to R 6 independently of each other, are saturated or unsaturated, linear, cyclic or branched C1-C30 hydrocarbon-based radicals, a preferably C 6 -Ci 4 aryl radical or an aralkyl radical, the alkyl part of which is C1-C3 alkyl,
  • ⁇ m, n and p are, independently of each other, integers between 0 and 100, with the proviso that the sum n+m is between 1 and 100.
  • Ri to R 6 independently of each other, represent a C1-C20, in particular Ci- C18, hydrocarbon-based, preferably alkyl, radical, or a C 6 -Ci 4 aryl radical which is monocyclic (preferably C 6 ) or polycyclic and in particular C10-C13, or an aralkyl radical (preferably the aryl part is C 6 aryl; the alkyl part is C1-C3 alkyl).
  • Ri to R 6 may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical.
  • Ri to R6 may in particular be identical, and in addition may be a methyl radical.
  • m 1 or 2 or 3
  • the non-volatile phenyl silicone oil is chosen from phenyl silicone oils bearing at least one dimethicone fragment.
  • oils correspond to compounds of formula (VI) in which:
  • n and p are, independently of each other, integers between 1 and 100.
  • Ri to R 6 are methyl radicals.
  • the silicone oil is preferably chosen from a diphenyl dimethicone such as KF-54 from Shin-Etsu (400 cSt), KF54HV from Shin-Etsu (5000 cSt), KF-50-300CS from Shin-Etsu (300 cSt), KF-53 from Shin-Etsu (175 cSt) or KF-50-100CS from Shin-Etsu (100 cSt).
  • a diphenyl dimethicone such as KF-54 from Shin-Etsu (400 cSt), KF54HV from Shin-Etsu (5000 cSt), KF-50-300CS from Shin-Etsu (300 cSt), KF-53 from Shin-Etsu (175 cSt) or KF-50-100CS from Shin-Etsu (100 cSt).
  • phenyl silicone oils optionally bear at least one dimethicone fragment correspond more particularly to formula (VII) below:
  • -OSiMe 3 and p is 0 or is between 1 and 1000, and m is between 1 and 1000.
  • m and p are such that the compound (VII) is a non-volatile oil.
  • non-volatile phenyl silicone bearing at least one dimethicone fragment p is between 1 and 1000 and m is more particularly such that compound (VII) is a non-volatile oil.
  • Trimethylsiloxyphenyldimethicone sold in particular under the reference Belsil PDM 1000 by the company Wacker, may, for example, be used.
  • non-volatile phenyl silicone not bearing a dimethicone fragment p is equal to 0 and m is between 1 and 1000, and in particular is such that the compound (VII) is a non-volatile oil.
  • Phenyltrimethylsiloxytrisiloxane sold in particular under the reference Dow Corning 556 Cosmetic Grade Fluid (DC556), may, for example, be used.
  • DC556 Cosmetic Grade Fluid
  • Ci- C 3 o hydrocarbon-based radicals preferably R is a C1-C30 alkyl radical, a preferably C 6 -Ci 4 aryl radical, or an aralkyl radical, the alkyl part of which is Ci-C 3 alkyl,
  • R independently of each other, represent a saturated or unsaturated, preferably saturated, linear or branched C1-C30 hydrocarbon-based radical, and in particular a preferably saturated, C1-C20, in particular C1-C18 and more particularly C4-C10, hydrocarbon- based radical, a monocyclic or polycyclic C 6 -Ci 4 , and in particular Cio"Ci3, aryl radical, or an aralkyl radical of which preferably the aryl part is C & aryl and the alkyl part is C1-C3 alkyl.
  • the groups R may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical.
  • the groups R may in particular be identical, and in addition may be a methyl radical.
  • m 1 or 2 or 3
  • n is an integer between 0 and 100 and m is an integer between 1 and 100, with the proviso that the sum n+m is between 1 and 100, in formula (VIII).
  • R is a methyl radical.
  • 25°C of between 5 and 1500 mm 2 /s (i.e. 5 to 1500 cSt), and preferably with a viscosity of between 5 and 1000 mm 2 /s (i.e. 5 to 1000 cSt), may be used.
  • diphenylsiloxyphenyl trimethicone oil when m and n are between 1 and 100
  • KF56 A from Shin-Etsu
  • the Silbione 70663V30 oil from Rhone-Poulenc
  • phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding to the following formula, and mixtures thereof:
  • R-i, R ⁇ , R5 and R 6 which may be identical or different, are an alkyl radical containing 1 to 6 carbon atoms,
  • R 3 and R 4 which may be identical or different, are an alkyl radical containing from 1 to 6 carbon atoms or an aryl radical (preferably C6-C14), with the proviso that at least one of R3 and R 4 is a phenyl radical,
  • X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical, n and p being an integer greater than or equal to 1 , chosen so as to give the oil a weight- average molecular weight preferably less than 150 000 g/mol and more preferably less than 100 000 g/mol. and a mixture thereof.
  • fluoro oil means an oil containing at least one fluorine atom.
  • non-volatile fluoro oils that may be used in the present invention, mention may be made in particular of fluorosilicone oils, fluoro polyethers and fluorosilicones especially as described in document EP-A-847 752, and perfluoro compounds.
  • perfluoro compounds means compounds in which all the hydrogen atoms have been replaced with fluorine atoms.
  • the fluoro oil is chosen from perfluoro oils.
  • perfluoro oils mention may be made of perfluorodecalins and perfluoroperhydro- phenanthrenes.
  • the fluoro oil is chosen from perfluoroperhydro- phenanthrenes, and especially the Fiflow® products sold by the company Creations Couliv.
  • the fluoro oil whose INCI name is perfluoroperhydrophenanthrene, sold under the reference Fiflow 220 by the company F2 Chemicals.
  • composition according to the invention preferably comprises at least one polar or apolar non-volatile hydrocarbon-based oil, at least one non-volatile silicone oil, which is preferably phenylated, and mixtures thereof.
  • the composition according to the invention comprises at least one non-volatile silicone oil, which is preferably phenylated.
  • non-volatile phenylated silicone oils are chosen from those of formula (II), more particularly non-volatile phenyl silicone oils of formula (III) or (III').
  • non-volatile hydrocarbon-based oil(s) are more particularly chosen from polar non-volatile oils, such as for example Ci 0 -C 2 6 alcohols, or ester oils; from apolar oils; and mixtures thereof.
  • the composition comprises at least one polar oil chosen from Ci 0 -C 2 6 alcohols; hydroxylated monoesters and diesters; monoesters comprising between 18 and 40 carbon atoms in total; triesters comprising between 35 and 70 carbon atoms in total, or mixtures thereof, or at least one apolar oil chosen from liquid paraffin or derivatives thereof, hydrogenated or non-hydrogenated poly(iso)butenes, and also mixtures thereof.
  • polar oil chosen from Ci 0 -C 2 6 alcohols
  • hydroxylated monoesters and diesters monoesters comprising between 18 and 40 carbon atoms in total
  • triesters comprising between 35 and 70 carbon atoms in total, or mixtures thereof, or at least one apolar oil chosen from liquid paraffin or derivatives thereof, hydrogenated or non-hydrogenated poly(iso)butenes, and also mixtures thereof.
  • composition according to the invention additionally comprises at least one silicone gum.
  • the silicone gum is chosen from polyorganosiloxanes with a weight- average molecular mass of greater than or equal to 400 000 g/mol.
  • the weight-average molecular masses are measured in a manner that is conventional in the field, for example using gel permeation chromatography coupled to static light scattering (GPC-MALLS).
  • the viscosity of the silicone gum is greater than 800 000 cSt and more particularly less than or equal to 10 000 000 cSt (at 25°C, measured by standard ASTM D- 445), more particularly between 1 000 000 and 5 000 000 cSt (at 25°C, measured by standard ASTM D-445).
  • silicone gum means more particularly polyorganosiloxanes, in particular linear non-crosslinked, optionally hydroxylated, phenylated or vinyl polydimethylsiloxane type, or combinations thereof. It should be noted that the silicone gums used according to the invention are not silicone elastomers.
  • the silicone gum corresponds to the following formula:
  • R7, R8, R1 1 and R12 are identical or different, and each is chosen from alkyl radicals comprising from 1 to 6 carbon atoms,
  • R9 and R10 are identical or different, and each is chosen from an alkyl radical comprising from 1 to 6 carbon atoms, an aryl radical, a hydroxyl radical, a vinyl radical, preferably an alkyl radical comprising from 1 to 6 carbon atoms, a hydroxyl radical;
  • X is chosen from an alkyl radical comprising from 1 to 6 carbon atoms, a hydroxyl radical, a vinyl radical, preferably an alkyl radical comprising from 1 to 6 carbon atoms, a hydroxyl radical;
  • n and p are chosen so as to give the silicone gum a molecular mass of greater than or equal to 400 000 g/mol.
  • n and p may each take values ranging from 0 to 5000 and more particularly from 0 to 3000, given that n and p are not simultaneously zero.
  • the silicone gum is a polydimethylsiloxane gum optionally comprising at least one aryl radical, a dimethiconol gum, or mixtures thereof, and preferably a dimethiconol gum.
  • the silicone gum(s) may be used alone or as a mixture, especially with a solvent chosen from volatile silicones, polydimethylsiloxane oils, polyphenylmethylsiloxane oils, isoparaffins, in particular of C 8 -Ci S , methylene chloride, pentane, dodecane, tridecane and tetradecane, or mixtures thereof.
  • the proportion of gum usually represents from 5% to 20% by weight and preferably from 10% to 15% by weight in a linear or cyclic, volatile or non-volatile polydimethylsiloxane of low molecular weight.
  • silicone gums that may be used, mention may be made of those for which:
  • R12 represent a methyl group
  • substituent X represents a hydroxyl group
  • the coefficients n and p being such that the molecular mass is greater than or equal to 400 000 g/mol:
  • the silicone gum is a polydimethylsiloxane gum optionally comprising at least one aryl radical, a dimethiconol gum, or mixtures thereof, and preferably a dimethiconol gum.
  • the silicone gum where appropriate in predissolved form, is incompatible with the film-forming polymer, the latter being, where appropriate, conveyed in at least one oil, preferably a volatile oil.
  • Each mixture is prepared at 25°C with stirring (magnetic bar) for one hour.
  • the resulting mixture appears to be one-phase, this mixture is observed with a phase- contrast microscope. If one phase is seen to be dispersed in the other, then said optionally predissolved silicone gum and the film-forming polymer in its vehicle (if present) are said to be incompatible in the evaluated mixture.
  • Silicone gums that are incompatible in all the tested mixtures are more particularly suitable for use. Use may also be made of gums that are incompatible for some of the tested mixtures, if these gums are used in the composition in a content in which they are incompatible. If necessary, on the basis of the results obtained previously, one or more tests may be repeated to check the compatibility at the envisaged content.
  • the composition according to the invention comprises at least one silicone gum in an active material content ranging from 0.1 % to 10% by weight, preferably from 0.2% to 8% by weight, in particular from 0.3% to 6% by weight, relative to the total weight of the composition.
  • composition according to the invention also preferably comprises at least one volatile oil.
  • volatile oil means an oil with a non-zero vapour pressure, at 25°C, in particular ranging from 0.13 Pa to 40 000 Pa, in particular ranging up to 13 000 Pa and more particularly ranging up to 1300 Pa ("closed cup").
  • the composition comprises at least one volatile oil in a content ranging from 0.1 to 30% by weight, preferably from 0.5 to 25% by weight and in particular from 1 to 20% by weight, relative to the total weight of the composition.
  • the composition comprises at least one volatile oil in a content of at least 10% by weight, preferably ranging from 40 to 75% by weight and in particular from 50 to 70% by weight, relative to the total weight of volatile and non-volatile oil(s) present in said composition.
  • the composition comprises a mixture of volatile oil(s) and of non-volatile oil(s) in respective weight contents such as that the ratio of the content of volatile oil(s) to the content of non-volatile oil(s) ranges from 0.7 to 3, preferably ranges from 0.8 to 2.
  • the volatile oil(s) may be chosen from hydrocarbon-based oils, silicone oils and fluoro oils, and mixtures thereof.
  • hydrocarbon-based volatile oils are preferably chosen from apolar hydrocarbon- based oils and may in particular be chosen from hydrocarbon-based volatile oils containing from 8 to 16 carbon atoms, and mixtures thereof, and especially:
  • C 8 -Ci 6 alkanes such as C 8 -Ci 6 isoalkanes (also known as isoparaffins), isododecane, isodecane and isohexadecane, and, for example, the oils sold under the trade names Isopar and Permethyl,
  • the volatile silicone oils may be chosen from silicone oils with a flash point ranging from 40°C to 102°C, preferably with a flash point of greater than 55°C and less than or equal to 95°C, and preferentially ranging from 65°C to 95°C.
  • volatile silicone oils that may be used in the invention, mention may be made of linear or cyclic silicones with a viscosity at 25°C of less than 8 centistokes (cSt) (8 ⁇ 10 "6 m 2 /s) and especially containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms.
  • cSt centistokes
  • volatile silicone oil(s) that may be used in the invention, mention may be made especially of dimethicones with a viscosity of 2, 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
  • the volatile oils may also be chosen from a fluoro oil, such as nonafluoromethoxy- butane or perfluoromethylcyclopentane, and mixtures thereof.
  • the composition according to the invention comprises at least one volatile oil, chosen more particularly from apolar volatile hydrocarbon-based oils and from volatile silicone oils, alone or as mixtures.
  • composition according to the invention may also comprise at least one hydrocarbon-based or silicone-based compound that is pasty at 23°C.
  • the term "pasty compound” means a water- immiscible compound with a reversible solid/liquid change of state, having in the solid state an anisotropic crystal organization, and comprising at a temperature of 23°C a liquid fraction and a solid fraction.
  • the starting melting point of the pasty compound can be less than 23°C.
  • the liquid fraction of the pasty compound, measured at 23°C can represent from 9% to 97% by weight of the pasty compound. This liquid fraction at 23°C preferably represents between 15% and 85% and more preferably between 40% and 85% by weight.
  • the melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in the standard ISO 1 1357-3; 1999.
  • the melting point of a pasty compound may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2920 by the company TA Instruments or under the name DSC Q100 by the company TA Instruments with the TA Universal Analysis software.
  • DSC differential scanning calorimeter
  • the measuring protocol is as follows: a sample of 5 mg of pasty compound 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, 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 pasty fatty substance is measured as a function of the temperature.
  • the melting point of the pasty 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 liquid fraction by weight of the pasty compound at 23°C is equal to the ratio of the heat of fusion consumed at 23°C to the heat of fusion of the pasty compound.
  • the heat of fusion (expressed in J/g) of the pasty compound is the amount of energy required to make the compound change from the solid state to the liquid state.
  • the pasty compound is said to be in the solid state when all of its mass is in crystalline solid form.
  • the pasty compound is said to be in the liquid state when all of its mass is in liquid form.
  • the heat of fusion consumed at 23°C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23°C, consisting of a liquid fraction and a solid fraction.
  • the heat of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name MDSC 2920 by the company TA Instrument, with a temperature rise of 5°C or 10°C per minute, according to the standard ISO 11357-3; 1999.
  • DSC differential scanning calorimeter
  • the liquid fraction of the pasty compound measured at 32°C preferably represents from 30% to 100% by weight of the pasty compound, preferably from 50% to 100% and more preferably from 60% to 100% by weight of the pasty compound.
  • the temperature of the end of the melting range of the pasty compound is less than or equal to 32°C.
  • the liquid fraction of the pasty compound measured at 32°C is equal to the ratio of the heat of fusion consumed at 32°C to the heat of fusion of the pasty compound.
  • the heat of fusion consumed at 32°C is calculated in the same way as the heat of fusion consumed at 23°C.
  • the pasty compound(s) may in particular be chosen from synthetic pasty compounds and fatty substances of plant origin.
  • the pasty compound(s) may be hydrocarbon-based or silicone-based.
  • the pasty compound(s) may be chosen in particular from:
  • lanolin and derivatives thereof such as lanolin alcohol, oxyethylenated lanolins, acetylated lanolin, lanolin esters such as isopropyl lanolate, and oxypropylenated lanolins,
  • polyol ethers chosen from C 2 -C 4 polyalkylene glycol pentaerythrityl ethers, fatty alcohol ethers of sugars, and mixtures thereof.
  • polyethylene glycol pentaerythrityl ether comprising 5 oxyethylene units (5 OE)
  • polypropylene glycol pentaerythrityl ether comprising five oxypropylene (5 OP) units CTFA name: PPG-5 Pentaerythrityl Ether
  • CTFA name: PPG-5 Pentaerythrityl Ether and mixtures thereof, and more especially the mixture PEG-5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether and soybean oil, sold under the name Lanolide by the company Vevy, which is a mixture in which the constituents are in a 46/46/8 weight ratio: 46% PEG-5 Pentaerythrityl Ether, 46% PPG-5 Pentaerythrityl Ether and
  • o oligomers which are homopolymers and copolymers of vinyl esters containing C 8 -
  • o oligomers which are homopolymers and copolymers of vinyl esters containing C 8 - C 30 alkyl groups
  • liposoluble polyethers resulting from the polyetherification between one or more C 2 -Ci 0 o and preferably C 2 -C 5 o diols.
  • the liposoluble polyethers that are particularly considered are copolymers of ethylene oxide and/or of propylene oxide with C 6 -C 3 o long-chain alkylene oxides, more preferably such that the weight ratio of the ethylene oxide and/or of the propylene oxide to the alkylene oxides in the copolymer is from 5:95 to 70:30.
  • copolymers such as long- chain alkylene oxides arranged in blocks with an average molecular weight from 1000 to 10 000, for example a polyoxyethylene/polydodecyl glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 OE) sold under the brand name Elfacos ST9 by Akzo Nobel,
  • esters and polyesters are especially considered: o esters of a glycerol oligomer, especially diglycerol esters, with linear or branched, saturated or unsaturated, preferably saturated, C 6 -C 2 o, optionally hydroxylated monocarboxylic acids, and/or linear or branched, saturated or unsaturated, preferably saturated, C 6 -Ci 0 dicarboxylic acids, in particular condensates of adipic acid and of diglycerol, for which some of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, isostearic acid and 12-hydroxystearic acid, for instance bis-diglyceryl polyacyladipate-2 sold under the reference Softisan® 649 by the company Sasol,
  • o vinyl ester homopolymers bearing C 8 -C 30 alkyl groups such as polyvinyl laurate (sold especially under the reference Mexomer PP by the company Chimex), o the arachidyl propionate sold under the brand name Waxenol 801 by Alzo, o phytosterol esters,
  • o fatty acid triglycerides and derivatives thereof in particular optionally hydrogenated (totally or partially), optionally monohydroxylated or polyhydroxylated, C 6 -C 30 and more particularly C 8 -Ci 8 , linear or branched, saturated or unsaturated fatty acid triglycerides; for example Softisan 100® sold by the company Sasol,
  • the aliphatic carboxylic acid is of C 4 -C 3 o and preferably of C 8 -C 3 o- It is preferably chosen from hexanoic, heptanoic, octanoic, 2-ethylhexanoic, nonanoic, decanoic, undecanoic, dodecanoic, tridecanoic, tetradecanoic, pentadecanoic, hexadecenoic, hexyldecanoic, heptadecanoic, octadecanoic, isostearic, nonadecanoic, eicosanoic, isoarachidic, octyldodecanoic, heneicosanoic and docosanoic acids, and mixtures
  • the aliphatic carboxylic acid is preferably branched.
  • the hydroxy carboxylic acid ester is advantageously derived from a C 2 -C 4 o, preferably C10-C34 and even more preferentially Ci 2 -C 2 8 hydroxylated carboxylic acid; the number of hydroxyl groups being between 1 and 20, more particularly between 1 and 10 and preferably between 1 and 6.
  • Said hydroxy carboxylic acid esters are preferably chosen from:
  • esters of a diol dimer and of a diacid dimer where appropriate esterified on their free alcohol or acid function(s) with acid or alcohol radicals, especially dimer dilinoleate esters; such esters may be chosen especially from the esters having the following INCI nomenclature: bis-behenyl/isostearyl/phytosteryl dimer dilinoleyl dimer dilinoleate (Plandool G), phytosteryl/isosteryl/cetyl/stearyl/behenyl dimer dilinoleate (Plandool H or Plandool S), and mixtures thereof,
  • butters of plant origin such as mango butter, such as the product sold under the reference Lipex 203 by the company Aarhuskarlshamn, shea butter, in particular the product whose INCI name is Butyrospermum Parkii Butter, such as the product sold under the reference Sheasoft® by the company Aarhuskarlshamn, cupuacu butter (Rain Forest RF3410 from the company Beraca Sabara), murumuru butter (Rain Forest RF3710 from the company Beraca Sabara), cocoa butter; babassu butter such as the product sold under the name Cropure Babassu SS-(LK) by Croda, and also orange wax, for instance the product sold under the reference Orange Peel Wax by the company Koster Keunen,
  • hydrogenated plant oils for instance hydrogenated soybean oil, hydrogenated coconut oil, hydrogenated rapeseed oil, mixtures of hydrogenated plant oils such as the mixture of hydrogenated soybean, coconut, palm and rapeseed plant oil, for example the mixture sold under the reference Akogel® by the company Aarhuskarlshamn (INCI name Hydrogenated Vegetable Oil), the trans-isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the commercial reference lso-Jojoba-50®, partially hydrogenated olive oil, for instance the compound sold under the reference Beurrolive by the company Soliance, hydrogenated castor oil esters, such as hydrogenated castor oil dimer dilinoleate, for example Risocast DA-L sold by Kokyu Alcohol Kogyo, and hydrogenated castor oil isostearate, for example Salacos HCIS (V-L) sold by Nisshin Oil,
  • the pasty compound(s) that are suitable for use in the invention are chosen from hydrocarbon-based compounds, in particular chosen from petroleum jelly, polyol ethers, vinyl polymers, liposoluble polyethers resulting from polyetherification between one or more C 2 -C50 diols, esters and polyesters, butters of plant origin, totally or partially hydrogenated plant oils, and mixtures thereof.
  • the pasty compound(s) are chosen from:
  • esters of a glycerol oligomer especially esters of diglycerol, with linear or branched, saturated or unsaturated, preferably saturated, C 6 -C 2 o, optionally hydroxylated monocarboxylic acids, and/or linear or branched, saturated or unsaturated, preferably saturated, C 6 -C 10 dicarboxylic acids;
  • esters obtained by condensation of a linear or branched C 4 -C 50 dicarboxylic or polycarboxylic acid and of a C 2 -C 5 o diol or polyol, the aliphatic esters obtained by reaction of an ester of a hydroxycarboxylic acid and of an aliphatic carboxylic acid, the carboxylic acid advantageously being C4-C30; - esters of a diol dimer and of a diacid dimer, for instance dilinoleate dimer esters;
  • the composition according to the invention comprises at least one pasty compound in a content of greater than 0.5% by weight, preferably in a content ranging from 2 to 20% by weight, in particular from 2 to 15% by weight and even more advantageously from 2 to 10% by weight, relative to the total weight of the composition.
  • the composition according to the invention comprises at least one semi-crystalline polymer, preferably derived from acrylic or methacrylic acid.
  • the term "semi-crystalline polymer” means polymers comprising a crystallizable portion, side chain or block in the backbone, and an amorphous portion in the backbone and having a first-order reversible phase-change temperature, in particular of melting (solid-liquid transition).
  • the crystallizable portion is in the form of a block of the polymer backbone, the chemical nature of this crystallizable block is different from that of the amorphous blocks; in this case, the semi-crystalline polymer is a block polymer, for example, of the diblock, triblock or multiblock type comprising at least one crystallizable block and at least one amorphous block.
  • block generally means at least 5 identical repeating units.
  • the crystallizable block(s) are then of different chemical nature from the amorphous block(s).
  • the semi-crystalline polymer(s) of the composition of the invention have an average molecular mass (Mn) of greater than or equal to about 2000 g/mol, preferably from about 2000 to 800 000 g/mol, preferably from about 3000 to 500 000 g/mol, preferably from about 4000 to 150 000 g/mol and preferably from about 4000 to 99 000 g/mol.
  • Mn average molecular mass
  • the semi-crystalline polymers are advantageously soluble in the oily phase to at least 1 % by weight, at a temperature above their melting point.
  • the polymer blocks are amorphous.
  • the term “crystallizable chain or block” means a chain or block which, if it were alone, would pass reversibly from the amorphous state to the crystalline state, depending on whether it is above or below its melting point.
  • a chain is a group of atoms, which is pendent or lateral relative to the polymer backbone.
  • a block is a group of atoms belonging to the backbone, this group constituting one of the repeating units of the polymer.
  • the "crystallizable side chain” may be a chain comprising at least 6 carbon atoms.
  • the polymer backbone of the semi-crystalline polymers is soluble in the oily phase.
  • the semi-crystalline polymer used in the composition of the invention is generally introduced into the oily phase of the composition.
  • the melting point may be measured especially by any known method and in particular with a differential scanning calorimeter (DSC).
  • the crystallizable blocks or chains of the semi-crystalline polymers represent at least 30% by weight and better still at least 40% by weight of the total weight of each polymer.
  • the semi-crystalline polymers containing crystallizable blocks used according to the invention are block or multiblock polymers. They may be obtained by polymerization of monomers containing reactive double bonds (or ethylenic bonds) or by polycondensation. When the polymers of the invention are polymers containing crystallizable side chains, they are advantageously in random or statistical form.
  • the semi-crystalline polymers of the invention may be of synthetic origin. In addition, they comprise no polysaccharide backbones.
  • the semi-crystalline polymers that may be used in the invention are in particular:
  • block copolymers of polyolefins with controlled crystallization that are suitable for use in the present invention are especially those whose monomers are described in EP-A-0 951 897.
  • the homopolymers or copolymers bearing at least one crystallizable side chain and the homopolymers or copolymers bearing in the backbone at least one crystallizable block are those described especially in US-A-5 156 91 1.
  • homopolymers or copolymers bearing at least one crystallizable side chain in particular containing fluoro group(s) are preferably those described in WO-A-01/19333.
  • the crystallizable side chains or blocks are hydrophobic. a) Semi-crystalline polymers bearing crystallizable side chains:
  • these polymers are chosen especially from homopolymers and copolymers resulting from the polymerization of at least one monomer bearing crystallizable chain(s), which represented by the following formula:
  • M representing an atom of the polymer backbone
  • S representing a spacer
  • C representing a crystallizable group
  • the crystallizable chains "-S-C” may be aliphatic or aromatic, and optionally fluorinated or perfluorinated.
  • S especially represents a group (CH 2 ) n , (CH 2 CH 2 0)n or (CH 2 0), which may be linear or branched or cyclic, with n being an integer ranging from 0 to 22.
  • n being an integer ranging from 0 to 22.
  • S is a linear group.
  • “S” and “C” are different.
  • crystallizable chains "-S-C” are hydrocarbon-based aliphatic chains, they comprise hydrocarbon-based alkyl chains containing at least 1 1 carbon atoms and not more than 40 carbon atoms and better still not more than 24 carbon atoms. They are especially aliphatic chains or alkyl chains containing at least 12 carbon atoms, and they are preferably Ci4-C 2 4, alkyl chains. When they are fluoroalkyl or perfluoroalkyl chains, they contain at least 6 fluorinated carbon atoms and especially at least 1 1 carbon atoms, at least 6 of which carbon atoms are fluorinated.
  • the invention relates to a composition for which the semi-crystalline polymer is chosen from a group comprising homopolymers and copolymers resulting from the polymerization of at least one monomer bearing crystallizable chain(s), these chains being chosen from alkyl chains comprising at least 11 carbon atoms and not more than 40 carbon atoms.
  • semi-crystalline polymers or copolymers bearing crystallizable chain(s) mention may be made of those resulting from the polymerization of one or more of the following monomers: (meth)acrylates of saturated alkyls with the alkyl group being Ci 4 -C 24 , perfluoroalkyl (meth)acrylates with a Cn-Ci 5 perfluoroalkyl group, N-alkyl(meth)acrylamides with the alkyl group being Ci to C 2 with or without a fluorine atom, vinyl esters containing alkyl or perfluoroalkyl chains with the alkyl group being CM to C 24 (with at least 6 fluorine atoms per perfluoroalkyl chain), vinyl ethers containing alkyl or perfluoroalkyl chains with the alkyl group being C M to C 24 and at least 6 fluorine atoms per perfluoroalkyl chain, d 4 to C 24 a-olefins such as, for example
  • the hydrocarbon-based and/or fluorinated crystallizable chains as defined above are borne by a monomer that may be a diacid, a diol, a diamine or a diisocyanate.
  • the polymers that are the subject of the invention are copolymers, they additionally contain from 0 to 50% of groups Y or Z resulting from the copolymerization of Y which is a polar or non-polar monomer or a mixture of the two:
  • Y when Y is a polar monomer, it is either a monomer bearing polyoxyalkylenated groups (especially oxyethylenated and/or oxypropylenated groups), a hydroxyalkyl (meth)acrylate, for instance hydroxyethyl acrylate, (meth)acrylamide, an N-alkyl(meth)acrylamide, an N,N- dialkyl(meth)acrylamide such as, for example, N,N-diisopropylacrylamide or N-vinylpyrrolidone (NVP), N-vinylcaprolactam, a monomer bearing at least one carboxylic acid group, for instance (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, or bearing a carboxylic acid anhydride group, for instance maleic anhydride,
  • Y when Y is a non-polar monomer, it may be an ester of the linear, branched or cyclic alkyl (meth)acrylate type, a vinyl ester, an alkyl vinyl ether, an a-olefin, styrene or styrene substituted with a Ci to Ci 0 alkyl group, for instance omethylstyrene.
  • alkyl means a saturated group especially of C 8 to C 24 , and better still of CM to C 24 , unless otherwise mentioned.
  • the polymers that are subjects of the invention are copolymers, they also contain from 0 to 50% of groups Y or Z resulting from the copolymerization of Z which is a polar monomer or a mixture of polar monomers.
  • Z has the same definition as the "polar Y" defined above.
  • the semi-crystalline polymers bearing a crystallizable side chain are alkyl (meth)acrylate or alkyl(meth)acrylamide homopolymers with an alkyl group as defined above, and especially of Ci 4 -C 24 , copolymers of these monomers with a hydrophilic monomer preferably of different nature from (meth)acrylic acid, for instance N-vinylpyrrolidone or hydroxyethyl (meth)acrylate, and mixtures thereof.
  • These polymers are especially block copolymers consisting of at least two blocks of different chemical nature, one of which is crystallizable.
  • block polymers defined in patent US-A-5 156 91 1 are particularly suitable for use.
  • block copolymers of olefin or of cycloolefin containing a crystallizable chain for instance those derived from the block polymerization of:
  • the copolymers of interest may also be copolymers bearing at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature). These copolymers may also have two crystallizable blocks of different chemical nature.
  • the preferred copolymers are those simultaneously bearing at room temperature a crystallizable block and an amorphous block which are both hydrophobic and lipophilic, distributed sequentially; mention may be made, for example, of polymers bearing one of the crystallizable blocks and one of the amorphous blocks that follow:
  • polyester type for instance poly(alkylene terephthalate), or of b) polyolefin type, for instance polyethylenes or polypropylenes.
  • amorphous and lipophilic block for instance amorphous polyolefins or copoly(olefin)s such as poly(isobutylene), hydrogenated polybutadiene or hydrogenated poly(isoprene).
  • poly( -caprolactone)-b-poly(butadiene) block copolymers preferably used hydrogenated, such as those described by Nojima, Macromolecules, 32, 3727-3734 (1999), - the hydrogenated block or multiblock poly(butylene terephthalate )-b-poly(isoprene) block copolymers cited by Boutevin et al., Polymer Bulletin, 34, 117-123 (1995),
  • the semi-crystalline polymers in the composition of the invention may or may not be partially crosslinked, provided that the degree of crosslinking does not interfere with their dissolution or dispersion in the oily phase by heating above their melting point. It may then be a chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It may also be a physical crosslinking which may, in this case, be due either to the establishment of bonds of hydrogen or dipolar type between groups borne by the polymer, such as, for example, the dipolar interactions between carboxylate ionomers, these interactions being of small amount and borne by the polymer backbone; or to a phase separation between the crystallizable blocks and the amorphous blocks borne by the polymer.
  • the semi-crystalline polymers in the composition according to the invention are non-crosslinked.
  • the polymer is chosen from copolymers resulting from the polymerization of at least one monomer bearing a crystallizable chain chosen from saturated CM to C 3 ⁇ 4 alkyl (meth)acrylates, Cn to C15 perfluoroalkyl (meth)acrylates, C14 to C 24 N-alkyl(meth)acrylamides with or without a fluorine atom, vinyl esters containing d 4 to C 24 alkyl or perfluoroalkyl chains, vinyl ethers containing
  • CM to C 24 alkyl or perfluoroalkyl chains C14 to C 24 alpha-olefins, para-alkylstyrenes with an alkyl group containing from 12 to 24 carbon atoms, with at least one optionally fluorinated Ci to C10 monocarboxylic acid ester or amide, which may be represented by the following formula:
  • R 1 O in which 1 is H or CH3
  • R represents an optionally fluorinated C1-C10 alkyl group
  • X represents O, NH or NR 2 in which R 2 represents an optionally fluorinated Ci C10 alkyl group.
  • the polymer is derived from a monomer containing a crystallizable chain, chosen from saturated C u to C 22 alkyl (meth)acrylates and even more particularly poly(stearyl acrylate) or poly(behenyl acrylate).
  • the semi-crystalline polymer is chosen from homopolymers obtained by polymerization of a monomer chosen from C 14 -C 2 4 alkyl acrylates and Ci 4 -C 2 4 alkyl methacrylates and from copolymers obtained by copolymerization of a monomer chosen from Ci 4 -C 24 alkyl acrylates and Ci 4 -C 24 alkyl methacrylates, with a hydrophilic monomer.
  • structuring semi-crystalline polymers that may be used in the composition according to the invention, mention may be made of the polymers having the INCI name Poly C10-30 Alkyl Acrylate, such as the "I ntelimer” products from the company Air Products, for instance the product I ntelimer IPA 13-1 , which is a polystearyl acrylate (Ci 2 compound) or the product I ntelimer I PA 13-6, which is a behenyl polymer (C 22 compound).
  • the product I ntelimer IPA 13-1 which is a polystearyl acrylate (Ci 2 compound)
  • the product I ntelimer I PA 13-6 which is a behenyl polymer (C 22 compound).
  • the semi-crystalline polymer is a polymer of INCI name: Poly C10-C30 Alkyl Acrylate.
  • the semi-crystalline polymer Intelimer I PA 13-1 NG is known for its SPF booster effects, but it is sparingly compatible or incompatible with standard silicone emulsifiers and, more generally, with standard silicone ingredients.
  • the semi-crystalline polymers may especially be those described in Examples 3, 4, 5,
  • the semi-crystalline polymers do not comprise any carboxylic groups.
  • the content of semi- crystalline polymer(s) ranges from 0.5 to 3% by weight and preferably from 0.5 to 2% by weight, relative to the total weight of the composition.
  • the composition according to the invention comprises at least one wax.
  • the term "wax” means a lipophilic compound, which is solid at 25°C, with a reversible solid/liquid change of state, which has a melting point of greater than or equal to 30°C that may be up to 120°C.
  • the melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 30 by the company Mettler, or under the name DSC Q100 by the company TA instruments with the TA Universal Analysis software.
  • DSC differential scanning calorimeter
  • the measuring protocol is as follows:
  • 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 increase ranging from -20°C to 100°C at a heating rate of 5°C/minute.
  • 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 wax may especially have a hardness ranging from 0.05 MPa to 15 MPa and preferably ranging from 6 MPa to 15 MPa.
  • the hardness is determined by measuring the compression force measured at 20°C using a texturometer sold under the name TA-TX2i by the company Rheo, equipped with a stainless-steel cylinder 2 mm in diameter, travelling at a measuring speed of 0.1 mm/s, and penetrating the wax to a penetration depth of 0.3 mm.
  • the waxes may be hydrocarbon waxes or fluoro waxes, and may be of plant, mineral, animal and/or synthetic origin.
  • the waxes have a melting point of greater than 30°C and better still greater than 45°C.
  • apolar hydrocarbon-based wax means a wax comprising only carbon or hydrogen atoms in its structure. In other words, such a wax is free of other atoms, in particular of heteroatoms, for instance nitrogen, oxygen or silicon.
  • hydrocarbon-based waxes for instance microcrystalline waxes, paraffin waxes, ozokerite, polymethylene waxes, polyethylene waxes and microwaxes, especially polyethylene waxes.
  • polar wax means a wax whose chemical structure is formed essentially from, or even is constituted by, carbon and hydrogen atoms, and comprising at least one heteroatom such as oxygen, nitrogen or silicon atoms, preferably at least one oxygen atom.
  • the polar waxes may especially be hydrocarbon-based, fluoro or silicone waxes.
  • the polar waxes may be hydrocarbon-based waxes or silicone waxes.
  • silicon wax means an oil comprising at least one silicon atom, and especially comprising Si-0 groups.
  • hydrocarbon-based wax means a wax formed essentially from, or even constituted of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and that does not contain any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
  • the polar wax is a hydrocarbon-based wax.
  • hydrocarbon-based polar wax a wax chosen from ester waxes and alcohol waxes is in particular preferred.
  • ester wax means a wax comprising at least one ester function.
  • the ester waxes may also be hydroxylated.
  • alcohol wax means a wax comprising at least one alcohol function, i.e. comprising at least one free hydroxyl (OH) group.
  • ester wax The following may especially be used as ester wax:
  • waxes of formula RiCOOR 2 in which R-i and R 2 represent linear, branched or cyclic aliphatic chains, the number of atoms of which varies from 10 to 50, which may contain a heteroatom such as O, N or P and the melting point of which varies from 25°C to 120°C.
  • R-i and R 2 represent linear, branched or cyclic aliphatic chains, the number of atoms of which varies from 10 to 50, which may contain a heteroatom such as O, N or P and the melting point of which varies from 25°C to 120°C.
  • an ester wax of a C 20 -C40 alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture, or a C 2 0-C40 alkyl stearate.
  • Such waxes are especially sold under the names Kester Wax K 82 P®, Hydroxypolyester K 82 P®, Kester Wa
  • Use may also be made of a glycol and butylene glycol montanate (octacosanoate) such as the wax Licowax KPS Flakes (INCI name: glycol montanate) sold by the company Clariant.
  • octacosanoate such as the wax Licowax KPS Flakes (INCI name: glycol montanate) sold by the company Clariant.
  • the C 4 -C 3 o aliphatic group is linear and unsaturated.
  • waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C 8 -C 32 fatty chains for example such as hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, and also the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, such as those sold under the names Phytowax Ricin 16L64® and 22L73® by the company Sophim.
  • Such waxes are described in patent application FR-A-2 792 190.
  • Mention may be made, as waxes obtained by hydrogenation of olive oil esterified with stearyl alcohol, of those sold under the name Phytowax Olive 18 L 57.
  • Alcohol waxes that may be mentioned include mixtures of linear, saturated C30-C50 alcohols, such as for example the wax Performacol 550-L Alcohol from New Phase Technologies, stearyl alcohol and cetyl alcohol.
  • silicone waxes that may be mentioned include mixtures comprising a compound of C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane type (INCI name), for instance the product Dow Corning SW-8005 C30 Resin Wax sold by the company Dow Corning. Mention may also be made of mixtures comprising a compound of the C30-45 Alkyl Methicone type (INCI name), for instance the product Dow Corning® AMS-C30 Cosmetic Wax. Mention may also be made of siliconized beeswax.
  • the wax(es) are chosen from compounds that are incompatible with the non-volatile oil(s) present in the composition.
  • Three mixtures of 100 g each are prepared comprising a non-volatile oil and a wax in the following proportions: 75/25, 50/50, 25/75: at a temperature above the melting point of the wax, with stirring using a Rayneri blender that is sufficient to create a vortex in the mixture (as a guide, 200 to 1000 rpm) for 1 hour while maintaining this temperature.
  • Each resulting mixture is then poured into a container, which is closed. The composition is left to stand at room temperature for a time of 24 hours.
  • the resulting mixture is then observed by eye and, if need be, with a phase-contrast microscope, and the viscosity of the resulting mixture is checked according to the protocol described earlier in the description.
  • the wax is said to be incompatible.
  • the incompatibility of the wax with the mixture of non-volatile oils used in the composition is checked, the oils being present in the proportions in the composition according to the same protocol as previously.
  • This viscosity may then be refined by varying the content of the chosen wax, for example.
  • the composition comprises at least one polar silicone wax, or at least one polar hydrocarbon-based wax such as waxes of animal or plant origin, optionally obtained by catalytic hydrogenation of animal or plant oils; alcohol waxes; and also mixtures thereof.
  • polar silicone wax or at least one polar hydrocarbon-based wax such as waxes of animal or plant origin, optionally obtained by catalytic hydrogenation of animal or plant oils; alcohol waxes; and also mixtures thereof.
  • the composition more particularly comprises a wax content ranging from 0.5 to 5% by weight, preferably from 0.5 to 2% by weight, relative to the total weight of the composition.
  • the composition comprises at least one surfactant.
  • the content of surfactant(s) usually ranges between 0.05% and 15% by weight and preferably between 0.5% and 10% by weight relative to the total weight of the composition.
  • the suitable surfactant(s) may be chosen from nonionic, anionic, cationic and amphoteric surfactants, and mixtures thereof; and preferably from nonionic or anionic hydrocarbon-based or silicone surfactants, and mixtures thereof.
  • At least one emulsifying surfactant having at 25°C an HLB (hydrophilic- lipophilic balance) within the Griffin sense of greater than or equal to 8 may be used.
  • the Griffin HLB value is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256.
  • An emulsifying surfactant having at 25°C an HLB (hydrophilic-lipophilic balance) within the Griffin sense of less than 8 may also optionally be used.
  • surfactant(s) as a function of the type of emulsion that he wishes to obtain, a water-in-oil or oil-in-water emulsion, on the basis of his general knowledge.
  • the nonionic surfactants may be chosen especially from alkyl and polyalkyl esters of poly(ethylene oxide), (poly)oxyalkylenated alcohols, alkyl and polyalkyl ethers of poly(ethylene oxide), optionally polyoxyethylenated alkyl and polyalkyl esters of sorbitan, optionally polyoxyethylenated alkyl and polyalkyl ethers of sorbitan, alkyl and polyalkyl glycosides or polyglycosides, in particular alkyl and polyalkyl glucosides or polyglucosides, alkyl and polyalkyl esters of sucrose, optionally polyoxyethylenated alkyl and polyalkyl esters of glycerol, and optionally polyoxyethylenated alkyl and polyalkyl ethers of glycerol, and mixtures thereof.
  • (C 8 -C 3 o)Alkyl and poly(C 8 -C 3 o)alkyl esters of poly(ethylene oxide) that are preferably used are those with a number of ethylene oxide (EO) units ranging from 2 to 200. Examples that may be mentioned include stearate 40 EO, stearate 50 EO, stearate 100 EO, laurate 20 EO, laurate 40 EO and distearate 150 EO.
  • C 8 -C 3 o)Alkyl and poly(C 8 -C 3 o)alkyl ethers of poly(ethylene oxide) that are preferably used are those with a number of ethylene oxide (EO) units ranging from 2 to 200. Examples that may be mentioned include cetyl ether 23 EO, oleyl ether 50 EO, phytosterol 30 EO, steareth 40, steareth 100 and beheneth 100.
  • EO ethylene oxide
  • (Poly)oxyalkylenated, in particular oxyethylenated and/or oxypropylenated, alcohols that are preferably used are those that can comprise from 1 to 150 oxyethylene and/or oxypropylene units, in particular containing from 20 to 100 oxyethylene units, in particular ethoxylated fatty alcohols, in particular of C 8 -C 2 4 and preferably of Ci 2 -Ci 8 , such as stearyl alcohol ethoxylated with 20 oxyethylene units (CTFA name Steareth-20), for instance Brij 78 sold by the company Uniqema, cetearyl alcohol ethoxylated with 30 oxyethylene units (CTFA name Ceteareth-30), and the mixture of Ci 2 -Ci 5 fatty alcohols comprising 7 oxyethylene units (CTFA name C12-15 Pareth-7), for instance the product sold under the name Neodol 25-7 ® by Shell Chemicals; or in particular oxyalkylenated (oxyethylen
  • Optionally polyoxyethylenated (C 8 -C 3 o)alkyl and poly(C 8 -C 3 o)alkyl esters of sorbitan that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100.
  • EO ethylene oxide
  • Examples that may be mentioned include sorbitan laurate 4 or 20 EO, in particular polysorbate 20 (or polyoxyethylene (20) sorbitan monolaurate) such as the product Tween 20 sold by the company Uniqema, sorbitan palmitate 20 EO, sorbitan stearate 20 EO, sorbitan oleate 20 EO, or the Cremophor products (RH 40, RH 60, etc.) from BASF.
  • Optionally polyoxyethylenated (C 8 -C 30 )alkyl and poly(C 8 -C 30 )alkyl ethers of sorbitan that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100.
  • EO ethylene oxide
  • Alkyl and polyalkyl glucosides or polyglucosides that are preferably used are those containing an alkyl group comprising from 6 to 30 carbon atoms and preferably from 6 to 18 or even from 8 to 16 carbon atoms, and containing a glucoside group preferably comprising from 1 to 5 and in particular 1 , 2 or 3 glucoside units.
  • alkylpolyglucosides may be chosen, for example, from decylglucoside (alkyl-Cg/Cn-polyglucoside (1 .4)), for instance the product sold under the name Mydol 10 ® by the company Kao Chemicals or the product sold under the name Plantacare 2000 UP ® by the company Henkel and the product sold under the name Oramix NS 10 ® by the company SEPPIC; caprylyl/capryl glucoside, for instance the product sold under the name Plantacare KE 371 1 ® by the company Cognis or Oramix CG 110 ® by the company SEPPIC; laurylglucoside, for instance the product sold under the name Plantacare 1200 UP ® by the company Henkel or Plantaren 1200 N ® by the company Henkel; cocoglucoside, for instance the product sold under the name Plantacare 818 UP ® by the company Henkel; caprylylglucoside, for instance the product sold under the name Plant
  • Ryoto Sugar Ester for instance sucrose palmitate sold under the reference Ryoto Sugar Ester P1670, Ryoto Sugar Ester LWA1695 or Ryoto Sugar Ester 01570.
  • Optionally polyoxyethylenated (C 8 -C 30 )alkyl and poly(C 8 -C 30 )alkyl esters of glycerol that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100 and a number of glycerol units ranging from 1 to 30.
  • EO ethylene oxide
  • Examples that may be mentioned include hexaglyceryl monolaurate, polyglyceryl-4 isostearate, for instance the product sold under the name Isolan Gl 34 by the company Evonik Goldschmidt, and PEG-30 glyceryl stearate.
  • Optionally polyoxyethylenated (C 8 -C 30 )alkyl and poly(C 8 -C 30 )alkyl ethers of glycerol that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100 and a number of glycerol units ranging from 1 to 30. Examples that may be mentioned include Nikkol Batyl Alcohol 100 and Nikkol Chimyl Alcohol 100.
  • the anionic surfactants may be chosen from alkyl ether sulfates, carboxylates, amino acid derivatives, sulfonates, isethionates, taurates, sulfosuccinates, alkylsulfoacetates, phosphates and alkyl phosphates, polypeptides, metal salts of C10-C30 and in particular C12- C20 fatty acids, in particular metal stearates, and mixtures thereof.
  • Examples of (C 8 -C 30 )alkyl ether sulfates that may be mentioned include sodium lauryl ether sulfate (70/30 C12-C14) (2.2 EO) sold under the names Sipon AOS225 or
  • Texapon N702 by the company Henkel, ammonium lauryl ether sulfate (70/30 C12-C14) (3 EO) sold under the name Sipon LEA 370 by the company Henkel, ammonium (C12-C14) alkyl ether (9 EO) sulfate sold under the name Rhodapex AB/20 by the company Rhodia Chimie, and the mixture of sodium magnesium lauryl oleyl ether sulfate sold under the name Empicol BSD 52 by the company Albright & Wilson.
  • carboxylates examples include salts (for example alkali metal salts) of N-acylamino acids, glycol carboxylates, amido ether carboxylates (AECs) and polyoxyethylenated carboxylic acid salts.
  • the surfactant of glycol carboxylate type may be chosen from alkyl glycol carboxylics or 2-(2-hydroxyalkyloxy acetate), salts thereof and mixtures thereof.
  • These alkyl glycol carboxylics comprise a linear or branched, saturated or unsaturated aliphatic and/or aromatic alkyl chain containing from 8 to 18 carbon atoms.
  • These carboxylics may be neutralized with mineral bases such as potassium hydroxide or sodium hydroxide.
  • surfactants of glycol carboxylic type include sodium lauryl glycol carboxylate or sodium 2-(2-hydroxyalkyloxy acetate) such as the product sold under the name Beaulight Shaa® by the company Sanyo, Beaulight LCA-25N® or the corresponding acid form Beaulight Shaa (Acid form)®.
  • amido ether carboxylate (AEC)
  • sodium lauryl amido ether carboxylate (3 EO) sold under the name Akypo Foam 30 ® by the company Kao Chemicals.
  • polyoxyethylenated carboxylic acid salts examples include oxyethylenated (6 EO) sodium lauryl ether carboxylate (65/25/10 C12-14-16) sold under the name Akypo Soft 45 NV ® by the company Kao Chemicals, polyoxyethylenated and carboxymethylated fatty acids of olive oil origin sold under the name Olivem 400 ® by the company Biologia e Tecnologia, and oxyethylenated (6 EO) sodium tridecyl ether carboxylate sold under the name Nikkol ECTD-6 NEX ® by the company Nikkol.
  • 6 EO oxyethylenated sodium lauryl ether carboxylate
  • Akypo Soft 45 NV ® by the company Kao Chemicals
  • polyoxyethylenated and carboxymethylated fatty acids of olive oil origin sold under the name Olivem 400 ® by the company Biologia e Tecnologia
  • Amino acid derivatives that may especially be mentioned include alkali metal salts of amino acids, such as:
  • (Cs-C3o)alkoyl sarcosinates for instance the sodium lauroyl sarcosinate sold under the name Sarkosyl NL 97® by the company Ciba or sold under the name Oramix L30® by the company SEPPIC, sodium myristoyl sarcosinate sold under the name Nikkol Sarcosinate MN® by the company Nikkol, and sodium palmitoyl sarcosinate sold under the name Nikkol Sarcosinate PN® by the company Nikkol;
  • (C 8 -C 3 o)alkoyl alaninates for instance sodium N-lauroyl N-methyl amidopropionate sold under the name Sodium Nikkol Alaninate LN30 ® by the company Nikkol, or sold under the name Alanone ALE ® by the company Kawaken, and triethanolamine N-lauroyl N-methyl alanine sold under the name Alanone Alta ® by the company Kawaken;
  • (C 8 -C 3 o)alkoyl glutamates for instance triethanolamine monococoyl glutamate sold under the name Acylglutamate CT-12 ® by the company Ajinomoto, or triethanolamine lauroyl glutamate sold under the name Acylglutamate LT-12 ® by the company Ajinomoto;
  • glycine derivatives ((C 8 -C 30 )alkoyl glycinates), for instance the sodium N-cocoyl glycinate sold under the names Amilite GCS-12 ® and Amilite GCK 12 by the company Ajinomoto;
  • citrates such as citric acid monoesters of C 8 -C 30 alcohols, such as the oxyethylenated (9 mol) citric monoester of cocoyl alcohols sold under the name Witconol EC 1 129 by the company Goldschmidt;
  • (C 8 -C 3 o)alkyl galacturonates such as the sodium dodecyl-D-galactoside uronate sold by the company Soliance.
  • sulfonates examples include a-olefin sulfonates, for instance the sodium a-olefin sulfonate (Ci 4 -i 6 ) sold under the name Bio-Terge AS-40 ® by the company Stepan, sold under the names Witconate AOS Protege ® and Sulframine AOS PH 12® by the company Witco or sold under the name Bio-Terge AS-40 CG ® by the company Stepan, and the sodium secondary olefin sulfonate sold under the name Hostapur SAS 30 ® by the company Clariant.
  • a-olefin sulfonates for instance the sodium a-olefin sulfonate (Ci 4 -i 6 ) sold under the name Bio-Terge AS-40 ® by the company Stepan, sold under the names Witconate AOS Protege ® and Sulframine AOS PH 12® by the company Witco or sold
  • alkoyl isethionates that may be mentioned include acylisethionates, for instance sodium cocoyl isethionate, such as the product sold under the name Jordapon CI P ® by the company Jordan.
  • (C 8 -C 3 o)Alkoyl taurates that may be mentioned include the sodium salt of palm kernel oil methyltaurate sold under the name Hostapon CT Pate ® by the company Clariant; N-acyl N-methyltaurates, for instance the sodium N-cocoyl N-methyltaurate sold under the name Hostapon LT-SF ® by the company Clariant or sold under the name Nikkol CMT-30-T ® by the company Nikkol, and the sodium palmitoyl methyltaurate sold under the name Nikkol PMT ® by the company Nikkol.
  • sulfosuccinates examples include the oxyethylenated (3
  • Polydimethylsiloxane sulfosuccinates may also be used, such as disodium PEG-12 dimethicone sulfosuccinate sold under the name Mackanate-DC30 by the company Maclntyre.
  • Examples of (Cs-C3o)alkyl sulfoacetates that may be mentioned include the mixture of sodium lauryl sulfoacetate and disodium lauryl ether sulfosuccinate, sold under the name Stepan-Mild LSB by the company Stepan.
  • Examples of phosphates and (C 8 -C 3 o)alkyl phosphates that may be mentioned include monoalkyl phosphates and dialkyl phosphates, such as the lauryl monophosphate sold under the name MAP 20 ® by the company Kao Chemicals, the potassium salt of dodecylphosphoric acid, the mixture of monoester and diester (predominantly diester) sold under the name Crafol AP-31 ® by the company Cognis, the mixture of octylphosphoric acid monoester and diester sold under the name Crafol AP-20 ® by the company Cognis, the mixture of ethoxylated (7 mol of EO) phosphoric acid monoester and diester of 2- butyloctanol, sold under the name Isofol 12 7 EO-Phosphate Ester ® by the company Condea, the potassium or triethanolamine salt of mono(Ci2-Ci3)alkyl phosphate sold under
  • polypeptides are obtained, for example, by condensation of a fatty chain onto amino acids from cereals and in particular from wheat and oat.
  • polypeptides that may be mentioned include the potassium salt of hydrolysed lauroyl wheat protein, sold under the name Aminofoam W OR by the company Croda, the triethanolamine salt of hydrolysed cocoyl soybean protein, sold under the name May-Tein SY by the company Maybrook, the sodium salt of lauroyl oat amino acids, sold under the name Proteol Oat by the company SEPPIC, collagen hydrolysate grafted onto coconut fatty acid, sold under the name Geliderm 3000 by the company Deutsche Gelatine, and soybean proteins acylated with hydrogenated coconut acids, sold under the name Proteol VS 22 by the company SEPPIC.
  • Ci 0 -C 30 and in particular Ci 2 -C 2 o fatty acids mention may be made in particular of metal stearates, such as sodium stearate and potassium stearate, and also polyhyd roxystea rates .
  • dimethicone copolyols which are more particularly oxypropylenated and/or oxyethylenated polydimethyl methyl siloxanes.
  • dimethicone copolyols use may be made of those corresponding particularly to formula (II) below:
  • R 2 and R 3 independently of each other, represent a CrC 6 alkyl radical or a radical at least one radical Ri, R 2 or R 3 not being an alky l radical or a C 2 -C 4 acyl radical;
  • - A is an integer ranging from 0 to 200;
  • - B is an integer ranging from 0 to 50; on condition that A and B are not simultaneously equal to zero;
  • - x is an integer ranging from 1 to 6;
  • - y is an integer ranging from 1 to 30;
  • - z is an integer ranging from 0 to 30, preferably to 20.
  • Dimethicone copolyols that may be used include those sold under the names DC 5329, DC 7439-146, DC 2-5695 and Q4-3667 by the company Dow Corning; KF-6013, KF-6015, KF-6016, KF-6017 (PEG-10 dimethicone) and KF-6028 (PEG-polydimethylsiloxyethyl dimethicone), KF-6050 L(PEG/PPG 18/18 dimethicone) by the company Shin-Etsu.
  • dimethicone copolyol such as the product sold under the name Q2-5220 ® by the company Dow Corning;
  • alkyl dimethicone copolyols such as the laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by the company Dow Corning; cetyl dimethicone copolyol such as the product sold under the name Abil EM 90 by the company Evonik Goldschmidt, and the mixture of cetyl dimethicone copolyol, polyglyceryl (4 mol) isostearate and hexyl laurate sold under the name Abil WE 09 by the company Evonik Goldschmidt, or alternatively phosphate-based surfactants.
  • dimethicone copolyol benzoate such as the product sold under the names Finsolv SLB 101 ® and 201 ® by the company Finetex.
  • Emulsion surfactants that may also be mentioned include, in particular for water-in-oil emulsions, crosslinked elastomeric solid organopolysiloxanes comprising at least one oxyalkylene group, such as the products obtained according to the procedure of Examples 3, 4 and 8 of document US-A-5 412 004 and the examples of document US-A-5 81 1 487, especially the product of Example 3 (synthetic example) of patent US-A-5 412 004, and such as the product sold under the reference KSG 21 by the company Shin-Etsu.
  • coemulsifiers which may be chosen advantageously from the group comprising polyol alkyl esters, may also be added thereto.
  • Polyol alkyl esters that may especially be mentioned include polyethylene glycol esters, for instance PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135 by the company I CI .
  • the surfactant(s) are chosen from nonionic surfactants and silicone surfactants, or mixtures thereof.
  • an emulsion according to the invention in particular a water-in-oil emulsion, comprises at least one silicone surfactant chosen from (alkyl)dimethicone copolyols, alone or as mixtures.
  • composition according to the invention comprises an aqueous phase.
  • the aqueous phase comprises water and optionally at least one water-soluble solvent.
  • water-soluble solvent means a compound that is liquid at room temperature and atmospheric pressure, and that is water-miscible (miscibility with water of greater than 50% by weight at 25°C and atmospheric pressure).
  • composition according to the invention preferentially comprises at least 10% by weight, in particular from 20% to 70% by weight and especially from 25% to 60% by weight of aqueous phase (water + water-soluble solvent), relative to the total weight of the composition.
  • aqueous phase water + water-soluble solvent
  • composition according to the invention preferentially comprises at least 10% by weight, in particular from 20% to 65% by weight and especially from 25% to 55% by weight of water, relative to the total weight of the composition.
  • the composition may comprise at least 60% by weight, preferably at least 70% by weight and in particular at least 75% by weight of water, relative to the total weight of the aqueous phase.
  • the composition comprises a total content of water and volatile oil(s) of greater than or equal to 40% by weight and in particular greater than or equal to 50% by weight relative to the total weight of the composition.
  • composition according to the invention may comprise at least one polyol, more particularly a saturated or unsaturated, linear or branched C 2 -C 8 and preferably C 3 -C 6 polyol that is liquid at room temperature, comprising from 2 to 6 hydroxyl groups.
  • the polyol is chosen from glycerol, diglycerol, linear or branched, saturated C 3 -C 8 glycols, in particular propylene glycol, butylene glycol, pentylene glycol, caprylyl glycol or dipropylene glycol, and also mixtures thereof, and preferably glycerol, propylene glycol or butylene glycol, and mixtures thereof.
  • the second oily phase comprises at least glycerol as polyol.
  • the composition according to the invention has a content of polyol(s) particularly between 2% and 10% by weight and preferably from 4% to 8% by weight relative to the total weight of the composition.
  • composition according to the invention may also comprise at least one dyestuff chosen especially from water-soluble or liposoluble dyestuffs, pigments and nacres, and mixtures thereof.
  • diestuff means a compound that is capable of producing a coloured optical effect when it is formulated in sufficient amount in a suitable cosmetic medium.
  • the water-soluble dyestuffs used according to the invention are more particularly water-soluble dyes.
  • water-soluble dye means any natural or synthetic, generally organic compound, which is soluble in an aqueous phase or water- miscible solvents and which is capable of imparting colour.
  • water- soluble is intended to characterize the capacity of a compound to be dissolved in water, measured at 25°C, to a concentration at least equal to 0.1 g/L (production of a macroscopically isotropic, transparent, coloured or colourless solution). This solubility is in particular greater than or equal to 1 g/L.
  • 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 (CI: 14700), DC Red 6 (Lithol Rubine Na; CI: 15850), DC Red 22 (CI: 45380), DC Red 27 (CI: 45410 Na salt), DC Red 30 (CI: 73360), DC Red 33 (CI: 17200), DC Orange 4 (CI: 15510), FDC Yellow 5 (CI: 19140), FDC Yellow 6 (CI: 15985), DC Yellow 8 (CI: 45350 Na salt), FDC Green 3 (CI: 42053), DC Green 5 (CI: 61570), FDC Blue 1 (CI: 42090).
  • sources of water-soluble dyestuff(s) that may be used in the context of the present invention, mention may be made in particular of those of natural origin, such as extracts of cochineal carmine, of beetroot, of grape, of carrot, of tomato, of annatto, of paprika, of henna, of caramel and of curcumin.
  • the water-soluble dyestuffs that are suitable for use in the invention are especially carminic acid, betanin, anthocyans, enocyanins, lycopene, ⁇ -carotene, bixin, norbixin, capsanthin, capsorubin, flavoxanthin, lutein, cryptoxanthin, rubixanthin, violaxanthin, riboflavin, rhodoxanthin, cantaxanthin and chlorophyll, and mixtures thereof.
  • They may also be copper sulfate, iron sulfate, water-soluble sulfopolyesters, rhodamine, betaine, methylene blue, the disodium salt of tartrazine and the disodium salt of fuchsin.
  • these water-soluble dyestuffs are in particular permitted for food use.
  • Representatives of these dyes that may be mentioned more particularly include dyes of the carotenoid family, referenced under the food codes E120, E162, E163, E160a-g, E150a, E101 , E100, E140 and E141.
  • the water-soluble dyestuff(s) are chosen from the disodium salt of brilliant yellow FCF sold by the company LCW under the name DC Yellow 6, the disodium salt of fuchsin acid D sold by the company LCW under the name DC Red 33, and the trisodium salt of Rouge Allura sold by the company LCW under the name FD & C Red 40.
  • the dyestuff(s) used in the context of the present invention may also be chosen from pigments.
  • pigments should be understood as meaning white or coloured, inorganic (mineral) or organic particles, which are insoluble in the liquid organic phase, and which are intended to colour and/or opacify the composition and/or the deposit produced with the composition.
  • the pigments may be chosen from mineral pigments, organic pigments and composite pigments (i.e. pigments based on mineral and/or organic materials).
  • the pigments may be chosen from monochromatic pigments, lakes, nacres, and pigments with an optical effect, for instance reflective pigments and goniochromatic pigments.
  • the coated or uncoated mineral pigments may be chosen from metal oxide pigments, chromium oxides, iron oxides, titanium dioxide, zinc oxides, cerium oxides, zirconium oxides, manganese violet, Prussian blue, ultramarine blue and ferric blue, and mixtures thereof.
  • Organic lakes are organic pigments formed from a dye attached to a substrate.
  • the lakes which are also known as organic pigments, may be chosen from:
  • organic pigments of azo dyes, anthraquinone dyes, indigoid dyes, xanthene dyes, pyrene dyes, quinoline dyes, triphenylmethane dyes or fluoran dyes are those known under the following names: D&C Blue No. 4, D&C Brown No. 1 , D&C Green No. 5, D&C Green No. 6, D&C Orange No.
  • D&C Orange No. 5 D&C Orange No. 10, D&C Orange No. 1 1 , D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21 , D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31 , D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 1 1 , FD&C Blue No. 1 , FD&C Green No. 3, FD&C Red No. 40, FD&C Yellow No.
  • the organic lakes may also be supported on an organic support such as rosin or aluminium benzoate, for example.
  • organic lakes mention may be made in particular of those known under the following names: D&C Red No. 2 Aluminium lake, D&C Red No. 3 Aluminium lake, D&C Red No. 4 Aluminium lake, D&C Red No. 6 Aluminium lake, D&C Red No. 6 Barium lake, D&C Red No. 6 Barium/Strontium lake, D&C Red No. 6 Strontium lake, D&C Red No. 6 Potassium lake, D&C Red No. 7 Aluminium lake, D&C Red No. 7 Barium lake, D&C Red No. 7 Calcium lake, D&C Red No. 7 Calcium/Strontium lake, D&C Red No. 7 Zirconium lake, D&C Red No. 8 Sodium lake, D&C Red No.
  • liposoluble dyes such as, for example, Sudan Red, DC
  • the pigments may also have been subjected to a hydrophobic treatment.
  • the hydrophobic treatment agent may be chosen from silicones such as methicones, dimethicones, alkoxylsilanes and perfluoroalkylsilanes; fatty acids such as stearic acid; metal soaps such as aluminium dimyristate, the aluminium salt of hydrogenated tallow glutamate, perfluoroalkyl phosphates, perfluoroalkylsilanes, perfluoroalkylsilazanes, polyhexafluoropropylene oxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups and amino acids; N-acylamino acids or salts thereof; lecithin, isopropyl triisostearyl titanate, and mixtures thereof.
  • silicones such as methicones, dimethicones, alkoxylsilanes and perfluoroalkylsilanes
  • fatty acids such as stearic acid
  • metal soaps such as
  • the N-acylamino acids can comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group.
  • the salts of these compounds can be the aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts.
  • the amino acid may be, for example, lysine, glutamic acid or alanine.
  • alkyl mentioned in the compounds cited above especially denotes an alkyl group containing from 1 to 30 carbon atoms and preferably containing from 5 to 16 carbon atoms.
  • Hydrophobic-treated pigments are described especially in patent application EP-A-1 086 683.
  • nacre means coloured particles of any form, which may or may not be iridescent, especially produced by certain molluscs in their shell, or alternatively synthesized, and which have a colour effect via optical interference.
  • nacres examples include nacreous pigments such as titanium mica coated with an iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye in particular of the abovementioned type, and also nacreous pigments based on bismuth oxychloride. They may also be mica particles, at the surface of which are superposed at least two successive layers of metal oxides and/or of organic dyestuffs.
  • the nacres may more particularly have a yellow, pink, red, bronze, orangey, brown, gold and/or coppery colour or tint.
  • nacres that may be introduced as interference pigments into the first composition
  • composition according to the invention may also comprise any additive chosen by a person skilled in the art such that the advantageous properties intrinsically associated with the compositions in accordance with the invention are not, or not substantially, adversely affected by the envisaged addition(s).
  • additives that may be incorporated into the compositions in accordance with the invention, mention may be made especially of hydrophilic thickeners, hydrophobic thickeners, fillers of organic or mineral nature, emollients, humectants other than the abovementioned polyols, stabilizers, preserving agents, pigment dispersers, film-forming agents other than those according to the invention, and organic solvents.
  • hydrophilic thickening polymers examples include:
  • polyacrylic acid/alkyl acrylate copolymers preferably modified or unmodified carboxyvinyl polymers, particularly acrylate/Ci 0 -C 3 o-alkylacrylate copolymers (INCI name:
  • Acrylat.es/C10-C30 Alkyl acrylate Crosspolymer such as the products sold by the company Lubrizol under the trade names Pemulen TR1 , Pemulen TR2, Carbopol 1382 and Carbopol EDT 2020, and even more preferentially Pemulen TR-2,
  • hydrophilic gelling polymers examples include:
  • alkylcelluloses such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, and also quaternized cellulose derivatives;
  • vinyl polymers for instance polyvinylpyrrolidones, copolymers of methyl vinyl ether and of malic anhydride, the copolymer of vinyl acetate and of crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate; copolymers of vinylpyrrolidone and of caprolactam; polyvinyl alcohol;
  • polymers of natural origin such as galactomannans and derivatives thereof, for instance konjac gum, gellan gum, locust bean gum, fenugreek gum, karaya gum, gum tragacanth, gum arabic, acacia gum, guar gum, hydroxypropyl guar, hydroxypropyl guar modified with sodium methylcarboxylate groups (Jaguar XC97-1 , Rhodia), hydroxypropyltrimethylammonium guar chloride, and xanthan gum and derivatives thereof;
  • the content of hydrophilic thickener ranges from 0.01 % to 3% by weight, preferably from 0.05% to 2% by weight and more advantageously from 0.1 % to 1 % by weight relative to the total weight of the composition.
  • hydrophobic thickener mention may be made most particularly of hydrophobic mineral thickeners, for instance modified clays and modified silicas, or mixtures thereof.
  • Clays are silicates containing a cation that may be chosen from calcium, magnesium, aluminium, sodium, potassium and lithium cations, and mixtures thereof.
  • clays of the smectite family and also of the vermiculite, stevensite or chlorite family examples include clays of the smectite family and also of the vermiculite, stevensite or chlorite family. These clays may be of natural or synthetic origin. Use is preferably made of organophilic clays, more particularly modified clays, such as montmorillonite, bentonite, hectorite, attapulgite and sepiolite, and mixtures thereof. The clay is preferably a bentonite or a hectorite.
  • These clays are modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylarylsulfonates and amine oxides, and mixtures thereof.
  • hectorites modified with a quaternary amine more specifically with a Cio to C 22 fatty acid ammonium halide, such as a chloride, optionally comprising an aromatic group, such as hectorite modified with a halide, preferably 2 distearyldimethylammonium chloride (CTFA name: Disteardimonium hectorite), for instance the product sold under the name Bentone 38V, Bentone 38V CG or Bentone EW CE by the company Elementis, or stearalkonium hectorites, in particular such as Bentone 27 V.
  • CFA name Disteardimonium hectorite
  • quaternium-18 bentonites such as those sold, inter alia, under the names Bentone 34 by the company Elementis, Tixogel VP by the company United Catalyst and Claytone 40 by the company Southern Clay; stearalkonium bentonites, such as those sold under the names Tixogel LG by the company United Catalyst and Claytone AF and Claytone APA by the company Southern Clay; or quaternium-18/benzalkonium bentonites, such as those sold under the name Claytone HT by the company Southern Clay.
  • the thickener is chosen from organophilic modified clays, in particular organophilic modified hectorites, in particular modified with halide, especially benzyldimethylammonium stearate chloride or with distearyldimethylammonium chloride.
  • the hydrophobic groups may be:
  • silica thus treated are known as "silica silylate” according to the CTFA (6th edition, 1995). They are sold, for example, under the references Aerosil R812 ® by the company Degussa, and Cab-O-Sil TS-530 ® by the company Cabot;
  • silica - dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane, for example hexamethyldisiloxane or dimethyldichlorosilane.
  • Silicas thus treated are known as "silica dimethyl silylate" according to the CTFA (6th edition, 1995). They are sold, for example, under the references Aerosil R972 ® and Aerosil R974 ® by the company Degussa, and Cab- O-Sil TS-610 ® and Cab-O-Sil TS-720 ® by the company Cabot.
  • the hydrophobic fumed silica in particular has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm.
  • composition according to the invention may also comprise at least silica aerogel particles.
  • Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air.
  • sol-gel processes are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, the one most commonly used being supercritical C0 2 . This type of drying makes it possible to avoid shrinkage of the pores and of the material.
  • the sol-gel process and the various drying processes are described in detail in Brinker CJ., and Scherer G.W., Sol-Gel Science: New York: Academic Press, 1990.
  • the hydrophobic silica aerogel particles that are suitable for use in the invention have a specific surface area per unit mass (S M ) ranging from 500 to 1500 m 2 /g, preferably from 600 to 1200 m 2 /g and better still from 600 to 800 m 2 /g, and a size expressed as the volume-mean diameter (D[0.5]) ranging from 1 to 1500 ⁇ , better still from 1 to 1000 ⁇ , preferably from 1 to 100 ⁇ , in particular from 1 to 30 ⁇ , more preferably from 5 to 25 ⁇ , better still from 5 to 20 ⁇ and even better still from 5 to 15 ⁇ .
  • S M specific surface area per unit mass
  • D[0.5] volume-mean diameter
  • the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit mass (SM) ranging from 600 to 800 m 2 /g and a size expressed as volume-mean diameter (D[0.5]) ranging from 5 to 20 ⁇ and better still from 5 to 15 ⁇ .
  • SM surface area per unit mass
  • D[0.5] volume-mean diameter
  • the specific surface area per unit mass may 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, which corresponds to international standard ISO 5794/1 (appendix D).
  • BET Brunauer-Emmett-Teller
  • the BET specific surface area corresponds to the total specific surface area of the particles under consideration.
  • the sizes of the silica aerogel particles may be measured by static light scattering using a commercial particle size analyser such as the MasterSizer 2000 machine from Malvern.
  • the data are processed on the basis of the Mie scattering theory.
  • This theory which is exact for isotropic particles, makes it possible to determine, in the case of non- spherical particles, an "effective" particle diameter. This theory is especially described in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957.
  • the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit volume S v ranging from 5 to 60 m 2 /cm 3 , preferably from 10 to 50 m 2 /cm 3 and better still from 15 to 40 m 2 /cm 3 .
  • the aerogels used according to the present invention are hydrophobic silica aerogels preferably of silyl silica (I NCI name silica silylate).
  • hydrophobic silica aerogel particles surface-modified by silylation As regards the preparation of the hydrophobic silica aerogel particles surface-modified by silylation, reference may be made to US 7 470 725. Hydrophobic silica aerogel particles surface-modified with trimethylsilyl groups will preferably be used.
  • hydrophobic silica aerogels that may be used in the invention, examples that may be mentioned include the aerogel sold under the name VM-2260 (INCI name: Silica silylate), by the company Dow Coming, the particles of which have a mean size of about 1000 microns and a specific surface area per unit of mass ranging from 600 to 800 m 2 /g.
  • Aerogel TLD 201 Mention may also be made of the aerogels sold by the company Cabot under the references Aerogel TLD 201 , Aerogel OGD 201 , Aerogel TLD 203, Enova® Aerogel MT 1 100 and Enova Aerogel MT 1200.
  • Silica silylate by the company Dow Corning, the particles of which have an average size ranging from 5-15 microns and a specific surface area per unit of mass ranging from 600 to 800 m 2 /g.
  • the mineral thickeners are chosen from organophilic clays, in particular modified hectorites; hydrophobic-treated fumed silica; hydrophobic silica aerogels, or mixtures thereof, and even more precisely at least one organophilic modified clay or at least one hydrophobic modified silica, in particular an organophilic modified clay.
  • the content of mineral thickener(s) represents from 0.2 to 2% by weight, expressed as active material, preferably 0.5 to 1.8% by weight, relative to the total weight of the composition.
  • filler should be understood as meaning colourless or white solid particles of any shape, which are in a form that is insoluble and dispersed in the medium of the composition. They are different from the dyestuffs and make it possible especially to thicken the lipophilic phase of the composition according to the invention.
  • fillers that may be used in the compositions according to the invention, mention may be made of silica, kaolin, bentone, starch, lauroyllysine, and fumed silica particles, optionally hydrophilically treated, and mixtures thereof.
  • a composition used according to the invention may comprise one or more fillers in a content ranging from 0.1 % to 15% by weight and in particular from 1 % to 10% by weight relative to the total weight of the composition.
  • composition according to the invention may be conditioned in any type of device that is common for fluid cosmetic compositions intended especially to be applied to the lips.
  • Such devices may or may not be provided with a mechanism for dispensing the composition making it possible to expel said composition from the container to the application member, or to the support. It should be noted that this mechanism may advantageously comprise a means for metering out the composition.
  • the composition is packaged in a container and is applied by means of an application member having a porous application surface.
  • the application member may be entirely porous, i.e. the composition may cross from an internal surface of the application member to an external surface of the application member, or vice versa.
  • the application member may in particular consist of one or more open-cell or semi- open-cell foams.
  • the application member may be made up of one of at least two portions of foam, of different compressibilities, which can be adhesively bonded together.
  • the foam may be non-crosslinked or preferentially crosslinked.
  • the foam(s) are elastically compressible.
  • the term "elastically compressible” is intended to mean that, starting from a position deformed by a pressure exerted on its surface, the foam returns to its initial shape when the pressure is released.
  • the releasing of the composition on the surface to be treated takes place either by capillary action on contact with the lips, or by expulsion of the composition, from the pores of the applicator, in response to a slight deformation (by pressure) of said applicator on the surface to be treated.
  • the application member may have a cylindrical shape and may have a circular cross section.
  • the application member may have any other shape, for example conical, flattened-cone, nose-cone or prism shape, and can have an oval, rectangular or polygonal cross section. It may also comprise a bevelled portion and/or a concave portion forming a hollow on the application surface.
  • the application member may be symmetrical or asymmetrical relative to a longitudinal plane of said application member.
  • the visible part of the application member may have a cross section which falls within a circle advantageously having a diameter of between 2 mm and 20 mm, and preferably between 5 mm and 15 mm.
  • the visible part of the application member, in the non- compressed position, may be between 2 mm and 20 mm in height.
  • the application member may consist of several different materials, in particular of a stack of foams having different characteristics.
  • the application member may consist of one or more foams chosen from polyether, polyester, polyurethane, polyester-polyurethane, NBR (natural butadiene rubber), SBR (synthetic butadiene rubber) or PVC (polyvinyl chloride) foams, or mixtures thereof, and quite particularly polyester-polyurethane, in particular the product S90 from Crest Foam Industries.
  • the density of the foam(s) forming the application member measured according to standard ASTM D 3574-05, may advantageously be between 0.02 g.cm 3 and 0.05 g.cm "3 , for example 0.03 g.cm "3 . This density makes it possible to release an appropriate amount of impregnated composition.
  • the average number of pores or cells of the foam(s) may advantageously be between
  • the average pore size may advantageously be between 0.2 mm and 0.5 mm. It should be noted that the evaluation of the average number of pores is conventionally carried out visually by counting.
  • the cells or pores communicate with one another omnidirectionally.
  • the hardness of the application surface of the applicator member measured by means of an F-type durometer from Asker, may advantageously be between 10 Asker F and 70 Asker F.
  • At least one part of the surface of the application member may be covered with a flock, in particular based on polyamide, rayon, cotton, viscose or nylon fibres.
  • the flock contributes to creating a store of product, immediately in the neighbourhood of the application surface.
  • it makes it possible to impart more softness on application, in particular when the application member is made of wide-cell foam.
  • the flock may contribute to the homogenization of the spreading of the composition to form a thin film.
  • the flock may consist of a mixture of fibres of various lengths and/or nature and/or diameters.
  • the length of the fibres may advantageously be between 0.2 mm and 1 mm, for example equal to 0.75 mm.
  • the fibre count grading unit may advantageously be between 0.3 dtex and 3.3 dtex, for example equal to 1.7 dtex.
  • the application surface can be covered with a permeable coating of textile, perforated plastic or felt type.
  • the device comprises a composition-dispensing mechanism which makes it possible to expel said composition from the container to the application member.
  • said dispensing mechanism advantageously comprises a composition-metering means.
  • FIG. 1 is a sectional view of an application device according to a first embodiment
  • FIG. 2 is an exploded view of an application device according to a second embodiment
  • FIG. 3 is a sectional view of the device of Figure 2.
  • the device 1 comprises a cylindrical polypropylene body 2 having a longitudinal axis X.
  • the body 2 denotes a first housing 3 (container), delimited by a cylindrical skirt 19, a first end 18 of which is open, and a second end of which, opposite the first, is closed by a transverse wall 16 comprising passages which emerge to form a grille 42.
  • the transverse wall 16 separates the first housing 3 from a second housing 6, located above the first housing 3.
  • the upper housing 6 has a bottom 7, in the shape of a hemisphere, into which the passages forming the grille 42 emerge.
  • the external surface of the housing 6 comprises a screw thread 10 intended to cooperate with a corresponding screw thread 11 provided for on the internal surface of a skirt 12 of a stopper 13.
  • the stopper is reversibly snap-fastened onto the external surface of the housing 6.
  • the stopper 13 is rigidly connected to an applicator 14 correspondingly made to match the hemispherical profile defined by the bottom 7 of the housing 6.
  • the application member 14 may be adhesively bonded, welded or crimped onto the cap 13.
  • the application member consists of an open-cell polyurethane foam.
  • the density of the foam forming the application member measured according to standard ASTM D 3574-05, is advantageously between 0.02 g.cm “3 and 0.05 g.cm “3 , for example equal to 0.03 g.cm "3 .
  • At least one part of the surface 14 of the application member is covered with a flock 15, in particular based on rayon, cotton, viscose or nylon fibres.
  • the length of the fibres is advantageously between 0.2 mm and 1 mm, for example 0.75 mm.
  • the fibre count grading unit is advantageously between 0.3 dtex and 3.3 dtex, for example equal to 1.7 dtex.
  • the application member 14 is proportioned relative to the housing 6 such that, when the stopper 13 is in the closed position, at least one portion of the application surface of the application member 14 is in contact with the bottom 7.
  • the application member 14 is proportioned such that, in this position, it is not appreciably axially compressed.
  • the composition of the invention is here referred to as product P.
  • This product P is contained inside the housing 3 forming a container, the open end 18 of the housing 3 being closed via a dispensing mechanism 30.
  • the latter is mounted by clip-fastening onto the body 2 of the housing 3, after filling with the product P inside the housing 3 through its open end 18.
  • the mechanism 30 comprises an actuating wheel 31 mounted to rotate freely with respect to the body 2, via a bulge/groove arrangement.
  • the wheel 31 is rigidly connected to a threaded rod 32 capable of axially driving a threaded piston 33, incapable of rotating inside the container, for example by virtue of a rib/notch assembly which prevents the piston from rotating inside the container.
  • the mechanism may also comprise a metering means, such as a ratchet system, capable of periodically generating an audible sound, so as to inform the user of the amount of product dispensed.
  • the mechanism associated with the first housing, for causing the product to exit may be different; for example, the walls of the body 2 may be deformable in order to apply, by crimping, an overpressure in the container so as to expel the product through the grille.
  • the user turns the actuating wheel through half or one turn, with the cap 13 in the closed position over the opening 9 of the housing 6, so as to cause a corresponding amount of product P to pass from the container to the applicator 14 contained in the housing 6, via the passage of the grille 42.
  • the product is taken up by the applicator 14, in particular by capillary action. All that then remains is for the cap 13 to be unscrewed so that the application member can be extracted therefrom and for the product P to be applied by moving the application surface of the application member 14 over lips, in order to deposit the product impregnated in the application member.
  • the application member 14 is axially oversized with respect to the housing 6.
  • the application member 14 is axially oversized with respect to the housing 6.
  • the device is in the form of an applicator bottle for a product P, and comprises mainly a container or reservoir 1 10 consisting of a body 11 1 , one end of which is closed by a bottom 1 12.
  • the other end of the reservoir 1 10 is surmounted by an application head which comprises an intermediate element 130 intended for mounting the head on the reservoir and an application member 120 housed in the intermediate element.
  • the intermediate element 130 comprises, on its external surface, means 132 (of screw thread or snap-fitting bead type) for enabling the removable mounting of a stopper 140 capable of covering the application member 120.
  • a dispensing mechanism can be combined with the reservoir, for example a piston mechanism as previously described, or flexible walls making it possible to generate an overpressure in the reservoir in order to expel the product.
  • a ball 160 can be placed inside the reservoir so as to homogenize the product in order to facilitate the flow thereof and/or to facilitate the conveying thereof to the application member.
  • the internal wall of the intermediate element 130 defines a cylindrical internal housing 133 which rotates about an axis X.
  • This housing 133 comprises a side wall 134 and a planar transverse wall 135 constituting the bottom of the housing.
  • a fitting skirt 136 extends the side wall beyond the transverse wall, on the opposite side from the opening 131 of the intermediate element.
  • the fitting skirt 136 is attached, by snap-fitting, onto the body of the reservoir, at the top of which a radial projection 1 14 is provided for, on the opposite side from the bottom 1 12.
  • This snap-fitting system can of course be replaced with any other system of attachment, in particular a screw attachment system.
  • a sealing skirt 137 is advantageously provided for on the transverse wall 135 of the housing so as to come into leaktight contact with the inside of the reservoir.
  • the body 1 1 1 of the reservoir, the intermediate element 130 and also the stopper 140 are made of rigid material, for example of polyethylene. It is obvious that these three independent elements can each be made of a different material. It is thus possible to envisage using a flexible material for at least one part of the reservoir.
  • the housing 133 communicates with the inside of the reservoir via a passage 139 which passes through a shaft 1 15 extending along the axis of the housing.
  • the shaft is made up of a single part with the transverse wall 135 from which it extends to a free end, located inside the housing 133.
  • the shaft has a circular internal cross section, which is constant throughout its axial height, whereas its external cross section decreases to the free end.
  • the diameter of the shaft is chosen according to the product contained in the reservoir, in such a way that the product coming from the reservoir can flow in the shaft, for example by simply shaking the assembly.
  • the application member 120 is mounted inside the housing 133 around the shaft 1 15.
  • the application member is in the form of a block of porous material(s), at least one part of which is elastically compressible.
  • the application member is made up of a block of open-cell foam, in particular a block of polyurethane foam.
  • the application member 120 may be made up of an axial succession of at least two portions of foam, of different compressibilities, which can be adhesively bonded together.
  • the application member has a cylindrical shape and has a circular cross section. It is obvious that the application member can have any other shape, and can have any other cross section.
  • the application member 120 has a side wall 121 , one end 122 of which constitutes a dome-shaped application surface.
  • the application surface 122 can be covered with a flock.
  • the flock may consist of hairs of various diameters and/or of various natures and/or of various heights, or of a mixture of such hairs.
  • the application member ends with a second open end 124 which comes into contact with the transverse wall 135 of the housing.
  • the end 124 can be permanently attached to the intermediate element 130.
  • this end is removably attached so as to make it possible to easily remove the application member in order, for example, to clean it.
  • the end 124 of the application member is covered with a permanent adhesive, for example an acrylic adhesive, which adheres more to the application member than to the wall 135.
  • a portion 123 of the side wall located on the side of the open end 124 acts as a support for the application member.
  • the portion 123 acting as a support for the application member is separated from the rest of the application member by an annular groove 150 which defines a zone of smaller cross section.
  • the annular groove 150 provided for on the periphery of the application member enables the zone of smaller cross section to have a greater compressibility than the rest of the application member.
  • the application member When the application member is mounted in the housing 133, it occupies approximately the entire housing, the application member having a shape approximately complementary to the shape of the housing.
  • the application member 120 has in particular an axial recess 125, the shape of which is adjusted so that the application member comes to press against the wall of the shaft, without being substantially laterally compressed by said shaft.
  • the side wall of the application member can be at a distance from the shaft.
  • the axial recess 125 When the application member is in the relaxed position, the axial recess 125 has an axial height which is substantially greater than the axial height of the shaft 115 so as to define an internal cavity inside the application member, between an internal surface 126 located facing the shaft and the free end of the shaft.
  • the portion 127 of the application member located above the cavity has an axial thickness which is smaller than the thickness of the lateral edge 121 of the application member, measured perpendicular to the axis X.
  • the cavity can thus constitute a store of product in proximity to the application surface, it being possible for the product to come into contact with the application member only in the cavity.
  • the application member has a diameter of between 2 mm and 20 mm, and preferably between 5 mm and 15 mm. Its height, in the non-compressed position, can range between 2 mm and 20 mm.
  • the application member 120 comprises pores or open cells which have an average size of between 0.3 mm and 0.5 mm.
  • the pores or cells communicate with one another omnidirectionally.
  • the user shakes the packaging and application assembly in order to bring the product into the shaft and into the application member.
  • the user actuates a dispensing mechanism in order to bring the product to the application member.
  • Product is then kept inside the block of foam 120 of the application member by capillary action. All that is then needed is to bring the application member 120 into contact with the area to be treated; a slight pressure can be applied so as to place the product present in the cells of the foam in proximity to the application surface 122.
  • Product is then spread by passing the application surface 122 over the support to be treated, by simple capillary contact, so as to draw the product in the form of a film, under the action of the affinity of the product that is exerted between the application surface and the support to be treated, without the slightest pressure being appreciably exerted on the application assembly.
  • the shape of the applicator may be different from the shape illustrated with reference to the embodiments that have just been described.
  • the shape of the applicator is chosen according to the area to be treated. For example, in the case of an applicator for the lips, an applicator approximately in the shape of a cone, a nose-cone or a hemisphere will more particularly be used, the applicator optionally comprising a bevelled face.
  • the applicator can be dissociated from a container containing the product without a dispensing mechanism.
  • the device is then used by dipping the applicator in the container and then by applying the product to the lips by means of the applicator.
  • composition is prepared (the contents are expressed as weight of starting material).
  • Pentaerythrityl tetraisostearate (Crodamol PTIS-LQ sold by Croda) 4.5
  • Ground pigmentary material (phase E) is prepared by dispersing the pigments in the pentaerythrityl tetraisostearate using an Exakt three-roll machine (at least 3 treatments).
  • the gel C is prepared by mixing the ingredients with a TM DAC 150.1 speed mixer from Hauschild, at 3500 rpm for 3 minutes.
  • Phase A, B, the ground material E and the gel C are stirred using a Moritz rotor-stator for 20 minutes at 70°C. Phase D is then added.
  • Phase F is prepared by mixing with magnetic stirring in a beaker.
  • phase G and then phase H are then successively added, after homogenization.
  • composition obtained is homogeneous and stable. There is no leaching or sedimentation after treatment in a centrifuge (900*g for 1 hour).
  • Pack 1 application member consisting of S90NR foam from the company Crest Foam Industries, covered with a flock from the company ERZI Flocktechnik (0.75 mm; 1.7 dtex).
  • Pack 2 applicator for compositions of lip gloss type (flexible flocked applicator 14030; GEKA GmbH).
  • Very thin, homogeneous and comfortable deposits are obtained, with a moisturizing sensation on application and without any dragging when the lips are slid one over the other, after 10 minutes, 30 minutes and 1 hour of drying.
  • the deposits migrate little and are sparingly tacky/non-tacky.
  • the composition obtained is homogeneous and stable, without leaching or sedimentation after treatment in a centrifuge (900g for 1 hour).
  • Very thin, homogeneous, sparingly tacky/non-tacky and sparingly migrating deposits are obtained. However, they are drier and less comfortable than in the case of the composition in accordance with the invention, with a dragging sensation when the lips are slid one over the other, this being the case 10 minutes after application.
  • compositions are prepared (the contents are expressed as weight of starting material).
  • Disteardimonium hectorite sold under the name
  • Ground pigmentary material (phase E) is prepared by dispersing the pigments in the pentaerythrityl tetraisostearate using an Exakt three-roll machine (at least 3 treatments).
  • the gel C is prepared by mixing the ingredients with a TM DAC 150.1 speed mixer from Hauschild, at 3500 rpm for 3 minutes.
  • Phase A, B, the ground material E and the gel C are stirred using a Moritz rotor-stator for 20 minutes at 70°C. Phase D is then added.
  • Phase F is prepared by mixing with magnetic stirring in a beaker.
  • phase G and then phase H are then successively added, after homogenization.
  • compositions obtained are homogeneous and stable. There is no leaching or sedimentation after treatment in the centrifuge (900g for 1 hour).
  • Pack 1 application member consisting of S90NR foam from the company Crest Foam Industries, covered with a flock from the company ERZI Flocktechnik (0.75 mm; 1 .7 dtex).
  • Pack 2 applicator for compositions of lip gloss type (flexible flocked applicator 14030;
  • Very thin, homogeneous and comfortable deposits are obtained, with a moisturizing sensation on application and without any dragging when the lips are slid one over the other, after 10 minutes, 30 minutes and 1 hour of drying.
  • the deposits migrate little and are sparingly tacky/non-tacky.
  • the composition obtained is homogeneous and stable, without leaching or sedimentation after treatment in a centrifuge (900*g for 1 hour).
  • Very thin, homogeneous, sparingly tacky/non-tacky and sparingly migrating deposits are obtained. However, they are drier and less comfortable than in the case of the composition in accordance with the invention, with a dragging sensation when the lips are slid one over the other, this being the case 10 minutes after application.

Abstract

The present invention relates to a composition for making up and/or caring for in particular the lips, in the form of an emulsion comprising: a.at least one film-forming polymer chosen from vinyl polymers comprising at least one carbosiloxane dendrimer-based unit, b.at least one non-volatile oil, c.at least one silicone gum, d.at least one semi-crystalline polymer or at least one wax, e.at least 10% by weight, relative to the total weight of the composition, of water. The present invention also relates to a process for making up and/or caring for the lips, comprising the application to the lips of a composition according to the invention. Finally, the present invention relates to a device comprising the composition according to the invention.

Description

AQUEOUS EMULSION COMPRISING A SILICONE-BASED DENDRITIC POLYMER, A SILICONE GUM AND A SEMI-CRYSTALLINE POLYMER OR A WAX AND TREATMENT
OF THE LIPS The present invention relates to a cosmetic composition for making up and/or caring for in particular the lips, in the form of an emulsion comprising an aqueous phase, at least one silicone-based dendritic film-forming polymer, at least one non-volatile oil, at least one silicone gum and at least one semi-crystalline polymer or at least one wax. The present invention also relates to a makeup and/or care process, preferably for the lips, which consists in applying said composition, and also to a device suitable for the composition.
The development of compositions for making up and/or caring for the lips, in particular fluid compositions such as liquid lipsticks, which are stable and endowed with satisfactory properties in terms of application (glidance on application, ease of spreading and fineness of the deposit), but also in terms of the makeup effect of the deposit on the lips, for instance the absence of migration of the deposit, preferably without becoming tacky, is an ongoing objective.
Until recently, when the term "liquid lipsticks" was used, lip glosses were essentially envisaged, which are anhydrous formulations whose relatively viscous texture is usually applied by means of a brush dipping into the composition.
With these compositions, it is observed that the deposit is relatively thick, which gives it a more or less tacky nature, especially induced by the use of ingredients, in particular nonvolatile oils or polymers that provide gloss. This tacky nature may be reflected by adhesion of the made-up lips to each other, resulting in a sensation of discomfort to the user. In addition, the coverage of the deposit is variable and it has rather limited persistence.
However, in recent years, new generations of liquid lip formulations have appeared, which are no longer anhydrous, but are in the form of aqueous emulsions whose viscosity is considerably lower than that of the existing glosses.
As examples of such compositions, mention may be made especially of those described in patent applications WO 2014/154700 and WO 2014/154701 , which are thus in emulsion form, comprising water, non-volatile and volatile oils and an acrylic film-forming polymer bearing silicone dendrimer-based units. These compositions make it possible to obtain an extremely thin deposit, which is virtually imperceptible on the lips, highly coloured and covering, non-tacky, non-migrating and with a matte result due to the large amounts of volatile species initially present in the composition.
However, in the field of very fluid compositions for the lips, the search continues for formulations that make it possible to obtain a satiny and thus more glossy deposit, which nevertheless maintains fineness properties, absence of tack and good persistence over time.
It is moreover desired to improve the comfort of these very fluid compositions, once they have been applied to the lips, in particular by giving them the ability to remain mobile on the lips for longer, without this prohibitively detracting from the good properties of the deposit, especially the absence of migration. Specifically, the very fluid compositions described previously attach rapidly to the lips once they have been applied, due to their very high content of volatile compounds. Now, consumers may wish to maintain a sensation of mobility or "modulability" of the deposit when they slide their lips one over the other. These objectives and others are achieved by the present invention, which relates to a make-up and/or care composition, in particular for the lips, comprising:
a. at least one film-forming polymer chosen from vinyl polymers comprising at least one carbosiloxane dendrimer-based unit,
b. at least one non-volatile oil,
c. at least one silicone gum,
d. at least one semi-crystalline polymer or at least one wax,
e. at least 10% by weight, relative to the total weight of the composition, of water.
The invention also relates to a make-up and/or care composition, in particular for the lips, comprising:
a. at least one film-forming polymer chosen from vinyl polymers comprising at least one carbosiloxane dendrimer-based unit,
b. at least one non-volatile oil,
c. at least one silicone gum,
d. at least one wax,
e. at least 1 0% by weight, relative to the total weight of the composition, of water.
The invention also relates to a process for making up and/or caring for the lips, which consists in applying said composition, and also to a device comprising the composition and suitable for using same. The compositions according to the invention are very fluid, homogeneous and stable over time, without sedimentation, for example of the pigments or fillers present, or exudation, in particular of the oil(s) present.
They are easy to apply, with good glidance, and the deposited film has the advantage of always being very thin, homogeneous, allowing a precise contour to be defined on the lips.
Furthermore, the deposit obtained is comfortable, not only in the sense that it is flexible on the lips and does not cause any sensation of dryness thereon, but also because it remains mobile and modulable once applied, without degradation of the other performance qualities, especially the absence of migration and the persistence.
It should also be noted that this comfort nature afforded by the deposit is persistent. In addition, and this represents a very desired advantage, this deposit is not tacky.
Throughout the application, the wording "comprising a" or "containing a" means "comprising at least one" or "containing at least one", unless otherwise specified. The expressions "at least one" and "several" are used without distinction.
Unless otherwise indicated, the limits indicated for a range are included in that range. The cosmetic composition for making up and/or caring for the lips according to the invention is in the form of an emulsion, especially a water-in-oil (inverse) or oil-in-water (direct) emulsion, preferably in the form of an (inverse) water-in-oil emulsion.
Advantageously, the composition according to the invention is in the form of a liquid emulsion.
The term "liquid" means a fluid texture, the viscosity of which at 25°C is more particularly between 0.005 and 12 Pa.s, preferably between 0.01 and 10 Pa.s and even more advantageously between 0.05 and 8 Pa.s.
Preferably, the viscosity at 25°C of a composition according to the invention is between 0.1 and 6 Pa.s.
Protocol for measuring the viscosity:
The viscosity measurement is generally performed at 25°C, using a Rheomat RM180 viscometer equipped with a No. 2 or 3 spindle, the measurement being performed after 10 minutes of rotation of the spindle in the composition, at a shear rate of 200 rpm.
Other characteristics and details of the invention will emerge more clearly on reading the description and the examples that follow. FILM-FORMING POLYMER
As indicated previously, the composition according to the invention comprises at least one film-forming polymer chosen from vinyl polymers comprising at least one carbosiloxane dendrimer-based unit.
The term "film-forming polymer" is intended to mean a polymer that is capable of forming, by itself or in the presence of an auxiliary film-forming agent, a continuous deposit on a support, in particular on keratin materials.
The vinyl polymer(s) have a backbone and at least one side chain, which comprises a carbosiloxane dendrimer-based unit having a carbosiloxane dendrimer structure.
The term "carbosiloxane dendrimer structure" in the context of the present invention represents a molecular structure bearing branched groups of high molecular masses, said structure having high regularity in the radial direction starting from the bond to the backbone. Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer in Japanese patent application JP 9-171 154.
A vinyl polymer according to the invention may contain carbosiloxane dendrimer-based units that may be represented by the general formula (I) below:
Figure imgf000004_0001
(I) in which:
- R j1 represents an aryl group containing from 5 to 10 carbon atoms or an alkyl group containing from 1 to 10 carbon atoms;
- X1 represents a silylalkyi group which, when i = 1 , is represented by formula (II):
Figure imgf000005_0001
in which:
. R1 is as defined above in formula (I),
. R2 represents an alkylene radical containing from 2 to 10 carbon atoms,
. R3 represents an alkyl group containing from 1 to 10 carbon atoms,
. Xl+1 is chosen from: a hydrogen atom, an alkyl group containing from 1 to 10 carbon atoms, an aryl group containing from 5 to 10 carbon atoms and a silylalkyi group defined above of formula (II) with i = i + 1 ,
. i is an integer from 1 to 10 which represents the generation of said silylalkyi group, and . a' is an integer from 0 to 3;
- Y represents a radical-polymerizable organic group chosen from:
. organic groups containing a methacrylic group or an acrylic group, said organic groups being represented by the formulae:
R4 O
FT O
H2C= =c— c- N- R°-
H2C= -c- -O— R- or H
in which:
* R4 represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms; and
* R5 represents an alkylene group containing from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, methylene and propylene groups being preferred; and
. organic groups containing a styryl group of formula:
Figure imgf000005_0002
in which:
* R6 represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, the methyl group being preferred;
* R7 represents an alkyl group containing from 1 to 10 carbon atoms; * R represents an alkylene group containing from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, the ethylene group being preferred;
* b is an integer from 0 to 4; and
* c is 0 or 1 , such that, if c is 0, -(R8)c- represents a bond.
According to one embodiment, R1 may represent an aryl group containing from 5 to 10 carbon atoms or an alkyi group containing from 1 to 10 carbon atoms. The alkyi group may preferably be represented by a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group or a cyclohexyl group. The aryl group may preferably be represented by a phenyl group and a naphthyl group. The methyl and phenyl groups are more particularly preferred, and the methyl group is preferred among all.
According to one embodiment, R2 represents an alkylene group containing from 2 to 10 carbon atoms, in particular a linear alkylene group, such as an ethylene, propylene, butylene or hexylene group; or a branched alkylene group, such as a methylmethylene, methylethylene, 1 -methylpentylene or 1 ,4-dimethylbutylene group. The ethylene, methylethylene, hexylene, 1 -methylpentylene and 1 ,4-dimethylbutylene groups are preferred among all.
According to one embodiment, R3 is chosen from methyl, ethyl, propyl, butyl and isopropyl groups.
In formula (II), i indicates the number of generations and thus corresponds to the number of repeats of the silylalkyl group.
For example, when the generation number is equal to 1 , the carbosiloxane dendrimer may be represented by the general formula shown below, in which Y, R1, R2 and R3 are as defined above, R12 represents a hydrogen atom or is identical to R1; a1 is identical to a'. Preferably, the total average number of groups OR3 in a molecule is within the range from 0 to 7.
Figure imgf000006_0001
When the generation number is equal to 2, the carbosiloxane dendrimer may be represented by the general formula below, in which Y, R1, R2, R3 and R12 are the same as defined above; a1 and a2 represent the a' of the indicated generation. Preferably, the total average number of groups OR3 in a molecule is within the range from 0 to 25. R R R1
I I
Y— Si- O- -Si- -Si- -0— Si -R
L L I
R1
3-a2
3-a
When the generation number is equal to 3, the carbosiloxane dendrimer is represented by the general formula below, in which Y, R1, R2, R3 and R12 are the same as defined above; a1, a2 and a3 represent the a' of the indicated generation. Preferably, the total average number of groups OR3 in a molecule is within the range from 0 to 79.
-Si- -0—
Figure imgf000007_0001
A vinyl polymer bearing at least one carbosiloxane dendrimer-based unit has a molecular side chain containing a carbosiloxane dendrimer structure, and may be derived from the polymerization of:
(A) from 0 to 99.9 parts by weight of a vinyl monomer; and
(B) from 100 to 0.1 parts by weight of a carbosiloxane dendrimer containing a radical- polymerizable organic group, represented by general formula (I) as defined above.
The monomer of vinyl type that is the component (A) in the vinyl polymer bearing at least one carbosiloxane dendrimer-based unit is a monomer of vinyl type that contains a radical-polymerizable vinyl group.
There is no particular limitation as regards such a monomer.
The following are examples of this monomer of vinyl type: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate or a methacrylate of lower alkyl analogue; glycidyl methacrylate; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate or a higher methacrylate analogue; vinyl acetate, vinyl propionate or a vinyl ester of a lower fatty acid analogue; vinyl caproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate or a higher fatty acid ester analogue; styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl methacrylate, vinylpyrrolidone or similar vinylaromatic monomers; methacrylamide, N-methylolmethacrylamide, N- methoxymethylmethacrylamide, isobutoxymethoxymethacrylamide, N,N- dimethylmethacrylamide or similar monomers of vinyl type containing amide groups; hydroxyethyl methacrylate, hydroxypropyl alcohol methacrylate or similar monomers of vinyl type containing hydroxyl groups; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or similar monomers of vinyl type containing a carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether or a similar monomer of vinyl type with ether bonds; methacryloxypropyltrimethoxysilane, polydimethylsiloxane containing a methacrylic group on one of its molecular ends, polydimethylsiloxane containing a styryl group on one of its molecular ends, or a similar silicone compound containing unsaturated groups; butadiene; vinyl chloride; vinylidene chloride; methacrylonitrile; dibutyl fumarate; anhydrous maleic acid; anhydrous succinic acid; methacryl glycidyl ether; an organic salt of an amine, an ammonium salt, and an alkali metal salt of methacrylic acid, of itaconic acid, of crotonic acid, of maleic acid or of fumaric acid; a radical-polymerizable unsaturated monomer containing a sulfonic acid group such as a styrenesulfonic acid group; a quaternary ammonium salt derived from methacrylic acid, such as 2-hydroxy-3- methacryloxypropyltrimethylammonium chloride; and a methacrylic acid ester of an alcohol containing a tertiary amine group, such as a methacrylic acid ester of diethylamine.
Multifunctional monomers of vinyl type may also be used. The following represent examples of such compounds: trimethylolpropane tnmethacrylate, pentaerythrityl tnmethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1 ,4-butanediol dimethacrylate, 1 ,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl methacrylate, tris(2-hydroxyethyl)isocyanurate dimethacrylate, tris(2-hydroxyethyl)isocyanurate tnmethacrylate, polydimethylsiloxane capped with styryl groups containing divinylbenzene groups on both ends, or similar silicone compounds containing unsaturated groups.
A carbosiloxane dendrimer, which is the component (B), may be represented by formula (I) as defined above.
The following represent the preferred examples of group Y of formula (I): an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3- methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4-(2- propenyl)phenyl group, a 3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a 2-(3- vinylphenyl)ethyl group, a vinyl group, an allyl group, a methallyl group and a 5-hexenyl group.
A carbosiloxane dendrimer according to the present invention may be represented by the formulae having the average structures below:
Y '— SiH-O—
Figure imgf000008_0001
CH, CH, CH,
H,C=C— C— O— C3H6— Si Ό— Si— CRH— Si+O— Si-CH
CH, CH,
Figure imgf000009_0001
Figure imgf000010_0001
Thus, according to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by the following formula:
Figure imgf000010_0002
in which:
. Y, R1, R2 and R3 are as defined in formulae (I) and (II) above;
. a1, a2 and a3 correspond to the definition of a' according to formula (II); and
. R12 is H, an aryl group containing from 5 to 10 carbon atoms or an alkyl group containing from 1 to 10 carbon atoms.
According to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by one of the following formulae:
Figure imgf000010_0003
Figure imgf000011_0001
The vinyl polymer comprising the carbosiloxane dendrimer according to the invention may be manufactured according to the process for manufacturing a branched silalkylene siloxane described in Japanese patent application Hei 9-171 154.
To facilitate the preparation of starting material for cosmetic products, the number- average molecular weight of the vinyl polymer bearing a carbosiloxane dendrimer may be chosen within the range between 3000 and 2 000 000 g/mol and preferably between 5000 and 800 000 g/mol. It may be a liquid, a gum, a paste, a solid, a powder, or any other form. The preferred forms are solutions consisting of the dilution of a dispersion or of a powder in solvents.
The vinyl polymer may be a dispersion of a polymer of vinyl type bearing a carbosiloxane dendrimer structure in its side molecular chain, in a liquid such as a silicone oil, an organic oil, an alcohol or water.
The silicone oil may be a dimethylpolysiloxane having the two molecular ends capped with trimethylsiloxy groups, a copolymer of methylphenylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, a copolymer of methyl- 3,3,3-trifluoropropylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, or similar unreactive linear silicone oils, and also hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane or a similar cyclic compound. In addition to the unreactive silicone oils, modified polysiloxanes containing functional groups such as silanol groups, amino groups and polyether groups on the ends or within the molecular side chains may be used.
The organic oils may be isododecane, liquid paraffin, isoparaffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum oil, sunflower oil, soybean oil, camelia oil, squalane, castor oil, cottonseed oil, coconut oil, egg yolk oil, polypropylene glycol monooleate, neopentyl glycol 2-ethylhexanoate or a similar glycol ester oil; triglyceryl isostearate, the triglyceride of a fatty acid of coconut oil, or a similar oil of a polyhydric alcohol ester; polyoxyethylene lauryl ether, polyoxypropylene cetyl ether or a similar polyoxyalkylene ether.
The alcohol may be any type that is suitable for use in combination with a cosmetic product starting material. For example, it may be methanol, ethanol, butanol, isopropanol or similar lower alcohols. A solution or a dispersion of the alcohol should have a viscosity within the range from 10 to 109 mPa at 25°C. To improve the sensory use properties in a cosmetic product, the viscosity should be within the range from 100 to 5 χ 108 mPa.s.
The solutions and dispersions may be readily prepared by mixing a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit with a silicone oil, an organic oil, an alcohol or water. The liquids may be present in the polymerization step. In this case, the unreacted residual vinyl monomer should be completely removed by heat treatment of the solution or dispersion under atmospheric pressure or reduced pressure.
In the case of a dispersion, the dispersity of the polymer of vinyl type may be improved by adding a surfactant.
Such an agent may be hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid or anionic surfactants of the sodium salts of these acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow-trimethylammonium hydroxide, coconut oil-trimethylammonium hydroxide, or a similar cationic surfactant; a polyoxyalkylene alkyl ether, a polyoxyalkylenealkylphenol, a polyoxyalkylene alkyl ester, the sorbitol ester of polyoxyalkylene, polyethylene glycol, polypropylene glycol, an ethylene oxide additive of diethylene glycol trimethylnonanol, and nonionic surfactants of polyester type, and also mixtures.
In the dispersion, a mean particle diameter of the polymer of vinyl type may be within a range of between 0.001 and 100 microns and preferably between 0.01 and 50 microns. The reason for this is that, outside the recommended range, a cosmetic product mixed with the emulsion will not have a nice enough feel on the lips or to the touch, nor sufficient spreading properties nor a pleasant feel.
A vinyl polymer contained in the dispersion or the solution may have a concentration within a range of between 0.1% and 95% by weight and preferably between 5% and 85% by weight. However, to facilitate the handling and the preparation of the mixture, the range should preferably be between 10% and 75% by weight.
A vinyl polymer that is suitable for use in the invention may also be one of the polymers described in the examples of patent application EP 0 963 751.
According to one preferred embodiment, a vinyl polymer grafted with a carbosiloxane dendrimer may be the product of polymerization of:
(A1 ) from 0 to 99.9 part by weight of one or more acrylate or methacrylate monomers; and (B1 ) from 100 to 0.1 part by weight of an acrylate or methacrylate monomer of a tris[tri(trimethylsiloxy)silylethyldimethylsiloxy]silylpropyl carbosiloxane dendrimer.
The monomers (A1 ) and (B1 ) correspond respectively to specific monomers (A) and
(B). According to one embodiment, a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit may comprise a tris[tri(trimethylsiloxy)silylethyldimethylsiloxy]silylpropyl carbosiloxane dendrimer-based unit corresponding to one of the formulae:
Figure imgf000013_0001
or
Figure imgf000013_0002
According to one preferred mode, a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit used in the invention comprises at least one butyl acrylate monomer.
According to one embodiment, a vinyl polymer may also comprise at least one fluoro organic group.
Structures in which the polymerized vinyl units constitute the backbone and carbosiloxane dendritic structures and also fluoro organic groups are attached to side chains are particularly preferred.
The fluoro organic groups may be obtained by replacing with fluorine atoms all or some of the hydrogen atoms of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl groups and other alkyl groups of 1 to 20 carbon atoms, and also alkyloxyalkylene groups of 6 to 22 carbon atoms.
The groups represented by the formula -(CH2)x-(CF2)y-R13 are suggested as examples of fluoroalkyl groups obtained by substituting fluorine atoms for hydrogen atoms of alkyl groups. In the formula, the index "x" is 0, 1 , 2 or 3, and "y" is an integer from 1 to 20. R13 is an atom or a group chosen from a hydrogen atom, a fluorine atom, -CH(CF3)2- or CF(CF3)2. Such fluorine-substituted alkyl groups are exemplified by linear or branched polyfluoroalkyi or perfluoroalkyl groups represented by the formulae shown below:
-CF3, -C2F5, -nC3F7, -CF(CF3)2, -nC4F9, CF2CF(CF3)2, -nC5Fn, -nCsF13, -nC8F17,
CH2CF3, -(CH(CF3)2, CH2CH(CF3)2-CH2(CF2)2F, -CH2(CF2)3F, -CH2(CF2)4F,CH2(CF2)6F, CH2(CF2)8F, -CH2CH2CF3, -CH2CH2(CF2)2F, -CH2CH2(CF2)3F, -CH2CH2(CF2)4F, - CH2CH2(CF2)6F, -CH2CH2(CF2)8F, -CH2CH2(CF2)10F, -CH2CH2(CF2)i2F, CH2CH2(CF2)14F, - CH2CH2(CF2)i6F, -CH2CH2CH2CF3, -CH2CH2CH2(CF2)2F, -CH2CH2CH2(CF2)2H, -CH2(CF2)4H and -CH2CH2(CF2)3H.
The groups represented by -CH2CH2-(CF2)m-CFR14-[OCF2CF(CF3)]n-OC3F7 are suggested as fluoroalkyloxyfluoroalkylene groups obtained by substituting fluorine atoms for hydrogen atoms of alkyloxyalkylene groups. In the formula, the index "m" is 0 or 1 , "n" is 0, 1 , 2, 3, 4 or 5, and R14 is a fluorine atom or CF3. Such fluoroalkyloxyfluoroalkylene groups are exemplified by the perfluoroalkyloxyfluoroalkylene groups represented by the formulae shown below: -CH2CH2CF(CF3)-[OCF2CF(CF3)]n-OC3F7, -CH2CH2CF2CF2-[OCF2CF(CF3)]n- OC3F7.
The number-average molecular weight of the vinyl polymer used in the present invention may be between 3000 and 2 000 000 g/mol and more preferably between 5000 and 800 000 g/mol.
This type of fluorinated vinyl polymer may be obtained by addition:
- of a vinyl monomer (M2) without a fluoro organic group,
- on a vinyl monomer (M1 ) containing fluoro organic groups, and
- a carbosiloxane dendrimer (B) as defined above, of general formula (I) as defined above, by subjecting them to a copolymerization.
Thus, according to one embodiment, a composition of the invention may comprise a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit and being derived from the copolymerization of a vinyl monomer (M1 ) as defined above, optionally of a vinyl monomer (M2) as defined above, and of a carbosiloxane dendrimer (B) as defined above, said vinyl polymer having a copolymerization ratio between the monomer (M1 ) and the monomer (M2) of from 0.1% to 100%/99.9% to 0% by weight, and a copolymerization ratio between the sum of the monomers (M1 ) and (M2) and the monomer (B) of from 0.1 % to 99.9%/99.9% to 0.1 % by weight.
The vinyl monomers (M1 ) containing fluoro organic groups in the molecule are preferably monomers represented by the general formula:
(CH2)=CR15COORf.
In this formula, R15 is a hydrogen atom or a methyl group and Rf is a fluoro organic group exemplified by the fluoroalkyl and fluoroalkyloxyfluoroalkylene groups described above. The compounds represented by the formulae presented below are suggested as specific examples of the component (M1 ). In the formulae present below, "z" is an integer from 1 to 4.
CH2=CCH3COO-CF3, CH2=CCH3COO-C2F5, CH2=CCH3COO-nC3F7,
CH2=CCH3COO-CF(CF3)2, CH2=CCH3COO-nC4F9,
CH2=CCH3COO-CF(CF3)2, CH2=CCH3COO-nC5Fn,
CH2=CCH3COO-nC6F13, CH2=CCH3COO-nC8F17, CH2=CCH3COO-CH2CF3,
CH2=CCH3COO-CH(CF3)2, CH2=CCH3COO-CH2CH(CF3)2,
CH2=CCH3COO-CH2 (CF2)2F, CH2=CCH3COO-CH2(CF2)2F,
CH2=CCH3COO-CH2(CF2)4F, CH2=CCH3COO-CH2(CF2)6F,
CH2=CCH3COO-CH2(CF2)8F, CH2=CCH3COO-CH2CH2CF3,
CH2=CCH3COO-CH2CH2(CF2)2F, CH2=CCH3COO-CH2CH2(CF2)3F,
CH2=CCH3COO-CH2CH2(CF2)4F, CH2=CCH3COO-CH2CH2(CF2)6F,
CH2=CCH3COO-CH2CH2(CF2)8F, CH2=CCH3COO-CH2CH2(CF2)10F,
Figure imgf000014_0001
CH2=CCH3COO-CH2-CH2-(CF2)16F, CH2=CCH3COO-CH2CH2CH2CF3,
CH2=CCH3COO-CH2CH2CH2(CF2)2F, CH2=CCH3COO-CH2CH2CH2(CF2)2H, CH2=CCH3COO-CH2 (CF2)4H, CH2=CCH3COO-(CF2)3H,
CH2=CCH3COO-CH2CH2CF(CF3)-[OCF2-CF(CF3)]z-OC3F7,
CH2=CCH3COO-CH2CH2CF2CF2-[OCF2-CF(CF3)]z-OC3F7,
CH2=CHCOO-CF3, CH2=CHCOO-C2F5, CH2=CHCOO-nC3F7,
CH2=CHCOO-CF(CF3)2, CH2=CHCOO-nC4F9, CH2=CHCOO-CF2CF(CF3)2,
CH2=CHCOO-nC5F11, CH2=CHCOO-nC6F13, CH2=CHCOO-nC8F17,
CH2=CHCOO-CH2CF3, CH2=CHCOO-CH(CF3)2, CH2=CHCOO-CH2CH(CF3)2,
CH2=CHCOO-CH2(CF2)2F, CH2=CHCOO-CH2(CF2)3F,
CH2=CHCOO-CH2(CF2)4F, CH2=CHCOO-CH2(CF2)6F,
CH2=CHCOO-CH2(CF2)8F, CH2=CHCOO-CH2CH2CF3,
CH2=CHCOO-CH2CH2 (CF2)2F, CH2=CHCOO-CH2CH2(CF2)3F,
CH2=CHCOO-CH2CH2(CF2)4F, CH2=CHCOO-CH2CH2(CF2)6F,
CH2=CHCOO-CH2CH2(CF2)8F, CH2=HCOO-CH2CH2(CF2)10F,
CH2-CHCOO-CH2CH2-(CF2)12F, CH2=CHCOO-CH2CH2(CF2)14F,
CH2=CHCOO-CH2CH2(CF2)16F, CH2=CHCOO-CH2CH2CH2CF3,
CH2=CHCOO-CH2CH2CH2(CF2)2F, CH2=CHCOO-CH2CH2CH2(CF)2H,
CH2=CHCOO-CH2(CF2)4H, CH2=CHCOO-CH2CH2(CF2)3H,
CH2=CHCOO-CH2CH2CF(CF3)-, [OCF2-CF(CF3)]z-OC3F7,
CH2=CHCOO-CH2CH2CF2CF2(CF3)-[OCF2-CF(CF3)]2-OC3F7.
Among these, the vinyl polymers represented below are preferred:
CH2=CHCOO-CH2CH2(CF2)6F, CH2=CHCOO-CH2CH2(CF2)8F,
CH2=CCH3COO-CH2CH2(CF2)6F, CH2=CCH3COO-CH2CH2(CF2)8F,
CH2=CHCOO-CH2CF3, CH2= CCH3COO-CH2CF3.
The vinyl polymers represented by the formulae presented below are particularly preferred:
CH2=CHCOO-CH2CF3,
CH2=CCHCOO-CH2CF3.
The vinyl monomers (M2) not containing any fluoro organic groups in the molecule may be any monomers containing radical-polymerizable vinyl groups which are exemplified, for example, by methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and other lower alkyl acrylates or methacrylates; glycidyl acrylate, glycidyl methacrylate; n-butyl acrylate, n- butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, and other higher acrylates and methacrylates; vinyl acetate, vinyl propionate and other lower fatty acid vinyl esters; vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, and other higher fatty acid esters; styrene, vinyltoluene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, vinylpyrrolidone, and other vinyl aromatic monomers; dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and other aminovinyl monomers, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N- methoxymethylacrylamide, N-methoxymethylmethacrylamide, isobutoxymethoxyacrylamide, isobutoxymethoxymethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, and other vinylamide monomers; hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylic acid hydroxypropyl alcohol, methacrylic acid hydroxypropyl alcohol, and other hydroxyvinyl monomers; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and other vinylcarboxylic acid monomers; tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, ethoxydiethylene glycol acrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and other vinyl monomers containing ether bonds; acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, polydimethylsiloxanes containing acryl or methacryl groups at one of the ends, polydimethylsiloxanes containing alkenylaryl groups at one of the ends and other silicone compounds containing unsaturated groups; butadiene; vinyl chloride; vinylidene chloride, acrylonitrile, methacrylonitrile; dibutyl fumarate; maleic anhydride; dodecylsuccinic anhydride; acryl glycidyl ether, methacryl glycidyl ether, 3,4- epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, alkali metal salts, ammonium salts and organic amine salts of acrylic acid, of methacrylic acid, of itaconic acid, of crotonic acid, of fumaric acid, of maleic acid and of other radical-polymerizable unsaturated carboxylic acids, radical-polymerizable unsaturated monomers containing sulfonic acid groups, such as styrene sulfonic acid and also the alkali metal salts thereof, the ammonium salts thereof and the organic amine salts thereof; the quaternary ammonium salts derived from acrylic acid or methacrylic acid, such as 2-hydroxy-3- methacryloxypropyltrimethylammonium chloride, methacrylic acid esters of a tertiary amine alcohol, such as the diethylamine ester of methacrylic acid and quaternary ammonium salts thereof.
In addition, it is also possible to use as vinyl monomers (M2) the polyfunctional vinyl monomers illustrated, for example, by trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythrityl triacrylate, pentaerythrityl trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1 ,4- butanediol diacrylate, 1 ,4-butanediol dimethacrylate, 1 ,6-hexanediol diacrylate, 1 ,6- hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl acrylate, trimethylolpropanetrioxyethyl methacrylate, tris(2- hydroxyethyl)isocyanurate diacrylate, tris(2-hydroxyethyl)isocyanurate dimethacrylate, tris(2- hydroxyethyl)isocyanurate triacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, polydimethylsiloxane in which the two ends of the molecular chain are blocked with alkenylaryl groups, and other silicone compounds containing unsaturated groups. As regards the ratio mentioned above in which (M1 ) and (M2) are copolymerized, the weight ratio between (M1 ) and (M2) is preferably within the range 1 :99 to 100:0.
Y can be chosen, for example, from organic groups containing acrylic or methacrylic groups, organic groups containing an alkenylaryl group, or alkenyl groups containing from 2 to 10 carbon atoms.
The organic groups containing acrylic or methacrylic groups and the alkenylaryl groups are as defined above.
Among the compounds (B), mention may, for example, be made of the following compounds:
CH, CH,
I 3 I
H2C=CH-Si- -o— Si- -C2H4- -Si- -o- -Si-CH
I I
CH, CH,
Figure imgf000017_0001
The carbosiloxane dendrimers (B) may be prepared using the process for preparing siloxane/silalkylene branched copolymers described in document EP 1 055 674.
For example, they may be prepared by subjecting organic alkenyl silicone compounds and silicone compounds comprising hydrogen atoms bonded to the silicon, represented by formula (IV) as defined above, to a hydrosilylation reaction.
The copolymerization ratio (by weight) between the monomer (B) and the monomers (M1 ) and (M2) is preferably within the range of 1 :99 to 99:1 and even more preferably within the range of 5:95 to 95:5.
Amino groups may be introduced into the side chains of the vinyl polymer by using, included in component (M2), vinyl monomers containing amino groups, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, followed by performing a modification with potassium acetate monochloride, ammonium acetate monochloride, the aminomethylpropanol salt of monochloroacetic acid, the triethanolamine salt of monobromoacetic acid, sodium monochloropropionate, and other alkali metal salts of halogenated fatty acids.
Alternatively, carboxylic acid groups may be introduced into the side chains of the vinyl polymer by using, included in component (M2), vinyl monomers containing carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid, and the like, followed by neutralizing the product with triethylamine, diethylamine, triethanolamine and other amines.
A fluorinated vinyl polymer may be one of the polymers described in the examples of patent application WO 03/045 337. According to one preferred embodiment, a vinyl polymer grafted in the sense of the present invention may be conveyed in an oil or a mixture of oils, which is/are preferably volatile, chosen in particular from silicone oils and hydrocarbon-based oils, and mixtures thereof.
According to one particular embodiment, a silicone oil that is suitable for use in the invention may be cyclopentasiloxane.
According to another particular embodiment, a hydrocarbon-based oil that is suitable for use in the invention may be isododecane.
Vinyl polymers grafted with at least one carbosiloxane dendrimer-based unit that may be particularly suitable for use in the present invention are the polymers whose I NCI name is Acrylates/polytrimethylsiloxy methacrylate copolymer, and especially sold under the names FA 4002 ID Silicone Acrylate, FA 4001 CM Silicone Acrylate by the company Dow Corning.
According to one embodiment, the composition according to the present invention comprises at least one vinyl polymer bearing at least one carbosiloxane dendrimer-based unit in an active material content ranging from 0.5% to 20% by weight, in particular from 1 % to 15% by weight, more particularly from 1 .5% to 10% by weight and preferably from 3% to 5% by weight, relative to the total weight of the composition.
NON-VOLATILE OILS
The composition according to the invention also comprises at least one non-volatile oil.
The term "oil" means a water-immiscible non-aqueous compound, which is liquid at 25°C and atmospheric pressure (1.013x105 Pa).
The term "immiscible" means that the mixture of the same amount of water and of oil, after stirring, does not lead to a stable solution comprising only one phase, under the above- mentioned temperature and pressure conditions. The observation is made by eye or using a phase-contrast microscope, if necessary, on 100 g of mixture obtained after sufficient stirring using a ayneri blender to create a vortex in the mixture (as a guide, 200 to 1000 rpm); the resulting mixture being left to stand, in a closed bottle, for 24 hours at room temperature before observation.
The term "non-volatile oil" means an oil whose vapour pressure at 25°C is non-zero and is less than 10~3 mmHg (0.13 Pa) ("closed cup").
As indicated previously, the composition comprises at least one non-volatile oil in a content of at least 5% by weight, preferably ranging from 5% to 30% by weight, more particularly from 10% to 20% by weight relative to the total weight of the composition.
According to one embodiment, the composition comprises at least one non-volatile oil in a content varying from 25% to 60% by weight and preferably from 30% to 50% by weight relative to the total weight of volatile and non-volatile oil(s) present in said composition.
In accordance with a particularly advantageous embodiment, at least one of the nonvolatile oils is compatible with the film-forming polymer, if appropriate conveyed in an oil or a mixture of oils, which are preferably volatile, used in the composition according to the invention. To check this compatibility, several mixtures of the non-volatile oil to be tested were made with the film-forming polymer, where appropriate conveyed in at least one oil, preferably a volatile oil: 30/70; 50/50; 70/30 (the ratios being expressed as weight, each mixture representing 10 g).
Each mixture is prepared at 25°C with stirring (magnetic bar) for one hour.
If the resulting mixture appears to be one-phase, this mixture is observed with a phase- contrast microscope. If there is no sign of one phase dispersed in the other, then said nonvolatile oil and the film-forming polymer in its vehicle (if present) are said to be compatible in the evaluated mixture.
Non-volatile oils that are compatible in all the tested mixtures are more particularly suitable for use. Use may also be made of non-volatile oils that are compatible for some of the tested mixtures, if these oils are used in the composition in a content in which they are compatible. If necessary, on the basis of the results obtained previously, one or more tests may be repeated to check the compatibility at the envisaged content.
Preferably, use is made of at least one non-volatile oil that is compatible with the film- forming polymer/vehicle if present, for the three mixtures described previously.
The non-volatile oil(s) may be chosen from polar or apolar hydrocarbon-based oils, silicone oils and fluoro oils, and mixtures thereof. Polar non-volatile hydrocarbon-based oils
The term "hydrocarbon-based oi!' means an oil formed essentially from, or even consisting of, carbon and hydrogen atoms, and possibly 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.
Preferably, the hydrocarbon-based oil, in addition to being free of silicon and fluorine, is free of heteroatoms such as nitrogen, sulfur and phosphorus. The hydrocarbon-based oil is therefore different from a silicone oil and from a fluoro oil.
In the present case, the polar non-volatile hydrocarbon-based oil comprises at least one oxygen atom.
In particular, this non-volatile hydrocarbon-based oil comprises at least one alcohol function (it is then an "alcohol oil") and/or at least one ester function (it is then an "ester oil").
The ester oils that may be used in the compositions according to the invention may in particular be hydroxylated. The composition may comprise one or more non-volatile hydrocarbon-based oils, in particular chosen from:
- Cin-C?g alcohols, preferably monoalcohols.
More particularly, the Ci0-C26 alcohols are saturated or unsaturated, and branched or unbranched, and comprise from 10 to 26 carbon atoms. Preferably, the C10-C26 alcohols are fatty alcohols, which are preferably branched when they comprise at least 16 carbon atoms.
As examples of fatty alcohols that may be used according to the invention, mention may be made of linear or branched fatty alcohols, of synthetic origin or alternatively of natural origin, for instance alcohols derived from plant material (coconut, palm kernel, palm, etc.) or animal material (tallow, etc.).
Needless to say, other long-chain alcohols may also be used, for instance ether alcohols or alternatively "Guerbet" alcohols.
Finally, use may also be made of certain more or less long fractions of alcohols of natural origin, for instance coconut (C12 to Ci6) or tallow (CiS to Ci8) or compounds of diol or cholesterol type.
Use is preferably made of a fatty alcohol comprising from 10 to 24 carbon atoms and more preferentially from 12 to 22 carbon atoms.
As particular examples of fatty alcohols that may preferably be used, mention may be made especially of lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2-butyloctanol, 2- undecylpentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol and octyldodecanol, and mixtures thereof.
According to one advantageous embodiment of the invention, the alcohol is chosen from octyldodecanol.
- optionally hydroxylated monoesters, diesters or triesters of a C?-Ca monocarboxylic or polycarboxylic acid and of a C?-Cg alcohol.
In particular:
* optionally hydroxylated monoesters of a C2-C8 carboxylic acid and of a C2-C8 alcohol, * optionally hydroxylated diesters of a C2-C8 dicarboxylic acid and of a C2-C8 alcohol, such as diisopropyl adipate, 2-diethylhexyl adipate, dibutyl adipate, diisostearyl adipate or 2- diethylhexyl succinate,
* optionally hydroxylated triesters of a C2-C8 tricarboxylic acid and of a C2-C8 alcohol, such as citric acid esters, such as trioctyl citrate, triethyl citrate, acetyl tributyl citrate, tributyl citrate or acetyl tributyl citrate;
- esters of a C?-C8 polyol and of one or more C?-C8 carboxylic acids, such as glycol diesters of monoacids, such as neopentyl glycol diheptanoate, or glycol triesters of monoacids, such as triacetin;
- ester oils, in particular having between 18 and 70 carbon atoms.
Examples that may be mentioned include monoesters, diesters or triesters.
The ester oils may be hydroxylated or non-hydroxylated.
The non-volatile ester oil may for example be chosen from:
* monoesters comprising between 18 and 40 carbon atoms in total, in particular the monoesters of formula RiCOOR2 in which represents a saturated or unsaturated, linear or branched or aromatic fatty acid residue comprising from 4 to 40 carbon atoms and R2 represents a hydrocarbon-based chain, which is in particular branched, containing from 4 to 40 carbon atoms, on condition that R-i + R2 > 18, for instance Purcellin oil (cetostearyl octanoate), isononyl isononanoate, Ci2 to Ci5 alkyl benzoate, 2-ethylhexyl palmitate, octyldodecyl neopentanoate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, 2-octyldodecyl benzoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, 2- ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate or 2-octyldodecyl myristate.
Preferably, they are esters of formula RiCOOR2 in which R-i represents a linear or branched fatty acid residue containing from 4 to 40 carbon atoms and R2 represents a hydrocarbon-based chain that is in particular branched, containing from 4 to 40 carbon atoms, Ri and R2 being such that Ri + R2 > 18.
Even more particularly, the ester comprises between 18 and 40 carbon atoms in total.
Preferred monoesters that may be mentioned include isononyl isononanoate, oleyl erucate and/or 2-octyldodecyl neopentanoate.
* monoesters of a fatty acid, in particular of 18 to 22 carbon atoms, and in particular of lanolic acid, oleic acid, lauric acid or stearic acid, and of diols, for instance propylene glycol monoisostearate;
* diesters, in particular comprising between 18 and 60 carbon atoms in total and in particular between 18 and 50 carbon atoms in total. Use may be made especially of diesters of a dicarboxylic acid and of monoalcohols, preferably such as diisostearyl malate, or glycol diesters of monocarboxylic acids, such as neopentyl glycol diheptanoate, propylene glycol dioctanoate, diethylene glycol diisononanoate or polyglyceryl-2 diisostearate (in particular such as the compound sold under the commercial reference Dermol DGDIS by the company Alzo);
* hydroxylated monoesters and diesters, preferably with a total carbon number ranging from 18 to 70, for instance polyglyceryl-3 diisostearate, isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate or glyceryl stearate;
* triesters, in particular comprising between 35 and 70 carbon atoms in total, in particular such as triesters of a tricarboxylic acid, such as triisostearyl citrate, or tridecyl trimellitate, or glycol triesters of monocarboxylic acids such as polyglyceryl-2 tri isostearate;
* tetraesters, in particular with a total carbon number ranging from 35 to 70, such as pentaerythritol or polyglycerol tetraesters of a monocarboxylic acid, for instance pentaerythrityl tetrapelargonate, pentaerythrityl tetraisostearate, pentaerythrityl tetraisononanoate, glyceryl tris(2-decyl)tetradecanoate, polyglyceryl-2 tetraisostearate or pentaerythrityl tetrakis(2-decyl)tetradecanoate;
* polyesters obtained by condensation of an unsaturated fatty acid dimer and/or trimer and of diol, such as those described in patent application FR 0 853 634, in particular such as dilinoleic acid and 1 ,4-butanediol. Mention may in particular be made in this respect of the polymer sold by Biosynthis under the name Viscoplast 14436H (INCI name: dilinoleic acid/butanediol copolymer), or else copolymers of polyols and of diacid dimers, and esters thereof, such as Hailucent ISDA;
* esters and polyesters of diol dimer and of monocarboxylic or dicarboxylic acid, such as esters of diol dimer and of fatty acid and esters of diol dimer and of dicarboxylic acid dimer, in particular which may be obtained from a dicarboxylic acid dimer derived in particular from the dimerization of an unsaturated fatty acid especially of C8 to C34, especially of C-12 to C22, in particular of Ci6 to C2o and more particularly of Ci8, such as esters of dilinoleic diacids and of dilinoleic diol dimers, for instance those sold by the company Nippon Fine Chemical under the trade names Lusplan DD-DA5® and DD-DA7®;
* polyesters resulting from the esterification of at least one triglyceride of hydroxylated carboxylic acid(s) with an aliphatic monocarboxylic acid and with an aliphatic dicarboxylic acid, which is optionally unsaturated, for instance the succinic acid and isostearic acid castor oil sold under the reference Zenigloss by Zenitech;
* hydrocarbon-based plant oils such as fatty acid triglycerides (which are liquid at room temperature), especially of fatty acids containing from 7 to 40 carbon atoms, such as heptanoic or octanoic acid triglycerides or jojoba oil; mention may be made in particular of saturated triglycerides such as caprylic/capric triglyceride and mixtures thereof, for example such as the product sold under the reference Myritol 318 from Cognis, glyceryl triheptanoate, glyceryl trioctanoate, and Ci8-36 acid triglycerides such as those sold under the reference Dub TGI 24 by Stearineries Dubois, and unsaturated triglycerides such as castor oil, olive oil, ximenia oil or pracaxi oil;
- vinylpyrrolidone/1 -hexadecene copolymers, for instance the product sold under the name Antaron V-216 (also known as Ganex V216) by the company ISP (MW = 7300 g/mol);
- Ci?-C?fi fatty acids, preferably C12-C22 fatty acids, which are preferably unsaturated, such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof;
- dialkyl carbonates, the 2 alkyl chains possibly being identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC® by Cognis;
- and mixtures thereof.
Apolar non-volatile hydrocarbon-based oils
The composition according to the invention may also comprise at least one apolar nonvolatile hydrocarbon-based oil.
These oils may be of plant, mineral or synthetic origin.
For the purposes of the present invention, the term "apolar hydrocarbon-based oil" means an oil comprising only carbon and hydrogen atoms in its structure.
More particularly, the non-volatile apolar hydrocarbon-based oils are chosen from linear or branched hydrocarbons of mineral or synthetic origin, such as: liquid paraffin or derivatives thereof (mineral oil),
squalane,
isoeicosane,
naphthalene oil,
- polybutenes, for instance Indopol H-100, Indopol H-300 and Indopol H-1500 sold by the company Amoco,
polyisobutenes, hydrogenated polyisobutenes such as especially Parleam®s sold by the company Nippon Oil Fats, Panalane H-300 E sold by the company Amoco, Viseal 20000 sold by the company Synteal and Rewopal PIB 1000 sold by the company Witco, or alternatively Parleam Lite sold by NOF Corporation,
decene/butene copolymers, polybutene/polyisobutene copolymers, especially Indopol
L-14,
polydecenes and hydrogenated polydecenes such as especially: Puresyn 10 and Puresyn 150, or alternatively Puresyn 6 sold by the company ExxonMobil Chemicals, - and mixtures thereof.
Non-volatile silicone oils
The term "silicone o/T means an oil containing at least one silicon atom, and in particular containing Si-0 groups.
Among the non-volatile silicone oils that may be used in the present invention, examples that may be mentioned include non-volatile non-phenyl silicone oils and nonvolatile phenyl silicone oils.
The silicone oils that may be used for the purposes of the invention advantageously have a molecular mass of less than or equal to 150 000 g/mol, preferably less than or equal to 100 000 g/mol and better still less than or equal to 10 000 g/mol.
Non-volatile non-phenyl silicone oils
The term "non-phenyl silicone oil" denotes a silicone oil not comprising any phenyl substituents.
Representative examples of these non-volatile non-phenyl silicone oils which may be mentioned include polydimethylsiloxanes; alkyl dimethicones; vinylmethyl methicones; and also silicones modified with aliphatic groups and/or with functional groups such as hydroxyl, thiol and/or amine groups, preferably hydroxyl groups.
It should be noted that "dimethicone" (INCI name) corresponds to a polydimethylsiloxane (chemical name).
In particular, these oils can be chosen from the following non-volatile oils:
polydimethylsiloxanes (PDMS),
alkyl dimethicones comprising aliphatic groups, in particular alkyl or alkoxy groups, which are pendent and/or at the end of the silicone chain, these groups each comprising from 2 to 24 carbon atoms. By way of example, mention may be made of the cetyl dimethicone sold under the commercial reference Abil Wax 9801 from Evonik Goldschmidt, PDMSs comprising functional groups such as hydroxyl, thiol and/or amine groups, preferably hydroxyl groups,
polydimethylsiloxanes substituted with aliphatic groups, in particular C2-C24 alkyl groups, pendent and/or at the end of the silicone chain, and functional groups such as hydroxyl, thiol and/or amine groups, preferably hydroxyl groups,
polysiloxanes modified with fatty acids, fatty alcohols, and
mixtures thereof.
Preferably, these non-volatile non-phenyl silicone oils are chosen from polydimethylsiloxanes; alkyl dimethicones and also polydimethylsiloxanes substituted with aliphatic groups, in particular C2-C24 alkyl groups, and functional groups such as hydroxyl groups.
The non-volatile non-phenyl silicone oil may be chosen in particular from silicones of formula (I):
Figure imgf000024_0002
Figure imgf000024_0001
(I)
in which:
Ri , R2, R5 and R6 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms,
R3 and R4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms or a hydroxyl radical,
X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical, n and p are integers chosen so as to have a fluid compound, in particular whose viscosity at 25°C is between 8 centistokes (cSt) (8 x 10"6 m2/s) and 800 000 cSt, advantageously less than 100 000 cSt, and advantageously a weight-average molecular mass of less than or equal to 150 000 g/mol, preferably less than or equal to 100 000 g/mol and better still less than or equal to 10 000 g/mol.
As non-volatile non-phenyl silicone oils that may be used according to the invention, mention may be made of those for which:
- the substituents Ri to R6 and X represent a methyl group, and p and n are such that the viscosity is 60 000 cSt, for example the product sold under the name Dow Corning 200 Fluid
60 000 CS by the company Dow Corning, and the product sold under the name Wacker Belsil DM 60 000 by the company Wacker,
- the substituents Ri to R6 and X represent a methyl group, and p and n are such that the viscosity is 100 cSt or 350 cSt, for example the products sold respectively under the names Belsil DM100 and Dow Corning 200 Fluid 350 CS by the company Dow Corning, and - the substituents Ri to R.6 represent a methyl group, the group X represents a hydroxyl group, and n and p are such that the viscosity is 700 cSt, for example the product sold under the name Baysilone Fluid TO.7 by the company Momentive. Non-volatile phenyl silicone oils
The expression "phenyl silicone oil" denotes a silicone oil bearing at least one phenyl substituent.
These non-volatile phenyl silicone oils may be chosen from those also bearing at least one dimethicone fragment, or from those not bearing one. It should be noted that the term "dimethicone fragment" denotes a divalent siloxane group whose silicon atom bears two methyl radicals, this group not being at the ends of the molecule. It may be represented by the following formula: -(Si(CH3)2-0)-.
The non-volatile phenyl silicone oil may thus be chosen from:
phenyl silicone oils optionally bearing a dimethicone fragment corresponding to formula (I) below:
Figure imgf000025_0001
in which the groups R, which are monovalent or divalent, represent, independently of each other, a methyl, methylene, phenyl or phenylene, with the proviso that at least one group R represents a phenyl.
Preferably, in this formula, the phenyl silicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six.
phenyl silicone oils optionally bearing a dimethicone fragment corresponding to formula (II) below:
R R R
R Si I O Si I O Si I R
R I R I R I (II)
in which the groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl.
Preferably, in this formula, the compound of formula (II) comprises at least three, for example at least four or at least five, phenyl groups.
Mixtures of different phenylorganopolysiloxane compounds described above can be used.
Examples that may be mentioned include mixtures of triphenyl-, tetraphenyl- or pentaphenyl-organopolysiloxanes. Among the compounds of formula (II), mention may be made more particularly of phenyl silicone oils not bearing any dimethicone fragments, corresponding to formula (II) in which at least 4 or at least 5 radicals R represent a phenyl radical, the remaining radicals representing methyls.
Such non-volatile phenyl silicone oils are preferably trimethylpentaphenyltrisiloxane or tetramethyltetraphenyltrisiloxane. They are in particular sold by Dow Corning under the reference PH-1555 HRI or Dow Corning 555 Cosmetic Fluid (chemical name: 1 ,3,5-trimethyl-
1 ,1 ,3,5,5-pentaphenyltrisiloxane; INCI name: trimethylpentaphenyltrisiloxane), or the tetramethyltetraphenyltrisiloxane sold under the reference Dow Corning 554 Cosmetic Fluid by Dow Coming can also be used.
They correspond especially to formulae (III) and (III*) below:
Ph Ph Ph Me Ph Me
Me-Si-O- Si-O— Si-Me Si-O-Si-O— Si-Ph
\ \ \ \ \ \
Ph Me Ph (III) M Mee Phn M lviee (III')
in which Me represents methyl, and Ph represents phenyl.
phenyl silicone oils bearing at least one dimethicone fragment corresponding to formula (IV) below:
Figure imgf000026_0001
in which Me represents methyl, y is between 1 and 1000 and X represents
-CH2-CH(CH3)(Ph).
ph reof:
Figure imgf000026_0002
(V) in which:
- R-i to Rio, independently of each other, are saturated or unsaturated, linear, cyclic or branched Ci-C30 hydrocarbon-based radicals,
- m, n, p and q are, independently of each other, integers between 0 and 900, with the proviso that the sum m+n+q is other than 0.
Preferably, the sum m+n+q is between 1 and 100. Advantageously, the sum m+n+p+q is between 1 and 900 and preferably between 1 and 800. Preferably, q is equal to 0.
More particularly, to R 0, independently of each other, represent a saturated or unsaturated, preferably saturated, linear or branched Ci-C30 hydrocarbon-based radical, and in particular a preferably saturated, C C2o, in particular C Ci8, hydrocarbon-based radical, or a monocyclic or polycyclic C6-Ci4, and in particular C10-C13, aryl radical, or an aralkyl radical, the alkyl part of which is preferably C1-C3 alkyl.
Preferably, Ri to R10 may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical. Ri to R10 may in particular be identical, and in addition may be a methyl radical.
As particular embodiments of formula (V), mention may be made of:
o phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding
Figure imgf000027_0001
(VI)
in which:
Ri to R6, independently of each other, are saturated or unsaturated, linear, cyclic or branched C1-C30 hydrocarbon-based radicals, a preferably C6-Ci4 aryl radical or an aralkyl radical, the alkyl part of which is C1-C3 alkyl,
■ m, n and p are, independently of each other, integers between 0 and 100, with the proviso that the sum n+m is between 1 and 100.
Preferably, Ri to R6, independently of each other, represent a C1-C20, in particular Ci- C18, hydrocarbon-based, preferably alkyl, radical, or a C6-Ci4 aryl radical which is monocyclic (preferably C6) or polycyclic and in particular C10-C13, or an aralkyl radical (preferably the aryl part is C6 aryl; the alkyl part is C1-C3 alkyl).
Preferably, Ri to R6 may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical.
Ri to R6 may in particular be identical, and in addition may be a methyl radical. Preferably, m = 1 or 2 or 3, and/or n = 0 and/or p = 0 or 1 can be applied, in formula (VI).
According to one particular embodiment, the non-volatile phenyl silicone oil is chosen from phenyl silicone oils bearing at least one dimethicone fragment.
Preferably, such oils correspond to compounds of formula (VI) in which:
■ m=0 and n and p are, independently of each other, integers between 1 and 100.
Preferably, Ri to R6 are methyl radicals. According to this embodiment, the silicone oil is preferably chosen from a diphenyl dimethicone such as KF-54 from Shin-Etsu (400 cSt), KF54HV from Shin-Etsu (5000 cSt), KF-50-300CS from Shin-Etsu (300 cSt), KF-53 from Shin-Etsu (175 cSt) or KF-50-100CS from Shin-Etsu (100 cSt).
p is between 1 and 100, the sum n+m is between 1 and 100, and n=0.
These phenyl silicone oils optionally bear at least one dimethicone fragment correspond more particularly to formula (VII) below:
Figure imgf000028_0001
in which Me is methyl and Ph is phenyl, OR' represents a group
-OSiMe3 and p is 0 or is between 1 and 1000, and m is between 1 and 1000. In particular, m and p are such that the compound (VII) is a non-volatile oil.
According to a first embodiment of non-volatile phenyl silicone bearing at least one dimethicone fragment, p is between 1 and 1000 and m is more particularly such that compound (VII) is a non-volatile oil. Trimethylsiloxyphenyldimethicone, sold in particular under the reference Belsil PDM 1000 by the company Wacker, may, for example, be used.
According to a second embodiment of non-volatile phenyl silicone not bearing a dimethicone fragment, p is equal to 0 and m is between 1 and 1000, and in particular is such that the compound (VII) is a non-volatile oil.
Phenyltrimethylsiloxytrisiloxane, sold in particular under the reference Dow Corning 556 Cosmetic Grade Fluid (DC556), may, for example, be used. o non-volatile phenyl silicone oils not bearing a dimethicone fragment corresponding to formula (VIII) below, and mixtures thereof:
Figure imgf000028_0002
(VIII)
in which:
- R, independently of each other, are saturated or unsaturated, linear, cyclic or branched Ci- C3o hydrocarbon-based radicals, preferably R is a C1-C30 alkyl radical, a preferably C6-Ci4 aryl radical, or an aralkyl radical, the alkyl part of which is Ci-C3 alkyl,
- m and n are, independently of each other, integers between 0 and 100, with the proviso that the sum n+m is between 1 and 100. Preferably, R, independently of each other, represent a saturated or unsaturated, preferably saturated, linear or branched C1-C30 hydrocarbon-based radical, and in particular a preferably saturated, C1-C20, in particular C1-C18 and more particularly C4-C10, hydrocarbon- based radical, a monocyclic or polycyclic C6-Ci4, and in particular Cio"Ci3, aryl radical, or an aralkyl radical of which preferably the aryl part is C& aryl and the alkyl part is C1-C3 alkyl.
Preferably, the groups R may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical.
The groups R may in particular be identical, and in addition may be a methyl radical. Preferably, m = 1 or 2 or 3, and/or n = 0 and/or p = 0 or 1 can be applied, in formula
(VIII).
According to a preferred embodiment, n is an integer between 0 and 100 and m is an integer between 1 and 100, with the proviso that the sum n+m is between 1 and 100, in formula (VIII). Preferably, R is a methyl radical.
According to one embodiment, a phenyl silicone oil of formula (VIII) with a viscosity at
25°C of between 5 and 1500 mm2/s (i.e. 5 to 1500 cSt), and preferably with a viscosity of between 5 and 1000 mm2/s (i.e. 5 to 1000 cSt), may be used.
According to this embodiment, the non-volatile phenyl silicone oil is preferably chosen from phenyl tnmethicones (when n=0) such as DC556 from Dow Corning (22.5 cSt), or else from diphenylsiloxyphenyl trimethicone oil (when m and n are between 1 and 100) such as KF56 A from Shin-Etsu, or the Silbione 70663V30 oil from Rhone-Poulenc (28 cSt). The values in parentheses represent the viscosities at 25°C.
phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding to the following formula, and mixtures thereof:
Figure imgf000029_0001
(IX)
in which:
R-i, R, R5 and R6, which may be identical or different, are an alkyl radical containing 1 to 6 carbon atoms,
R3 and R4, which may be identical or different, are an alkyl radical containing from 1 to 6 carbon atoms or an aryl radical (preferably C6-C14), with the proviso that at least one of R3 and R4 is a phenyl radical,
X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical, n and p being an integer greater than or equal to 1 , chosen so as to give the oil a weight- average molecular weight preferably less than 150 000 g/mol and more preferably less than 100 000 g/mol. and a mixture thereof.
Non-volatile fluoro oils
The term "fluoro oil" means an oil containing at least one fluorine atom.
Among the non-volatile fluoro oils that may be used in the present invention, mention may be made in particular of fluorosilicone oils, fluoro polyethers and fluorosilicones especially as described in document EP-A-847 752, and perfluoro compounds.
The term "perfluoro compounds" means compounds in which all the hydrogen atoms have been replaced with fluorine atoms.
According to one embodiment, the fluoro oil is chosen from perfluoro oils. As examples of perfluoro oils, mention may be made of perfluorodecalins and perfluoroperhydro- phenanthrenes.
According to one embodiment, the fluoro oil is chosen from perfluoroperhydro- phenanthrenes, and especially the Fiflow® products sold by the company Creations Couleurs. In particular, use may be made of the fluoro oil whose INCI name is perfluoroperhydrophenanthrene, sold under the reference Fiflow 220 by the company F2 Chemicals.
The composition according to the invention preferably comprises at least one polar or apolar non-volatile hydrocarbon-based oil, at least one non-volatile silicone oil, which is preferably phenylated, and mixtures thereof.
In accordance with an even more particular embodiment, the composition according to the invention comprises at least one non-volatile silicone oil, which is preferably phenylated.
Preferably, said non-volatile phenyl silicone oils are chosen from phenyl silicones not bearing any dimethicone fragments. More particularly, the non-volatile phenyl silicone oils not having a dimethicone fragment are chosen from (I), with radicals R such that the silicone has no dimethicone fragment; (II) with radicals R such that the silicone has no dimethicone fragment, in particular formulae (III) and (ΙΙΓ); (V) with p = 0; (VI) with p=0; (VII) with p=0; (VIII); (IX) with radicals R such that the silicone has no dimethicone fragment; or mixtures thereof.
Furthermore, preferably, the non-volatile phenylated silicone oils are chosen from those of formula (II), more particularly non-volatile phenyl silicone oils of formula (III) or (III').
In addition, the non-volatile hydrocarbon-based oil(s) are more particularly chosen from polar non-volatile oils, such as for example Ci0-C26 alcohols, or ester oils; from apolar oils; and mixtures thereof.
Preferably, the composition comprises at least one polar oil chosen from Ci0-C26 alcohols; hydroxylated monoesters and diesters; monoesters comprising between 18 and 40 carbon atoms in total; triesters comprising between 35 and 70 carbon atoms in total, or mixtures thereof, or at least one apolar oil chosen from liquid paraffin or derivatives thereof, hydrogenated or non-hydrogenated poly(iso)butenes, and also mixtures thereof. SILICONE GUM
The composition according to the invention additionally comprises at least one silicone gum.
More particularly, the silicone gum is chosen from polyorganosiloxanes with a weight- average molecular mass of greater than or equal to 400 000 g/mol.
The weight-average molecular masses are measured in a manner that is conventional in the field, for example using gel permeation chromatography coupled to static light scattering (GPC-MALLS).
Preferably, the viscosity of the silicone gum is greater than 800 000 cSt and more particularly less than or equal to 10 000 000 cSt (at 25°C, measured by standard ASTM D- 445), more particularly between 1 000 000 and 5 000 000 cSt (at 25°C, measured by standard ASTM D-445).
The term "silicone gum" means more particularly polyorganosiloxanes, in particular linear non-crosslinked, optionally hydroxylated, phenylated or vinyl polydimethylsiloxane type, or combinations thereof. It should be noted that the silicone gums used according to the invention are not silicone elastomers.
According to a preferred embodiment of the invention, the silicone gum corresponds to the following formula:
Figure imgf000031_0001
n p in which:
R7, R8, R1 1 and R12 are identical or different, and each is chosen from alkyl radicals comprising from 1 to 6 carbon atoms,
R9 and R10 are identical or different, and each is chosen from an alkyl radical comprising from 1 to 6 carbon atoms, an aryl radical, a hydroxyl radical, a vinyl radical, preferably an alkyl radical comprising from 1 to 6 carbon atoms, a hydroxyl radical;
X is chosen from an alkyl radical comprising from 1 to 6 carbon atoms, a hydroxyl radical, a vinyl radical, preferably an alkyl radical comprising from 1 to 6 carbon atoms, a hydroxyl radical;
n and p are chosen so as to give the silicone gum a molecular mass of greater than or equal to 400 000 g/mol.
In general, n and p may each take values ranging from 0 to 5000 and more particularly from 0 to 3000, given that n and p are not simultaneously zero.
According to a particular embodiment, the silicone gum is a polydimethylsiloxane gum optionally comprising at least one aryl radical, a dimethiconol gum, or mixtures thereof, and preferably a dimethiconol gum. The silicone gum(s) may be used alone or as a mixture, especially with a solvent chosen from volatile silicones, polydimethylsiloxane oils, polyphenylmethylsiloxane oils, isoparaffins, in particular of C8-CiS, methylene chloride, pentane, dodecane, tridecane and tetradecane, or mixtures thereof.
If the silicone gums are sold in predissolved form, the proportion of gum usually represents from 5% to 20% by weight and preferably from 10% to 15% by weight in a linear or cyclic, volatile or non-volatile polydimethylsiloxane of low molecular weight.
Among the silicone gums that may be used, mention may be made of those for which:
7 to R12 represent a methyl group, the substituent X represents a hydroxyl group, the coefficients n and p being such that the molecular mass is greater than or equal to 400 000 g/mol:
o product sold or manufactured under the name Xiameter® PMX-1401 Fluid by the company Dow Corning, in the form of a solution at 13% in cyclopentasiloxane, o product sold or manufactured under the name Xiameter® PMX-1503 Fluid by the company Dow Corning, in the form of a solution at 12% in polydimethylsiloxane, o product sold or manufactured under the name Xiameter® PMX-1 03 Fluid by the company Dow Corning, in the form of a solution at 13% in polydimethylsiloxane, R7, R8, R1 1 , R12 and X represent a methyl group and the substituents R9 and R10 represent an aryl group, the coefficients n and p being such that the molecular mass is greater than or equal to 400 000 g/mol:
o product sold or manufactured under the name Mirasil® C-DPDM by the company Bluestar.
According to a preferred embodiment of the invention, the silicone gum is a polydimethylsiloxane gum optionally comprising at least one aryl radical, a dimethiconol gum, or mixtures thereof, and preferably a dimethiconol gum.
In accordance with a particularly advantageous embodiment of the invention, the silicone gum, where appropriate in predissolved form, is incompatible with the film-forming polymer, the latter being, where appropriate, conveyed in at least one oil, preferably a volatile oil.
To check this absence of compatibility, several mixtures of the silicone gum, where appropriate predissolved, were made with the film-forming polymer, where appropriate conveyed in at least one oil, preferably a volatile oil: 30/70; 50/50; 70/30 (the ratios being expressed by weight, each mixture representing 10 g).
Each mixture is prepared at 25°C with stirring (magnetic bar) for one hour.
If the resulting mixture appears to be one-phase, this mixture is observed with a phase- contrast microscope. If one phase is seen to be dispersed in the other, then said optionally predissolved silicone gum and the film-forming polymer in its vehicle (if present) are said to be incompatible in the evaluated mixture.
Silicone gums that are incompatible in all the tested mixtures are more particularly suitable for use. Use may also be made of gums that are incompatible for some of the tested mixtures, if these gums are used in the composition in a content in which they are incompatible. If necessary, on the basis of the results obtained previously, one or more tests may be repeated to check the compatibility at the envisaged content.
Preferably, use is made of at least one silicone gum that is incompatible with the film- forming polymer/vehicle if present, for the three mixtures described previously.
According to a preferred embodiment, the composition according to the invention comprises at least one silicone gum in an active material content ranging from 0.1 % to 10% by weight, preferably from 0.2% to 8% by weight, in particular from 0.3% to 6% by weight, relative to the total weight of the composition. VOLATILE OILS
The composition according to the invention also preferably comprises at least one volatile oil.
The term "volatile oil" means an oil with a non-zero vapour pressure, at 25°C, in particular ranging from 0.13 Pa to 40 000 Pa, in particular ranging up to 13 000 Pa and more particularly ranging up to 1300 Pa ("closed cup").
According to one embodiment, the composition comprises at least one volatile oil in a content ranging from 0.1 to 30% by weight, preferably from 0.5 to 25% by weight and in particular from 1 to 20% by weight, relative to the total weight of the composition.
In one embodiment, the composition comprises at least one volatile oil in a content of at least 10% by weight, preferably ranging from 40 to 75% by weight and in particular from 50 to 70% by weight, relative to the total weight of volatile and non-volatile oil(s) present in said composition.
According to one embodiment, the composition comprises a mixture of volatile oil(s) and of non-volatile oil(s) in respective weight contents such as that the ratio of the content of volatile oil(s) to the content of non-volatile oil(s) ranges from 0.7 to 3, preferably ranges from 0.8 to 2.
The volatile oil(s) may be chosen from hydrocarbon-based oils, silicone oils and fluoro oils, and mixtures thereof.
The hydrocarbon-based volatile oils are preferably chosen from apolar hydrocarbon- based oils and may in particular be chosen from hydrocarbon-based volatile oils containing from 8 to 16 carbon atoms, and mixtures thereof, and especially:
branched C8-Ci6 alkanes such as C8-Ci6 isoalkanes (also known as isoparaffins), isododecane, isodecane and isohexadecane, and, for example, the oils sold under the trade names Isopar and Permethyl,
- linear alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol, respectively, under the references Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture (Cetiol UT), mixtures of n-undecane (C1 1 ) and of n- tridecane (C13) obtained in Examples 1 and 2 of patent application WO 2008/155059 from the company Cognis, and
- mixtures thereof. The volatile silicone oils may be chosen from silicone oils with a flash point ranging from 40°C to 102°C, preferably with a flash point of greater than 55°C and less than or equal to 95°C, and preferentially ranging from 65°C to 95°C.
As volatile silicone oils that may be used in the invention, mention may be made of linear or cyclic silicones with a viscosity at 25°C of less than 8 centistokes (cSt) (8 χ 10"6 m2/s) and especially containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms.
As volatile silicone oil(s) that may be used in the invention, mention may be made especially of dimethicones with a viscosity of 2, 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
The volatile oils may also be chosen from a fluoro oil, such as nonafluoromethoxy- butane or perfluoromethylcyclopentane, and mixtures thereof.
Preferably, the composition according to the invention comprises at least one volatile oil, chosen more particularly from apolar volatile hydrocarbon-based oils and from volatile silicone oils, alone or as mixtures.
PASTY COMPOUNDS
The composition according to the invention may also comprise at least one hydrocarbon-based or silicone-based compound that is pasty at 23°C.
For the purposes of the present invention, the term "pasty compound" means a water- immiscible compound with a reversible solid/liquid change of state, having in the solid state an anisotropic crystal organization, and comprising at a temperature of 23°C a liquid fraction and a solid fraction. In other words, the starting melting point of the pasty compound can be less than 23°C. The liquid fraction of the pasty compound, measured at 23°C, can represent from 9% to 97% by weight of the pasty compound. This liquid fraction at 23°C preferably represents between 15% and 85% and more preferably between 40% and 85% by weight.
For the purposes of the invention, the melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in the standard ISO 1 1357-3; 1999. The melting point of a pasty compound may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2920 by the company TA Instruments or under the name DSC Q100 by the company TA Instruments with the TA Universal Analysis software.
The measuring protocol is as follows: a sample of 5 mg of pasty compound 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, 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 pasty fatty substance is measured as a function of the temperature. The melting point of the pasty 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 liquid fraction by weight of the pasty compound at 23°C is equal to the ratio of the heat of fusion consumed at 23°C to the heat of fusion of the pasty compound.
The heat of fusion (expressed in J/g) of the pasty compound is the amount of energy required to make the compound change from the solid state to the liquid state. The pasty compound is said to be in the solid state when all of its mass is in crystalline solid form. The pasty compound is said to be in the liquid state when all of its mass is in liquid form. The heat of fusion consumed at 23°C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23°C, consisting of a liquid fraction and a solid fraction.
The heat of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name MDSC 2920 by the company TA Instrument, with a temperature rise of 5°C or 10°C per minute, according to the standard ISO 11357-3; 1999.
The liquid fraction of the pasty compound measured at 32°C preferably represents from 30% to 100% by weight of the pasty compound, preferably from 50% to 100% and more preferably from 60% to 100% by weight of the pasty compound. When the liquid fraction of the pasty compound measured at 32°C is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32°C.
The liquid fraction of the pasty compound measured at 32°C is equal to the ratio of the heat of fusion consumed at 32°C to the heat of fusion of the pasty compound. The heat of fusion consumed at 32°C is calculated in the same way as the heat of fusion consumed at 23°C.
The pasty compound(s) may in particular be chosen from synthetic pasty compounds and fatty substances of plant origin. The pasty compound(s) may be hydrocarbon-based or silicone-based.
The pasty compound(s) may be chosen in particular from:
lanolin and derivatives thereof, such as lanolin alcohol, oxyethylenated lanolins, acetylated lanolin, lanolin esters such as isopropyl lanolate, and oxypropylenated lanolins,
petroleum jelly (also known as petrolatum),
polyol ethers chosen from C2-C4 polyalkylene glycol pentaerythrityl ethers, fatty alcohol ethers of sugars, and mixtures thereof. For example, mention may be made of polyethylene glycol pentaerythrityl ether comprising 5 oxyethylene units (5 OE) (CTFA name: PPG-5 Pentaerythrityl Ether), polypropylene glycol pentaerythrityl ether comprising five oxypropylene (5 OP) units (CTFA name: PPG-5 Pentaerythrityl Ether) and mixtures thereof, and more especially the mixture PEG-5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether and soybean oil, sold under the name Lanolide by the company Vevy, which is a mixture in which the constituents are in a 46/46/8 weight ratio: 46% PEG-5 Pentaerythrityl Ether, 46% PPG-5 Pentaerythrityl Ether and 8% soybean oil,
polymeric or non-polymeric silicone compounds,
polymeric or non-polymeric fluoro compounds,
vinyl polymers, especially:
o olefin homopolymers and copolymers,
o hydrogenated diene homopolymers and copolymers,
o linear or branched oligomers, which are homopolymers or copolymers of alkyl
(meth)acrylates preferably containing a C8-C3o alkyl group,
o oligomers, which are homopolymers and copolymers of vinyl esters containing C8-
C30 alkyl groups, and
o oligomers, which are homopolymers and copolymers of vinyl esters containing C8- C30 alkyl groups,
liposoluble polyethers resulting from the polyetherification between one or more C2-Ci0o and preferably C2-C5o diols. Among the liposoluble polyethers that are particularly considered are copolymers of ethylene oxide and/or of propylene oxide with C6-C3o long-chain alkylene oxides, more preferably such that the weight ratio of the ethylene oxide and/or of the propylene oxide to the alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, mention will be made especially of copolymers such as long- chain alkylene oxides arranged in blocks with an average molecular weight from 1000 to 10 000, for example a polyoxyethylene/polydodecyl glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 OE) sold under the brand name Elfacos ST9 by Akzo Nobel,
esters and polyesters. Among the esters, the following are especially considered: o esters of a glycerol oligomer, especially diglycerol esters, with linear or branched, saturated or unsaturated, preferably saturated, C6-C2o, optionally hydroxylated monocarboxylic acids, and/or linear or branched, saturated or unsaturated, preferably saturated, C6-Ci0 dicarboxylic acids, in particular condensates of adipic acid and of diglycerol, for which some of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, isostearic acid and 12-hydroxystearic acid, for instance bis-diglyceryl polyacyladipate-2 sold under the reference Softisan® 649 by the company Sasol,
o vinyl ester homopolymers bearing C8-C30 alkyl groups, such as polyvinyl laurate (sold especially under the reference Mexomer PP by the company Chimex), o the arachidyl propionate sold under the brand name Waxenol 801 by Alzo, o phytosterol esters,
o fatty acid triglycerides and derivatives thereof, in particular optionally hydrogenated (totally or partially), optionally monohydroxylated or polyhydroxylated, C6-C30 and more particularly C8-Ci8, linear or branched, saturated or unsaturated fatty acid triglycerides; for example Softisan 100® sold by the company Sasol,
o pentaerythritol esters,
o aliphatic esters resulting from the esterification of an aliphatic hydroxycarboxylic acid ester with an aliphatic carboxylic acid. More particularly, the aliphatic carboxylic acid is of C4-C3o and preferably of C8-C3o- It is preferably chosen from hexanoic, heptanoic, octanoic, 2-ethylhexanoic, nonanoic, decanoic, undecanoic, dodecanoic, tridecanoic, tetradecanoic, pentadecanoic, hexadecenoic, hexyldecanoic, heptadecanoic, octadecanoic, isostearic, nonadecanoic, eicosanoic, isoarachidic, octyldodecanoic, heneicosanoic and docosanoic acids, and mixtures thereof. The aliphatic carboxylic acid is preferably branched. The hydroxy carboxylic acid ester is advantageously derived from a C2-C4o, preferably C10-C34 and even more preferentially Ci2-C28 hydroxylated carboxylic acid; the number of hydroxyl groups being between 1 and 20, more particularly between 1 and 10 and preferably between 1 and 6.
Said hydroxy carboxylic acid esters are preferably chosen from:
a) total or partial esters of saturated, linear and monohydroxylated aliphatic monocarboxylic acids;
b) total or partial esters of saturated, monohydroxylated aliphatic monocarboxylic acids;
c) total or partial esters of saturated, monohydroxylated aliphatic polycarboxylic acids;
d) total or partial esters of saturated, polyhydroxylated aliphatic polycarboxylic acids;
e) partial or total esters of C2-C1S aliphatic polyols with a monohydroxylated or polyhydroxylated aliphatic monocarboxylic or polycarboxylic acid;
f) mixtures thereof;
o esters of a diol dimer and of a diacid dimer, where appropriate esterified on their free alcohol or acid function(s) with acid or alcohol radicals, especially dimer dilinoleate esters; such esters may be chosen especially from the esters having the following INCI nomenclature: bis-behenyl/isostearyl/phytosteryl dimer dilinoleyl dimer dilinoleate (Plandool G), phytosteryl/isosteryl/cetyl/stearyl/behenyl dimer dilinoleate (Plandool H or Plandool S), and mixtures thereof,
o hydrogenated esters of rosin (Lusplan DD-DHR or DD-DHR from Nippon Fine Chemical);
butters of plant origin, such as mango butter, such as the product sold under the reference Lipex 203 by the company Aarhuskarlshamn, shea butter, in particular the product whose INCI name is Butyrospermum Parkii Butter, such as the product sold under the reference Sheasoft® by the company Aarhuskarlshamn, cupuacu butter (Rain Forest RF3410 from the company Beraca Sabara), murumuru butter (Rain Forest RF3710 from the company Beraca Sabara), cocoa butter; babassu butter such as the product sold under the name Cropure Babassu SS-(LK) by Croda, and also orange wax, for instance the product sold under the reference Orange Peel Wax by the company Koster Keunen,
totally or partially hydrogenated plant oils, for instance hydrogenated soybean oil, hydrogenated coconut oil, hydrogenated rapeseed oil, mixtures of hydrogenated plant oils such as the mixture of hydrogenated soybean, coconut, palm and rapeseed plant oil, for example the mixture sold under the reference Akogel® by the company Aarhuskarlshamn (INCI name Hydrogenated Vegetable Oil), the trans-isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the commercial reference lso-Jojoba-50®, partially hydrogenated olive oil, for instance the compound sold under the reference Beurrolive by the company Soliance, hydrogenated castor oil esters, such as hydrogenated castor oil dimer dilinoleate, for example Risocast DA-L sold by Kokyu Alcohol Kogyo, and hydrogenated castor oil isostearate, for example Salacos HCIS (V-L) sold by Nisshin Oil,
- and mixtures thereof.
Preferably, the pasty compound(s) that are suitable for use in the invention are chosen from hydrocarbon-based compounds, in particular chosen from petroleum jelly, polyol ethers, vinyl polymers, liposoluble polyethers resulting from polyetherification between one or more C2-C50 diols, esters and polyesters, butters of plant origin, totally or partially hydrogenated plant oils, and mixtures thereof.
In accordance with an even more preferred embodiment of the invention, the pasty compound(s) are chosen from:
- petroleum jelly;
- pentaerythrityl ethers of C2-C4 polyalkylene glycol;
- fatty acid ethers of sugars;
- copolymers of ethylene oxide and/or of propylene oxide with C6-C30 long-chain alkylene oxides;
- esters of a glycerol oligomer, especially esters of diglycerol, with linear or branched, saturated or unsaturated, preferably saturated, C6-C2o, optionally hydroxylated monocarboxylic acids, and/or linear or branched, saturated or unsaturated, preferably saturated, C6-C10 dicarboxylic acids;
- vinyl ester homopolymers bearing C8-C3o alkyl groups;
- arachidyl propionate;
- saturated or unsaturated, linear or branched, optionally monohydroxylated or polyhydroxylated, C6-C3o, more particularly C8-Ci8, optionally hydrogenated fatty acid triglycerides;
- pentaerythritol esters;
- non-crosslinked esters obtained by condensation of a linear or branched C4-C50 dicarboxylic or polycarboxylic acid and of a C2-C5o diol or polyol, the aliphatic esters obtained by reaction of an ester of a hydroxycarboxylic acid and of an aliphatic carboxylic acid, the carboxylic acid advantageously being C4-C30; - esters of a diol dimer and of a diacid dimer, for instance dilinoleate dimer esters;
- butters of plant origin;
- totally or partially hydrogenated plant oils;
- and mixtures thereof.
According to a particular embodiment, the composition according to the invention comprises at least one pasty compound in a content of greater than 0.5% by weight, preferably in a content ranging from 2 to 20% by weight, in particular from 2 to 15% by weight and even more advantageously from 2 to 10% by weight, relative to the total weight of the composition.
SEMI-CRYSTALLINE POLYMER
According to a first embodiment, and as indicated previously, the composition according to the invention comprises at least one semi-crystalline polymer, preferably derived from acrylic or methacrylic acid.
For the purposes of the invention, the term "semi-crystalline polymer" means polymers comprising a crystallizable portion, side chain or block in the backbone, and an amorphous portion in the backbone and having a first-order reversible phase-change temperature, in particular of melting (solid-liquid transition). When the crystallizable portion is in the form of a block of the polymer backbone, the chemical nature of this crystallizable block is different from that of the amorphous blocks; in this case, the semi-crystalline polymer is a block polymer, for example, of the diblock, triblock or multiblock type comprising at least one crystallizable block and at least one amorphous block.
The term "block" generally means at least 5 identical repeating units. The crystallizable block(s) are then of different chemical nature from the amorphous block(s).
Advantageously, the semi-crystalline polymer(s) of the composition of the invention have an average molecular mass (Mn) of greater than or equal to about 2000 g/mol, preferably from about 2000 to 800 000 g/mol, preferably from about 3000 to 500 000 g/mol, preferably from about 4000 to 150 000 g/mol and preferably from about 4000 to 99 000 g/mol.
In the composition according to the invention, the semi-crystalline polymers are advantageously soluble in the oily phase to at least 1 % by weight, at a temperature above their melting point.
Besides the crystallizable chains or blocks, the polymer blocks are amorphous.
For the purposes of the invention, the term "crystallizable chain or block" means a chain or block which, if it were alone, would pass reversibly from the amorphous state to the crystalline state, depending on whether it is above or below its melting point. For the purposes of the invention, a chain is a group of atoms, which is pendent or lateral relative to the polymer backbone. A block is a group of atoms belonging to the backbone, this group constituting one of the repeating units of the polymer. Advantageously, the "crystallizable side chain" may be a chain comprising at least 6 carbon atoms. Preferably, the polymer backbone of the semi-crystalline polymers is soluble in the oily phase. Thus, the semi-crystalline polymer used in the composition of the invention is generally introduced into the oily phase of the composition.
Preferably, the semi-crystalline polymers used in the composition of the invention have a melting point, m.p., of less than 70° C (25° C =¾ m.p. < 70° C), this temperature being at least equal to the temperature of the keratin material that is to receive the composition according to the invention, especially the skin. The melting point may be measured especially by any known method and in particular with a differential scanning calorimeter (DSC).
Preferably, the crystallizable blocks or chains of the semi-crystalline polymers represent at least 30% by weight and better still at least 40% by weight of the total weight of each polymer. The semi-crystalline polymers containing crystallizable blocks used according to the invention are block or multiblock polymers. They may be obtained by polymerization of monomers containing reactive double bonds (or ethylenic bonds) or by polycondensation. When the polymers of the invention are polymers containing crystallizable side chains, they are advantageously in random or statistical form.
The semi-crystalline polymers of the invention may be of synthetic origin. In addition, they comprise no polysaccharide backbones.
The semi-crystalline polymers that may be used in the invention are in particular:
- block copolymers of polyolefins with controlled crystallization,
- polycondensates of aliphatic or aromatic polyester type or aliphatic/aromatic copolyester type,
- homopolymers or copolymers bearing at least one crystallizable side chain and homopolymers or copolymers bearing in the backbone at least one crystallizable block,
- homopolymers or copolymers bearing at least one crystallizable side chain in particular containing fluoro group(s), and
- mixtures thereof.
For example, the block copolymers of polyolefins with controlled crystallization that are suitable for use in the present invention are especially those whose monomers are described in EP-A-0 951 897.
For example, the homopolymers or copolymers bearing at least one crystallizable side chain and the homopolymers or copolymers bearing in the backbone at least one crystallizable block, which are particularly suitable for use in the invention, are those described especially in US-A-5 156 91 1.
Finally, the homopolymers or copolymers bearing at least one crystallizable side chain in particular containing fluoro group(s) are preferably those described in WO-A-01/19333.
In a particular embodiment, the crystallizable side chains or blocks are hydrophobic. a) Semi-crystalline polymers bearing crystallizable side chains:
Mention may be made in particular of those defined in documents US-A-5 156 91 1 and WO-A-01/19333. They are homopolymers or copolymers comprising from 50% to 100% by weight of units resulting from the polymerization of one or more monomers bearing a crystal lizable hydrophobic side chain.
These homopolymers or copolymers are of any nature, provided that they meet the conditions indicated previously.
They can result:
from the polymerization, especially the free-radical polymerization, of one or more monomers containing reactive or ethylenic double bond(s) with respect to a polymerization, namely a vinyl, (meth)acrylic or allylic group;
- from the polycondensation of one or more monomers bearing co-reactive groups (carboxylic acid, sulfonic acid, alcohol, amine or isocyanate), for instance polyesters, polyurethanes, polyethers, polyureas or polyamides.
In general, these polymers are chosen especially from homopolymers and copolymers resulting from the polymerization of at least one monomer bearing crystallizable chain(s), which represented by the following formula:
Figure imgf000041_0001
with M representing an atom of the polymer backbone, S representing a spacer, and C representing a crystallizable group.
The crystallizable chains "-S-C" may be aliphatic or aromatic, and optionally fluorinated or perfluorinated. "S" especially represents a group (CH2)n, (CH2CH20)n or (CH20), which may be linear or branched or cyclic, with n being an integer ranging from 0 to 22. Preferably, "S" is a linear group. Preferably, "S" and "C" are different.
When the crystallizable chains "-S-C" are hydrocarbon-based aliphatic chains, they comprise hydrocarbon-based alkyl chains containing at least 1 1 carbon atoms and not more than 40 carbon atoms and better still not more than 24 carbon atoms. They are especially aliphatic chains or alkyl chains containing at least 12 carbon atoms, and they are preferably Ci4-C24, alkyl chains. When they are fluoroalkyl or perfluoroalkyl chains, they contain at least 6 fluorinated carbon atoms and especially at least 1 1 carbon atoms, at least 6 of which carbon atoms are fluorinated.
According to a particular embodiment, the invention relates to a composition for which the semi-crystalline polymer is chosen from a group comprising homopolymers and copolymers resulting from the polymerization of at least one monomer bearing crystallizable chain(s), these chains being chosen from alkyl chains comprising at least 11 carbon atoms and not more than 40 carbon atoms.
As examples of semi-crystalline polymers or copolymers bearing crystallizable chain(s), mention may be made of those resulting from the polymerization of one or more of the following monomers: (meth)acrylates of saturated alkyls with the alkyl group being Ci4-C24, perfluoroalkyl (meth)acrylates with a Cn-Ci5 perfluoroalkyl group, N-alkyl(meth)acrylamides with the alkyl group being Ci to C2 with or without a fluorine atom, vinyl esters containing alkyl or perfluoroalkyl chains with the alkyl group being CM to C24 (with at least 6 fluorine atoms per perfluoroalkyl chain), vinyl ethers containing alkyl or perfluoroalkyl chains with the alkyl group being CM to C24 and at least 6 fluorine atoms per perfluoroalkyl chain, d4 to C24 a-olefins such as, for example, octadecene, para-alkylstyrenes with an alkyl group containing from 12 to 24 carbon atoms, and mixtures thereof.
When the polymers result from a polycondensation, the hydrocarbon-based and/or fluorinated crystallizable chains as defined above are borne by a monomer that may be a diacid, a diol, a diamine or a diisocyanate.
When the polymers that are the subject of the invention are copolymers, they additionally contain from 0 to 50% of groups Y or Z resulting from the copolymerization of Y which is a polar or non-polar monomer or a mixture of the two:
- when Y is a polar monomer, it is either a monomer bearing polyoxyalkylenated groups (especially oxyethylenated and/or oxypropylenated groups), a hydroxyalkyl (meth)acrylate, for instance hydroxyethyl acrylate, (meth)acrylamide, an N-alkyl(meth)acrylamide, an N,N- dialkyl(meth)acrylamide such as, for example, N,N-diisopropylacrylamide or N-vinylpyrrolidone (NVP), N-vinylcaprolactam, a monomer bearing at least one carboxylic acid group, for instance (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, or bearing a carboxylic acid anhydride group, for instance maleic anhydride,
- when Y is a non-polar monomer, it may be an ester of the linear, branched or cyclic alkyl (meth)acrylate type, a vinyl ester, an alkyl vinyl ether, an a-olefin, styrene or styrene substituted with a Ci to Ci0 alkyl group, for instance omethylstyrene.
For the purposes of the invention, the term "alkyl" means a saturated group especially of C8 to C24, and better still of CM to C24, unless otherwise mentioned.
When the polymers that are subjects of the invention are copolymers, they also contain from 0 to 50% of groups Y or Z resulting from the copolymerization of Z which is a polar monomer or a mixture of polar monomers. In this case, Z has the same definition as the "polar Y" defined above.
Preferably, the semi-crystalline polymers bearing a crystallizable side chain are alkyl (meth)acrylate or alkyl(meth)acrylamide homopolymers with an alkyl group as defined above, and especially of Ci4-C24, copolymers of these monomers with a hydrophilic monomer preferably of different nature from (meth)acrylic acid, for instance N-vinylpyrrolidone or hydroxyethyl (meth)acrylate, and mixtures thereof.
b) Polymers bearing at least one crystallizable block in the backbone:
These polymers are especially block copolymers consisting of at least two blocks of different chemical nature, one of which is crystallizable.
For example, the block polymers defined in patent US-A-5 156 91 1 are particularly suitable for use.
They are, for example, block copolymers of olefin or of cycloolefin containing a crystallizable chain, for instance those derived from the block polymerization of:
- cyclobutene, cyclohexene, cyclooctene, norbornene (i.e. bicyclo(2.2.1 )-2-heptene), 5- methylnorbornene, 5-ethylnorbornene, 5,6-dimethylnorbornene, 5,5,6-trimethylnorbornene,
5-ethylidenenorbornene, 5 phenylnorbornene, 5-benzylnorbornene, 5-vinylnorbornene, 1 ,4,5,8-dimethano-1 ,2,3,4,4a,5,8a-octahydronaphthalene, dicyclopentadiene, or mixtures thereof,
- with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1 -hexene, 4-methyl-1 - pentene, 1 -octene, 1 decene or 1 -eicosene, or mixtures thereof, and in particular
- copoly(ethylene/norbomene) blocks and (ethylene/propylene/ethylidene-norbornene) block terpolymers.
Polymers resulting from the block copolymerization of at least two C2-Ci6, preferably C2-C12 and preferably C4-C12 α-olefins, such as those mentioned previously and in particular block bipolymers of ethylene and of 1 -octene, may also be used.
The copolymers of interest may also be copolymers bearing at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature). These copolymers may also have two crystallizable blocks of different chemical nature. The preferred copolymers are those simultaneously bearing at room temperature a crystallizable block and an amorphous block which are both hydrophobic and lipophilic, distributed sequentially; mention may be made, for example, of polymers bearing one of the crystallizable blocks and one of the amorphous blocks that follow:
- block that is crystallizable by nature, of a) polyester type, for instance poly(alkylene terephthalate), or of b) polyolefin type, for instance polyethylenes or polypropylenes.
- amorphous and lipophilic block, for instance amorphous polyolefins or copoly(olefin)s such as poly(isobutylene), hydrogenated polybutadiene or hydrogenated poly(isoprene).
As examples of such copolymers containing a crystallizable block and an amorphous block, mention may be made of:
poly( -caprolactone)-b-poly(butadiene) block copolymers, preferably used hydrogenated, such as those described by Nojima, Macromolecules, 32, 3727-3734 (1999), - the hydrogenated block or multiblock poly(butylene terephthalate )-b-poly(isoprene) block copolymers cited by Boutevin et al., Polymer Bulletin, 34, 117-123 (1995),
- the poly(ethylene)-b-copoly(ethylene/propylene) block copolymers cited by Rangarajan et al., Macromolecules, 26, 4640-4645 (1993) and by Richter et al., Macromolecules, 30, 1053-1068 (1997),
- the poly(ethylene)-b-poly(ethylethylene) block copolymers cited by Hamley, Advances in Polymer Science, Vol. 148, 1 13-137 (1999).
The semi-crystalline polymers in the composition of the invention may or may not be partially crosslinked, provided that the degree of crosslinking does not interfere with their dissolution or dispersion in the oily phase by heating above their melting point. It may then be a chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It may also be a physical crosslinking which may, in this case, be due either to the establishment of bonds of hydrogen or dipolar type between groups borne by the polymer, such as, for example, the dipolar interactions between carboxylate ionomers, these interactions being of small amount and borne by the polymer backbone; or to a phase separation between the crystallizable blocks and the amorphous blocks borne by the polymer. Preferably, the semi-crystalline polymers in the composition according to the invention are non-crosslinked.
According to a particular embodiment of the invention, the polymer is chosen from copolymers resulting from the polymerization of at least one monomer bearing a crystallizable chain chosen from saturated CM to C¾ alkyl (meth)acrylates, Cn to C15 perfluoroalkyl (meth)acrylates, C14 to C24 N-alkyl(meth)acrylamides with or without a fluorine atom, vinyl esters containing d4 to C24 alkyl or perfluoroalkyl chains, vinyl ethers containing
CM to C24 alkyl or perfluoroalkyl chains, C14 to C24 alpha-olefins, para-alkylstyrenes with an alkyl group containing from 12 to 24 carbon atoms, with at least one optionally fluorinated Ci to C10 monocarboxylic acid ester or amide, which may be represented by the following formula:
H2C:=C C X R
R1 O in which 1 is H or CH3, R represents an optionally fluorinated C1-C10 alkyl group and X represents O, NH or NR2 in which R2 represents an optionally fluorinated Ci C10 alkyl group.
According to a more particular embodiment of the invention, the polymer is derived from a monomer containing a crystallizable chain, chosen from saturated Cu to C22 alkyl (meth)acrylates and even more particularly poly(stearyl acrylate) or poly(behenyl acrylate).
According to a particular embodiment, the semi-crystalline polymer is chosen from homopolymers obtained by polymerization of a monomer chosen from C14-C24 alkyl acrylates and Ci4-C24 alkyl methacrylates and from copolymers obtained by copolymerization of a monomer chosen from Ci4-C24 alkyl acrylates and Ci4-C24 alkyl methacrylates, with a hydrophilic monomer.
As particular examples of structuring semi-crystalline polymers that may be used in the composition according to the invention, mention may be made of the polymers having the INCI name Poly C10-30 Alkyl Acrylate, such as the "I ntelimer" products from the company Air Products, for instance the product I ntelimer IPA 13-1 , which is a polystearyl acrylate (Ci2 compound) or the product I ntelimer I PA 13-6, which is a behenyl polymer (C22 compound).
According to a particular embodiment, the semi-crystalline polymer is a polymer of INCI name: Poly C10-C30 Alkyl Acrylate.
The semi-crystalline polymer Intelimer I PA 13-1 NG is known for its SPF booster effects, but it is sparingly compatible or incompatible with standard silicone emulsifiers and, more generally, with standard silicone ingredients.
The semi-crystalline polymers may especially be those described in Examples 3, 4, 5,
7, 9 and 13 of patent US-A-5 156 91 1 , bearing a -COOH group, resulting from the copolymerization of acrylic acid and of a C5 to C16 alkyl (meth)acrylate and more particularly from the copolymerization:
- of acrylic acid, of hexadecyl acrylate and of isodecyl acrylate in a 1/16/3 weight ratio, - of acrylic acid and of pentadecyl acrylate in a 1/19 weight ratio,
- of acrylic acid, of hexadecyl acrylate and of ethyl acrylate in a 2.5/76.5/20 weight ratio,
- of acrylic acid, of hexadecyl acrylate and of methyl acrylate in a 5/85/10 weight ratio, - of acrylic acid and of octadecyl methacrylate in a 2.5/97.5 weight ratio,
- of hexadecyl acrylate, of polyethylene glycol methacrylate monomethyl ether containing 8 ethylene glycol units, and of acrylic acid in an 8.5/1/0.5 weight ratio.
It is also possible to use the polymer of structure "0" from National Starch, as described in US A 5 736 125, with a melting point of 44°C, and also semi-crystalline polymers bearing crystallizable side chains comprising fluoro groups, as described in Examples 1 , 4, 6, 7 and 8 of WO-A-01/19333.
It is also possible to use the semi-crystalline polymers obtained by copolymerization of stearyl acrylate and of acrylic acid or NVP as described in US-A-5 519 063 or EP-A-550 745, with melting points of 40°C and 38°C, respectively.
It is also possible to use the semi-crystalline polymers obtained by copolymerization of behenyl acrylate and of acrylic acid or NVP, as described in documents US-A-5 519 063 and EP-A-550 745, with melting points of 60°C and 58°C, respectively.
Preferably, the semi-crystalline polymers do not comprise any carboxylic groups.
According to a more particular embodiment of the invention, the content of semi- crystalline polymer(s) ranges from 0.5 to 3% by weight and preferably from 0.5 to 2% by weight, relative to the total weight of the composition.
WAX
According to a second embodiment, the composition according to the invention comprises at least one wax.
For the purposes of the present invention, the term "wax" means a lipophilic compound, which is solid at 25°C, with a reversible solid/liquid change of state, which has a melting point of greater than or equal to 30°C that may be up to 120°C.
The melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 30 by the company Mettler, or under the name DSC Q100 by the company TA instruments with the TA Universal Analysis software.
Preferably, the measuring protocol is as follows:
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 increase 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 wax may especially have a hardness ranging from 0.05 MPa to 15 MPa and preferably ranging from 6 MPa to 15 MPa. The hardness is determined by measuring the compression force measured at 20°C using a texturometer sold under the name TA-TX2i by the company Rheo, equipped with a stainless-steel cylinder 2 mm in diameter, travelling at a measuring speed of 0.1 mm/s, and penetrating the wax to a penetration depth of 0.3 mm.
The waxes may be hydrocarbon waxes or fluoro waxes, and may be of plant, mineral, animal and/or synthetic origin.
In particular, the waxes have a melting point of greater than 30°C and better still greater than 45°C.
Apolar hydrocarbon-based wax
For the purposes of the present invention, the term "apolar hydrocarbon-based wax" means a wax comprising only carbon or hydrogen atoms in its structure. In other words, such a wax is free of other atoms, in particular of heteroatoms, for instance nitrogen, oxygen or silicon.
As illustrations of apolar waxes that are suitable for use in the invention, mention may be made especially of hydrocarbon-based waxes, for instance microcrystalline waxes, paraffin waxes, ozokerite, polymethylene waxes, polyethylene waxes and microwaxes, especially polyethylene waxes.
Polar wax
For the purposes of the present invention, the term "polar wax" means a wax whose chemical structure is formed essentially from, or even is constituted by, carbon and hydrogen atoms, and comprising at least one heteroatom such as oxygen, nitrogen or silicon atoms, preferably at least one oxygen atom.
The polar waxes may especially be hydrocarbon-based, fluoro or silicone waxes.
Preferentially, the polar waxes may be hydrocarbon-based waxes or silicone waxes.
The term "silicone wax" means an oil comprising at least one silicon atom, and especially comprising Si-0 groups.
The term "hydrocarbon-based wax" means a wax formed essentially from, or even constituted of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and that does not contain any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
According to a first preferred embodiment, the polar wax is a hydrocarbon-based wax.
As a hydrocarbon-based polar wax, a wax chosen from ester waxes and alcohol waxes is in particular preferred.
According to the invention, the term "ester wax" means a wax comprising at least one ester function. The ester waxes may also be hydroxylated. According to the invention, the term "alcohol wax" means a wax comprising at least one alcohol function, i.e. comprising at least one free hydroxyl (OH) group.
The following may especially be used as ester wax:
- ester waxes such as those chosen from:
i) waxes of formula RiCOOR2 in which R-i and R2 represent linear, branched or cyclic aliphatic chains, the number of atoms of which varies from 10 to 50, which may contain a heteroatom such as O, N or P and the melting point of which varies from 25°C to 120°C. In particular, use may be made, as an ester wax, of a C20-C40 alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture, or a C20-C40 alkyl stearate. Such waxes are especially sold under the names Kester Wax K 82 P®, Hydroxypolyester K 82 P®, Kester Wax K 80 P® and Kester Wax K82H by the company Koster Keunen.
Use may also be made of a glycol and butylene glycol montanate (octacosanoate) such as the wax Licowax KPS Flakes (INCI name: glycol montanate) sold by the company Clariant.
ii) di(1 ,1 ,1-trimethylolpropane) tetrastearate, sold under the name Hest 2T-4S® by the company Heterene.
iii) dicarboxylic acid diester waxes of general formula
R3-(-OCO-R4-COO-R5), in which R3 and R5 are identical or different, preferably identical and represent a C4-C30 alkyl group (alkyl group comprising from 4 to 30 carbon atoms) and R4 represents a linear or branched C4-C30 aliphatic group (alkyl group comprising from 4 to 30 carbon atoms) which may or may not contain one or more unsaturated groups. Preferably, the C4-C3o aliphatic group is linear and unsaturated.
iv) Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains, for example such as hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, and also the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, such as those sold under the names Phytowax Ricin 16L64® and 22L73® by the company Sophim. Such waxes are described in patent application FR-A-2 792 190. Mention may be made, as waxes obtained by hydrogenation of olive oil esterified with stearyl alcohol, of those sold under the name Phytowax Olive 18 L 57.
v) Mention may also be made of beeswax, synthetic beeswax, polyglycerolated beeswax, carnauba wax, candelilla wax, oxypropylenated lanolin wax, rice bran wax, ouricury wax, esparto grass wax, cork fibre wax, sugar cane wax, Japan wax, sumach wax, montan wax, orange wax, laurel wax, hydrogenated jojoba wax and sunflower wax, in particular refined sunflower wax as waxes of animal or plant origin.
Alcohol waxes that may be mentioned include mixtures of linear, saturated C30-C50 alcohols, such as for example the wax Performacol 550-L Alcohol from New Phase Technologies, stearyl alcohol and cetyl alcohol. Examples of silicone waxes that may be mentioned include mixtures comprising a compound of C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane type (INCI name), for instance the product Dow Corning SW-8005 C30 Resin Wax sold by the company Dow Corning. Mention may also be made of mixtures comprising a compound of the C30-45 Alkyl Methicone type (INCI name), for instance the product Dow Corning® AMS-C30 Cosmetic Wax. Mention may also be made of siliconized beeswax.
In accordance with a particularly advantageous embodiment of the invention, the wax(es) are chosen from compounds that are incompatible with the non-volatile oil(s) present in the composition.
Compatibility tests
Three mixtures of 100 g each are prepared comprising a non-volatile oil and a wax in the following proportions: 75/25, 50/50, 25/75: at a temperature above the melting point of the wax, with stirring using a Rayneri blender that is sufficient to create a vortex in the mixture (as a guide, 200 to 1000 rpm) for 1 hour while maintaining this temperature. Each resulting mixture is then poured into a container, which is closed. The composition is left to stand at room temperature for a time of 24 hours.
The resulting mixture is then observed by eye and, if need be, with a phase-contrast microscope, and the viscosity of the resulting mixture is checked according to the protocol described earlier in the description.
If the cooled mixture is homogeneous and has a higher viscosity than that of the oil alone, then the wax is said to be incompatible.
Finally, the incompatibility of the wax with the mixture of non-volatile oils used in the composition is checked, the oils being present in the proportions in the composition according to the same protocol as previously. This viscosity may then be refined by varying the content of the chosen wax, for example.
Preferably, the composition comprises at least one polar silicone wax, or at least one polar hydrocarbon-based wax such as waxes of animal or plant origin, optionally obtained by catalytic hydrogenation of animal or plant oils; alcohol waxes; and also mixtures thereof.
The composition more particularly comprises a wax content ranging from 0.5 to 5% by weight, preferably from 0.5 to 2% by weight, relative to the total weight of the composition. SURFACTANTS
According to a particular embodiment of the invention, the composition comprises at least one surfactant.
The content of surfactant(s) usually ranges between 0.05% and 15% by weight and preferably between 0.5% and 10% by weight relative to the total weight of the composition. The suitable surfactant(s) may be chosen from nonionic, anionic, cationic and amphoteric surfactants, and mixtures thereof; and preferably from nonionic or anionic hydrocarbon-based or silicone surfactants, and mixtures thereof.
For the choice of these surfactants, reference may be made to the document "Encyclopaedia of Chemical Technology, Kirk-Othmer", volume 22, pp. 333-432, 3rd edition, 1979, Wiley, for the definition of the properties and functions (emulsifying) of surfactants, in particular pp. 347-377 of this reference, for anionic and nonionic surfactants.
In particular, at least one emulsifying surfactant having at 25°C an HLB (hydrophilic- lipophilic balance) within the Griffin sense of greater than or equal to 8 may be used. The Griffin HLB value is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256.
An emulsifying surfactant having at 25°C an HLB (hydrophilic-lipophilic balance) within the Griffin sense of less than 8 may also optionally be used.
A person skilled in the art will select the surfactant(s) as a function of the type of emulsion that he wishes to obtain, a water-in-oil or oil-in-water emulsion, on the basis of his general knowledge.
Nonionic surfactants
The nonionic surfactants may be chosen especially from alkyl and polyalkyl esters of poly(ethylene oxide), (poly)oxyalkylenated alcohols, alkyl and polyalkyl ethers of poly(ethylene oxide), optionally polyoxyethylenated alkyl and polyalkyl esters of sorbitan, optionally polyoxyethylenated alkyl and polyalkyl ethers of sorbitan, alkyl and polyalkyl glycosides or polyglycosides, in particular alkyl and polyalkyl glucosides or polyglucosides, alkyl and polyalkyl esters of sucrose, optionally polyoxyethylenated alkyl and polyalkyl esters of glycerol, and optionally polyoxyethylenated alkyl and polyalkyl ethers of glycerol, and mixtures thereof.
1 ) (C8-C3o)Alkyl and poly(C8-C3o)alkyl esters of poly(ethylene oxide) that are preferably used are those with a number of ethylene oxide (EO) units ranging from 2 to 200. Examples that may be mentioned include stearate 40 EO, stearate 50 EO, stearate 100 EO, laurate 20 EO, laurate 40 EO and distearate 150 EO.
2) (C8-C3o)Alkyl and poly(C8-C3o)alkyl ethers of poly(ethylene oxide) that are preferably used are those with a number of ethylene oxide (EO) units ranging from 2 to 200. Examples that may be mentioned include cetyl ether 23 EO, oleyl ether 50 EO, phytosterol 30 EO, steareth 40, steareth 100 and beheneth 100.
3) (Poly)oxyalkylenated, in particular oxyethylenated and/or oxypropylenated, alcohols that are preferably used are those that can comprise from 1 to 150 oxyethylene and/or oxypropylene units, in particular containing from 20 to 100 oxyethylene units, in particular ethoxylated fatty alcohols, in particular of C8-C24 and preferably of Ci2-Ci8, such as stearyl alcohol ethoxylated with 20 oxyethylene units (CTFA name Steareth-20), for instance Brij 78 sold by the company Uniqema, cetearyl alcohol ethoxylated with 30 oxyethylene units (CTFA name Ceteareth-30), and the mixture of Ci2-Ci5 fatty alcohols comprising 7 oxyethylene units (CTFA name C12-15 Pareth-7), for instance the product sold under the name Neodol 25-7® by Shell Chemicals; or in particular oxyalkylenated (oxyethylenated and/or oxypropylenated) alcohols containing from 1 to 15 oxyethylene and/or oxypropylene units, in particular C8-C24 and preferably Ci2-Ci8 fatty alcohols, such as stearyl alcohol ethoxylated with 2 oxyethylene units (CTFA name Steareth-2), for instance Brij 72 sold by the company Uniqema.
4) Optionally polyoxyethylenated (C8-C3o)alkyl and poly(C8-C3o)alkyl esters of sorbitan that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100. Examples that may be mentioned include sorbitan laurate 4 or 20 EO, in particular polysorbate 20 (or polyoxyethylene (20) sorbitan monolaurate) such as the product Tween 20 sold by the company Uniqema, sorbitan palmitate 20 EO, sorbitan stearate 20 EO, sorbitan oleate 20 EO, or the Cremophor products (RH 40, RH 60, etc.) from BASF.
5) Optionally polyoxyethylenated (C8-C30)alkyl and poly(C8-C30)alkyl ethers of sorbitan that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100.
6) Alkyl and polyalkyl glucosides or polyglucosides that are preferably used are those containing an alkyl group comprising from 6 to 30 carbon atoms and preferably from 6 to 18 or even from 8 to 16 carbon atoms, and containing a glucoside group preferably comprising from 1 to 5 and in particular 1 , 2 or 3 glucoside units. The alkylpolyglucosides may be chosen, for example, from decylglucoside (alkyl-Cg/Cn-polyglucoside (1 .4)), for instance the product sold under the name Mydol 10® by the company Kao Chemicals or the product sold under the name Plantacare 2000 UP® by the company Henkel and the product sold under the name Oramix NS 10® by the company SEPPIC; caprylyl/capryl glucoside, for instance the product sold under the name Plantacare KE 371 1® by the company Cognis or Oramix CG 110® by the company SEPPIC; laurylglucoside, for instance the product sold under the name Plantacare 1200 UP® by the company Henkel or Plantaren 1200 N® by the company Henkel; cocoglucoside, for instance the product sold under the name Plantacare 818 UP® by the company Henkel; caprylylglucoside, for instance the product sold under the name Plantacare 810 UP® by the company Cognis; and mixtures thereof.
7) Examples of (C8-C3o)alkyl and poly(C8-C30)alkyl esters of sucrose that may be mentioned include Crodesta F150, sucrose monolaurate sold under the name Crodesta SL
40, and the products sold by Ryoto Sugar Ester, for instance sucrose palmitate sold under the reference Ryoto Sugar Ester P1670, Ryoto Sugar Ester LWA1695 or Ryoto Sugar Ester 01570.
8) Optionally polyoxyethylenated (C8-C30)alkyl and poly(C8-C30)alkyl esters of glycerol that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100 and a number of glycerol units ranging from 1 to 30. Examples that may be mentioned include hexaglyceryl monolaurate, polyglyceryl-4 isostearate, for instance the product sold under the name Isolan Gl 34 by the company Evonik Goldschmidt, and PEG-30 glyceryl stearate.
9) Optionally polyoxyethylenated (C8-C30)alkyl and poly(C8-C30)alkyl ethers of glycerol that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100 and a number of glycerol units ranging from 1 to 30. Examples that may be mentioned include Nikkol Batyl Alcohol 100 and Nikkol Chimyl Alcohol 100.
Anionic surfactants
The anionic surfactants may be chosen from alkyl ether sulfates, carboxylates, amino acid derivatives, sulfonates, isethionates, taurates, sulfosuccinates, alkylsulfoacetates, phosphates and alkyl phosphates, polypeptides, metal salts of C10-C30 and in particular C12- C20 fatty acids, in particular metal stearates, and mixtures thereof.
1 ) Examples of (C8-C30)alkyl ether sulfates that may be mentioned include sodium lauryl ether sulfate (70/30 C12-C14) (2.2 EO) sold under the names Sipon AOS225 or
Texapon N702 by the company Henkel, ammonium lauryl ether sulfate (70/30 C12-C14) (3 EO) sold under the name Sipon LEA 370 by the company Henkel, ammonium (C12-C14) alkyl ether (9 EO) sulfate sold under the name Rhodapex AB/20 by the company Rhodia Chimie, and the mixture of sodium magnesium lauryl oleyl ether sulfate sold under the name Empicol BSD 52 by the company Albright & Wilson.
2) Examples of carboxylates that may be mentioned include salts (for example alkali metal salts) of N-acylamino acids, glycol carboxylates, amido ether carboxylates (AECs) and polyoxyethylenated carboxylic acid salts.
The surfactant of glycol carboxylate type may be chosen from alkyl glycol carboxylics or 2-(2-hydroxyalkyloxy acetate), salts thereof and mixtures thereof. These alkyl glycol carboxylics comprise a linear or branched, saturated or unsaturated aliphatic and/or aromatic alkyl chain containing from 8 to 18 carbon atoms. These carboxylics may be neutralized with mineral bases such as potassium hydroxide or sodium hydroxide.
Examples of surfactants of glycol carboxylic type that may be mentioned include sodium lauryl glycol carboxylate or sodium 2-(2-hydroxyalkyloxy acetate) such as the product sold under the name Beaulight Shaa® by the company Sanyo, Beaulight LCA-25N® or the corresponding acid form Beaulight Shaa (Acid form)®.
An example of an amido ether carboxylate (AEC) that may be mentioned is sodium lauryl amido ether carboxylate (3 EO) sold under the name Akypo Foam 30® by the company Kao Chemicals.
Examples of polyoxyethylenated carboxylic acid salts that may be mentioned include oxyethylenated (6 EO) sodium lauryl ether carboxylate (65/25/10 C12-14-16) sold under the name Akypo Soft 45 NV® by the company Kao Chemicals, polyoxyethylenated and carboxymethylated fatty acids of olive oil origin sold under the name Olivem 400® by the company Biologia e Tecnologia, and oxyethylenated (6 EO) sodium tridecyl ether carboxylate sold under the name Nikkol ECTD-6 NEX® by the company Nikkol.
3) Amino acid derivatives that may especially be mentioned include alkali metal salts of amino acids, such as:
(Cs-C3o)alkoyl sarcosinates, for instance the sodium lauroyl sarcosinate sold under the name Sarkosyl NL 97® by the company Ciba or sold under the name Oramix L30® by the company SEPPIC, sodium myristoyl sarcosinate sold under the name Nikkol Sarcosinate MN® by the company Nikkol, and sodium palmitoyl sarcosinate sold under the name Nikkol Sarcosinate PN® by the company Nikkol;
(C8-C3o)alkoyl alaninates, for instance sodium N-lauroyl N-methyl amidopropionate sold under the name Sodium Nikkol Alaninate LN30® by the company Nikkol, or sold under the name Alanone ALE® by the company Kawaken, and triethanolamine N-lauroyl N-methyl alanine sold under the name Alanone Alta® by the company Kawaken;
(C8-C3o)alkoyl glutamates, for instance triethanolamine monococoyl glutamate sold under the name Acylglutamate CT-12® by the company Ajinomoto, or triethanolamine lauroyl glutamate sold under the name Acylglutamate LT-12® by the company Ajinomoto;
- (C8-C3o)alkoyl aspartates, for instance the mixture of triethanolamine N-lauroyl aspartate and of triethanolamine N-myristoyl aspartate, sold under the name Asparack® by the company Mitsubishi;
glycine derivatives ((C8-C30)alkoyl glycinates), for instance the sodium N-cocoyl glycinate sold under the names Amilite GCS-12® and Amilite GCK 12 by the company Ajinomoto;
citrates such as citric acid monoesters of C8-C30 alcohols, such as the oxyethylenated (9 mol) citric monoester of cocoyl alcohols sold under the name Witconol EC 1 129 by the company Goldschmidt;
(C8-C3o)alkyl galacturonates, such as the sodium dodecyl-D-galactoside uronate sold by the company Soliance.
4) Examples of sulfonates that may be mentioned include a-olefin sulfonates, for instance the sodium a-olefin sulfonate (Ci4-i6) sold under the name Bio-Terge AS-40® by the company Stepan, sold under the names Witconate AOS Protege® and Sulframine AOS PH 12® by the company Witco or sold under the name Bio-Terge AS-40 CG® by the company Stepan, and the sodium secondary olefin sulfonate sold under the name Hostapur SAS 30® by the company Clariant.
5) (C8-C30)Alkoyl isethionates that may be mentioned include acylisethionates, for instance sodium cocoyl isethionate, such as the product sold under the name Jordapon CI P® by the company Jordan.
6) (C8-C3o)Alkoyl taurates that may be mentioned include the sodium salt of palm kernel oil methyltaurate sold under the name Hostapon CT Pate® by the company Clariant; N-acyl N-methyltaurates, for instance the sodium N-cocoyl N-methyltaurate sold under the name Hostapon LT-SF® by the company Clariant or sold under the name Nikkol CMT-30-T® by the company Nikkol, and the sodium palmitoyl methyltaurate sold under the name Nikkol PMT® by the company Nikkol.
7) Examples of sulfosuccinates that may be mentioned include the oxyethylenated (3
EO) lauryl alcohol monosulfosuccinate (70/30 C12/C14) sold under the names Setacin 103 Special® and Rewopol SB-FA 30 K 4® by the company Witco, the disodium salt of a C12-C14 alkyl hemisulfosuccinate, sold under the name Setacin F Special Paste® by the company Zschimmer Schwarz, the oxyethylenated (2 EO) disodium oleamidosulfosuccinate sold under the name Standapol SH 135® by the company Henkel, the oxyethylenated (5 EO) laurylamide monosulfosuccinate sold under the name Lebon A-5000 by the company Sanyo, the oxyethylenated (10 EO) disodium salt of lauryl citrate monosulfosuccinate sold under the name Rewopol SB CS 50® by the company Witco, and the ricinoleic monoethanolamide monosulfosuccinate sold under the name Rewoderm S 1333® by the company Witco. Polydimethylsiloxane sulfosuccinates may also be used, such as disodium PEG-12 dimethicone sulfosuccinate sold under the name Mackanate-DC30 by the company Maclntyre.
8) Examples of (Cs-C3o)alkyl sulfoacetates that may be mentioned include the mixture of sodium lauryl sulfoacetate and disodium lauryl ether sulfosuccinate, sold under the name Stepan-Mild LSB by the company Stepan.
9) Examples of phosphates and (C8-C3o)alkyl phosphates that may be mentioned include monoalkyl phosphates and dialkyl phosphates, such as the lauryl monophosphate sold under the name MAP 20® by the company Kao Chemicals, the potassium salt of dodecylphosphoric acid, the mixture of monoester and diester (predominantly diester) sold under the name Crafol AP-31® by the company Cognis, the mixture of octylphosphoric acid monoester and diester sold under the name Crafol AP-20® by the company Cognis, the mixture of ethoxylated (7 mol of EO) phosphoric acid monoester and diester of 2- butyloctanol, sold under the name Isofol 12 7 EO-Phosphate Ester® by the company Condea, the potassium or triethanolamine salt of mono(Ci2-Ci3)alkyl phosphate sold under the references Arlatone MAP 230K-40® and Arlatone MAP 230T-60® by the company Uniqema, the potassium lauryl phosphate sold under the name Dermalcare MAP XC-99/09® by the company Rhodia Chimie, and the potassium cetyl phosphate sold under the name Arlatone MAP 160K by the company Uniqema.
10) The polypeptides are obtained, for example, by condensation of a fatty chain onto amino acids from cereals and in particular from wheat and oat. Examples of polypeptides that may be mentioned include the potassium salt of hydrolysed lauroyl wheat protein, sold under the name Aminofoam W OR by the company Croda, the triethanolamine salt of hydrolysed cocoyl soybean protein, sold under the name May-Tein SY by the company Maybrook, the sodium salt of lauroyl oat amino acids, sold under the name Proteol Oat by the company SEPPIC, collagen hydrolysate grafted onto coconut fatty acid, sold under the name Geliderm 3000 by the company Deutsche Gelatine, and soybean proteins acylated with hydrogenated coconut acids, sold under the name Proteol VS 22 by the company SEPPIC.
1 1 ) As metal salts of Ci0-C30 and in particular Ci2-C2o fatty acids, mention may be made in particular of metal stearates, such as sodium stearate and potassium stearate, and also polyhyd roxystea rates .
Silicone surfactants
As regards the silicone surfactants, mention may be made of dimethicone copolyols, which are more particularly oxypropylenated and/or oxyethylenated polydimethyl methyl siloxanes. As examples of dimethicone copolyols, use may be made of those corresponding particularly to formula (II) below:
Figure imgf000054_0001
in which:
- Ri, R2 and R3, independently of each other, represent a CrC6 alkyl radical or a radical at least one radical Ri, R2 or R3 not being an alky
Figure imgf000054_0002
l radical or a C2-C4 acyl radical;
- A is an integer ranging from 0 to 200;
- B is an integer ranging from 0 to 50; on condition that A and B are not simultaneously equal to zero;
- x is an integer ranging from 1 to 6;
- y is an integer ranging from 1 to 30; and
- z is an integer ranging from 0 to 30, preferably to 20.
Dimethicone copolyols that may be used include those sold under the names DC 5329, DC 7439-146, DC 2-5695 and Q4-3667 by the company Dow Corning; KF-6013, KF-6015, KF-6016, KF-6017 (PEG-10 dimethicone) and KF-6028 (PEG-polydimethylsiloxyethyl dimethicone), KF-6050 L(PEG/PPG 18/18 dimethicone) by the company Shin-Etsu.
Use may also be made of:
dimethicone copolyol, such as the product sold under the name Q2-5220® by the company Dow Corning;
the mixture of cyclomethicone/dimethicone copolyol sold under the name Q2-3225C® by the company Dow Corning; and
the mixture of cyclomethicone and dimethicone copolyol sold under the name DC- 5225C by the company Dow Corning;
- alkyl dimethicone copolyols such as the laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by the company Dow Corning; cetyl dimethicone copolyol such as the product sold under the name Abil EM 90 by the company Evonik Goldschmidt, and the mixture of cetyl dimethicone copolyol, polyglyceryl (4 mol) isostearate and hexyl laurate sold under the name Abil WE 09 by the company Evonik Goldschmidt, or alternatively phosphate-based surfactants.
Use may also be made of dimethicone copolyol benzoate, such as the product sold under the names Finsolv SLB 101® and 201® by the company Finetex.
Emulsion surfactants that may also be mentioned include, in particular for water-in-oil emulsions, crosslinked elastomeric solid organopolysiloxanes comprising at least one oxyalkylene group, such as the products obtained according to the procedure of Examples 3, 4 and 8 of document US-A-5 412 004 and the examples of document US-A-5 81 1 487, especially the product of Example 3 (synthetic example) of patent US-A-5 412 004, and such as the product sold under the reference KSG 21 by the company Shin-Etsu.
One or more coemulsifiers, which may be chosen advantageously from the group comprising polyol alkyl esters, may also be added thereto. Polyol alkyl esters that may especially be mentioned include polyethylene glycol esters, for instance PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135 by the company I CI . According to a particular embodiment of the invention, and irrespective of the sense of the emulsion, the surfactant(s) are chosen from nonionic surfactants and silicone surfactants, or mixtures thereof.
According to a particularly preferred embodiment, an emulsion according to the invention, in particular a water-in-oil emulsion, comprises at least one silicone surfactant chosen from (alkyl)dimethicone copolyols, alone or as mixtures.
AQUEOUS PHASE
The composition according to the invention comprises an aqueous phase.
The aqueous phase comprises water and optionally at least one water-soluble solvent. In the present invention, the term "water-soluble solvent" means a compound that is liquid at room temperature and atmospheric pressure, and that is water-miscible (miscibility with water of greater than 50% by weight at 25°C and atmospheric pressure).
The composition according to the invention preferentially comprises at least 10% by weight, in particular from 20% to 70% by weight and especially from 25% to 60% by weight of aqueous phase (water + water-soluble solvent), relative to the total weight of the composition.
The composition according to the invention preferentially comprises at least 10% by weight, in particular from 20% to 65% by weight and especially from 25% to 55% by weight of water, relative to the total weight of the composition.
According to one embodiment, the composition may comprise at least 60% by weight, preferably at least 70% by weight and in particular at least 75% by weight of water, relative to the total weight of the aqueous phase.
According to a preferred embodiment, the composition comprises a total content of water and volatile oil(s) of greater than or equal to 40% by weight and in particular greater than or equal to 50% by weight relative to the total weight of the composition.
Among the water-soluble solvents that may be used in the composition in accordance with the invention, mention may be made especially of monoalcohols containing from 1 to 5 carbon atoms, such as ethanol and isopropanol, ethylene glycol, ketones containing three or four carbon atoms, and aldehydes containing from two to four carbon atoms.
POLYOLS The composition according to the invention may comprise at least one polyol, more particularly a saturated or unsaturated, linear or branched C2-C8 and preferably C3-C6 polyol that is liquid at room temperature, comprising from 2 to 6 hydroxyl groups.
Preferably, the polyol is chosen from glycerol, diglycerol, linear or branched, saturated C3-C8 glycols, in particular propylene glycol, butylene glycol, pentylene glycol, caprylyl glycol or dipropylene glycol, and also mixtures thereof, and preferably glycerol, propylene glycol or butylene glycol, and mixtures thereof.
In accordance with a preferred embodiment of the invention, the second oily phase comprises at least glycerol as polyol.
If it comprises any, the composition according to the invention has a content of polyol(s) particularly between 2% and 10% by weight and preferably from 4% to 8% by weight relative to the total weight of the composition. DYESTUFFS
The composition according to the invention may also comprise at least one dyestuff chosen especially from water-soluble or liposoluble dyestuffs, pigments and nacres, and mixtures thereof.
The term "dyestuff" means a compound that is capable of producing a coloured optical effect when it is formulated in sufficient amount in a suitable cosmetic medium.
The water-soluble dyestuffs used according to the invention are more particularly water-soluble dyes.
For the purposes of the invention, the term "water-soluble dye" means any natural or synthetic, generally organic compound, which is soluble in an aqueous phase or water- miscible solvents and which is capable of imparting colour. In particular, the term "water- soluble" is intended to characterize the capacity of a compound to be dissolved in water, measured at 25°C, to a concentration at least equal to 0.1 g/L (production of a macroscopically isotropic, transparent, coloured or colourless solution). This solubility is in particular greater than or equal to 1 g/L.
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 (CI: 14700), DC Red 6 (Lithol Rubine Na; CI: 15850), DC Red 22 (CI: 45380), DC Red 27 (CI: 45410 Na salt), DC Red 30 (CI: 73360), DC Red 33 (CI: 17200), DC Orange 4 (CI: 15510), FDC Yellow 5 (CI: 19140), FDC Yellow 6 (CI: 15985), DC Yellow 8 (CI: 45350 Na salt), FDC Green 3 (CI: 42053), DC Green 5 (CI: 61570), FDC Blue 1 (CI: 42090).
As non-limiting illustrations of sources of water-soluble dyestuff(s) that may be used in the context of the present invention, mention may be made in particular of those of natural origin, such as extracts of cochineal carmine, of beetroot, of grape, of carrot, of tomato, of annatto, of paprika, of henna, of caramel and of curcumin.
Thus, the water-soluble dyestuffs that are suitable for use in the invention are especially carminic acid, betanin, anthocyans, enocyanins, lycopene, β-carotene, bixin, norbixin, capsanthin, capsorubin, flavoxanthin, lutein, cryptoxanthin, rubixanthin, violaxanthin, riboflavin, rhodoxanthin, cantaxanthin and chlorophyll, and mixtures thereof.
They may also be copper sulfate, iron sulfate, water-soluble sulfopolyesters, rhodamine, betaine, methylene blue, the disodium salt of tartrazine and the disodium salt of fuchsin.
Some of these water-soluble dyestuffs are in particular permitted for food use. Representatives of these dyes that may be mentioned more particularly include dyes of the carotenoid family, referenced under the food codes E120, E162, E163, E160a-g, E150a, E101 , E100, E140 and E141.
According to a particularly preferred embodiment, the water-soluble dyestuff(s) are chosen from the disodium salt of brilliant yellow FCF sold by the company LCW under the name DC Yellow 6, the disodium salt of fuchsin acid D sold by the company LCW under the name DC Red 33, and the trisodium salt of Rouge Allura sold by the company LCW under the name FD & C Red 40.
The dyestuff(s) used in the context of the present invention may also be chosen from pigments.
The term "pigments" should be understood as meaning white or coloured, inorganic (mineral) or organic particles, which are insoluble in the liquid organic phase, and which are intended to colour and/or opacify the composition and/or the deposit produced with the composition.
The pigments may be chosen from mineral pigments, organic pigments and composite pigments (i.e. pigments based on mineral and/or organic materials).
The pigments may be chosen from monochromatic pigments, lakes, nacres, and pigments with an optical effect, for instance reflective pigments and goniochromatic pigments.
The coated or uncoated mineral pigments may be chosen from metal oxide pigments, chromium oxides, iron oxides, titanium dioxide, zinc oxides, cerium oxides, zirconium oxides, manganese violet, Prussian blue, ultramarine blue and ferric blue, and mixtures thereof.
Organic lakes are organic pigments formed from a dye attached to a substrate. The lakes, which are also known as organic pigments, may be chosen from:
cochineal carmine;
organic pigments of azo dyes, anthraquinone dyes, indigoid dyes, xanthene dyes, pyrene dyes, quinoline dyes, triphenylmethane dyes or fluoran dyes. Among the organic pigments that may in particular be mentioned are those known under the following names: D&C Blue No. 4, D&C Brown No. 1 , D&C Green No. 5, D&C Green No. 6, D&C Orange No.
4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 1 1 , D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21 , D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31 , D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 1 1 , FD&C Blue No. 1 , FD&C Green No. 3, FD&C Red No. 40, FD&C Yellow No.
5, FD&C Yellow No. 6; insoluble sodium, potassium, calcium, barium, aluminium, zirconium, strontium or titanium salts of acid dyes such as azo, anthraquinone, indigoid, xanthene, pyrene, quinoline, triphenylmethane or fluoran dyes, these dyes possibly comprising at least one carboxylic or sulfonic acid group; and
- mixtures thereof.
The organic lakes may also be supported on an organic support such as rosin or aluminium benzoate, for example.
Among the organic lakes, mention may be made in particular of those known under the following names: D&C Red No. 2 Aluminium lake, D&C Red No. 3 Aluminium lake, D&C Red No. 4 Aluminium lake, D&C Red No. 6 Aluminium lake, D&C Red No. 6 Barium lake, D&C Red No. 6 Barium/Strontium lake, D&C Red No. 6 Strontium lake, D&C Red No. 6 Potassium lake, D&C Red No. 7 Aluminium lake, D&C Red No. 7 Barium lake, D&C Red No. 7 Calcium lake, D&C Red No. 7 Calcium/Strontium lake, D&C Red No. 7 Zirconium lake, D&C Red No. 8 Sodium lake, D&C Red No. 9 Aluminium lake, D&C Red No. 9 Barium lake, D&C Red No. 9 Barium/Strontium lake, D&C Red No. 9 Zirconium lake, D&C Red No. 10 Sodium lake, D&C Red No. 19 Aluminium lake, D&C Red No. 19 Barium lake, D&C Red No. 19 Zirconium lake, D&C Red No. 21 Aluminium lake, D&C Red No. 21 Zirconium lake, D&C Red No. 22 Aluminium lake, D&C Red No. 27 Aluminium lake, D&C Red No. 27 Aluminium/Titanium/Zirconium lake, D&C Red No. 27 Barium lake, D&C Red No. 27 Calcium lake, D&C Red No. 27 Zirconium lake, D&C Red No. 28 Aluminium lake, D&C Red No. 30 lake, D&C Red No. 31 Calcium lake, D&C Red No. 33 Aluminium lake, D&C Red No. 34 Calcium lake, D&C Red No. 36 lake, D&C Red No. 40 Aluminium lake, D&C Blue No. 1 Aluminium lake, D&C Green No. 3 Aluminium lake, D&C Orange No. 4 Aluminium lake, D&C Orange No. 5 Aluminium lake, D&C Orange No. 5 Zirconium lake, D&C Orange No. 10 Aluminium lake, D&C Orange No. 17 Barium lake, D&C Yellow No. 5 Aluminium lake, D&C Yellow No. 5 Zirconium lake, D&C Yellow No. 6 Aluminium lake, D&C Yellow No. 7 Zirconium lake, D&C Yellow No. 10 Aluminium lake, FD&C Blue No. 1 Aluminium lake, FD&C Red No. 4 Aluminium lake, FD&C Red No. 40 Aluminium lake, FD&C Yellow No. 5 Aluminium lake, FD&C Yellow No. 6 Aluminium lake.
Mention may also be made of liposoluble dyes, such as, for example, Sudan Red, DC
Red 17, DC Green 6, β-carotene, soybean oil, Sudan Brown, DC Yellow 1 1 , DC Violet 2, DC Orange 5 and quinoline yellow.
The chemical substances corresponding to each of the organic dyestuffs cited above are mentioned in the publication "International Cosmetic Ingredient Dictionary and Handbook", 1997 edition, pages 371 to 386 and 524 to 528, published by The Cosmetic, Toiletries and Fragrance Association, the content of which is incorporated into the present patent application by way of reference.
The pigments may also have been subjected to a hydrophobic treatment.
The hydrophobic treatment agent may be chosen from silicones such as methicones, dimethicones, alkoxylsilanes and perfluoroalkylsilanes; fatty acids such as stearic acid; metal soaps such as aluminium dimyristate, the aluminium salt of hydrogenated tallow glutamate, perfluoroalkyl phosphates, perfluoroalkylsilanes, perfluoroalkylsilazanes, polyhexafluoropropylene oxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups and amino acids; N-acylamino acids or salts thereof; lecithin, isopropyl triisostearyl titanate, and mixtures thereof.
The N-acylamino acids can comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group. The salts of these compounds can be the aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts. The amino acid may be, for example, lysine, glutamic acid or alanine.
The term "alkyl" mentioned in the compounds cited above especially denotes an alkyl group containing from 1 to 30 carbon atoms and preferably containing from 5 to 16 carbon atoms.
Hydrophobic-treated pigments are described especially in patent application EP-A-1 086 683.
For the purposes of the present patent application, the term "nacre" means coloured particles of any form, which may or may not be iridescent, especially produced by certain molluscs in their shell, or alternatively synthesized, and which have a colour effect via optical interference.
Examples of nacres that may be mentioned include nacreous pigments such as titanium mica coated with an iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye in particular of the abovementioned type, and also nacreous pigments based on bismuth oxychloride. They may also be mica particles, at the surface of which are superposed at least two successive layers of metal oxides and/or of organic dyestuffs.
The nacres may more particularly have a yellow, pink, red, bronze, orangey, brown, gold and/or coppery colour or tint.
As illustrations of nacres that may be introduced as interference pigments into the first composition, mention may be made of the gold-coloured nacres sold in particular by the company Engelhard under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold in particular by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company Engelhard under the name Super bronze (Cloisonne); the orange nacres sold in particular by the company Engelhard under the name Orange 363C (Cloisonne) and Orange MC 101 (Cosmica) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown nacres sold in particular by the company Engelhard under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper tint sold in particular by the company Engelhard under the name Copper 340A (Timica); the nacres with a red tint sold in particular by the company Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow tint sold in particular by the company Engelhard under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold in particular by the company Engelhard under the name Sunstone G012 (Gemtone); the pink nacres sold in particular by the company Engelhard under the name Tan opale G005 (Gemtone); the black nacres with a gold tint sold in particular by the company Engelhard under the name Nu antique bronze 240 AB (Timica), the blue nacres sold in particular by the company Merck under the name Matte blue (17433) (Microna), the white nacres with a silvery tint sold in particular by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold in particular by the company Merck under the name Indian summer (Xirona), and mixtures thereof. ADDITIVES
The composition according to the invention may also comprise any additive chosen by a person skilled in the art such that the advantageous properties intrinsically associated with the compositions in accordance with the invention are not, or not substantially, adversely affected by the envisaged addition(s).
As additives that may be incorporated into the compositions in accordance with the invention, mention may be made especially of hydrophilic thickeners, hydrophobic thickeners, fillers of organic or mineral nature, emollients, humectants other than the abovementioned polyols, stabilizers, preserving agents, pigment dispersers, film-forming agents other than those according to the invention, and organic solvents.
As examples of hydrophilic thickening polymers, mention may be made more particularly of:
- acrylic or methacrylic acid homopolymers or copolymers or salts and esters thereof and in particular the products sold under the names Versicol F or Versicol K by the company Allied Colloid, Ultrahold 8 by the company Ciba-Geigy, and polyacrylic acids of Synthalen K type, and salts, in particular sodium salts, of polyacrylic acid (corresponding to the I NCI name sodium acrylate copolymer) and more particularly a crosslinked sodium polyacrylate (corresponding to the INCI name sodium acrylate copolymer (and) caprylic/capric triglyceride) sold under the name Luvigel EM by the company BASF,
- copolymers of acrylic acid and of acrylamide sold in the form of the sodium salt thereof under the name Reten by the company Hercules, the sodium polymethacrylate sold under the name Darvan No. 7 by the company Vanderbilt, and the sodium salts of polyhydroxycarboxylic acids sold under the name Hydagen F by the company Henkel,
- polyacrylic acid/alkyl acrylate copolymers, preferably modified or unmodified carboxyvinyl polymers, particularly acrylate/Ci0-C3o-alkylacrylate copolymers (INCI name:
Acrylat.es/C10-C30 Alkyl acrylate Crosspolymer) such as the products sold by the company Lubrizol under the trade names Pemulen TR1 , Pemulen TR2, Carbopol 1382 and Carbopol EDT 2020, and even more preferentially Pemulen TR-2,
- polyacrylamidomethylpropanesulfonic acid partially neutralized with aqueous ammonia and highly crosslinked, sold by the company Clariant, - acrylamidopropanesulfonic/acrylamide copolymers of Sepigel or Simulgel type sold by the company SEPPIC,
- polyoxyethylenated acrylamidopropanesulfonic/alkyl methacrylate copolymers (crosslinked or non-crosslinked) of the Aristoflex HMS type sold by the company Clariant, - copolymers of hydroxyalkylacrylic acid or salts thereof and of acryloyldimethyl taurate monomers such as the product Sepinov EMT 10 sold by the company SEPPIC,
- and mixtures thereof.
Other examples of hydrophilic gelling polymers that may be mentioned include:
- anionic, cationic, amphoteric or nonionic chitin or chitosan polymers;
- cellulose polymers, for instance alkylcelluloses such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, and also quaternized cellulose derivatives;
- vinyl polymers, for instance polyvinylpyrrolidones, copolymers of methyl vinyl ether and of malic anhydride, the copolymer of vinyl acetate and of crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate; copolymers of vinylpyrrolidone and of caprolactam; polyvinyl alcohol;
- optionally modified polymers of natural origin, such as galactomannans and derivatives thereof, for instance konjac gum, gellan gum, locust bean gum, fenugreek gum, karaya gum, gum tragacanth, gum arabic, acacia gum, guar gum, hydroxypropyl guar, hydroxypropyl guar modified with sodium methylcarboxylate groups (Jaguar XC97-1 , Rhodia), hydroxypropyltrimethylammonium guar chloride, and xanthan gum and derivatives thereof;
- alginates and carrageenans;
- muccopolysaccharides such as hyaluronic acid,
- and mixtures thereof.
If the composition comprises any, the content of hydrophilic thickener ranges from 0.01 % to 3% by weight, preferably from 0.05% to 2% by weight and more advantageously from 0.1 % to 1 % by weight relative to the total weight of the composition.
As hydrophobic thickener, mention may be made most particularly of hydrophobic mineral thickeners, for instance modified clays and modified silicas, or mixtures thereof.
Hydrophobic modified clays
Clays are silicates containing a cation that may be chosen from calcium, magnesium, aluminium, sodium, potassium and lithium cations, and mixtures thereof.
Examples of such products that may be mentioned include clays of the smectite family and also of the vermiculite, stevensite or chlorite family. These clays may be of natural or synthetic origin. Use is preferably made of organophilic clays, more particularly modified clays, such as montmorillonite, bentonite, hectorite, attapulgite and sepiolite, and mixtures thereof. The clay is preferably a bentonite or a hectorite.
These clays are modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylarylsulfonates and amine oxides, and mixtures thereof.
Mention may thus be made of hectorites modified with a quaternary amine, more specifically with a Cio to C22 fatty acid ammonium halide, such as a chloride, optionally comprising an aromatic group, such as hectorite modified with a halide, preferably 2 distearyldimethylammonium chloride (CTFA name: Disteardimonium hectorite), for instance the product sold under the name Bentone 38V, Bentone 38V CG or Bentone EW CE by the company Elementis, or stearalkonium hectorites, in particular such as Bentone 27 V.
Mention may also be made of quaternium-18 bentonites, such as those sold, inter alia, under the names Bentone 34 by the company Elementis, Tixogel VP by the company United Catalyst and Claytone 40 by the company Southern Clay; stearalkonium bentonites, such as those sold under the names Tixogel LG by the company United Catalyst and Claytone AF and Claytone APA by the company Southern Clay; or quaternium-18/benzalkonium bentonites, such as those sold under the name Claytone HT by the company Southern Clay.
According to a preferred embodiment, the thickener is chosen from organophilic modified clays, in particular organophilic modified hectorites, in particular modified with halide, especially benzyldimethylammonium stearate chloride or with distearyldimethylammonium chloride.
Modified silicas
Mention may also be made of fumed silica subjected to a hydrophobic surface treatment, the particle size of which is advantageously less than 1 μιτι. Specifically, it is possible to chemically modify the surface of the silica, by chemical reaction generating a reduced number of silanol groups present at the surface of the silica. Silanol groups can in particular be replaced by hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be:
- trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "silica silylate" according to the CTFA (6th edition, 1995). They are sold, for example, under the references Aerosil R812® by the company Degussa, and Cab-O-Sil TS-530® by the company Cabot;
- dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane, for example hexamethyldisiloxane or dimethyldichlorosilane. Silicas thus treated are known as "silica dimethyl silylate" according to the CTFA (6th edition, 1995). They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab- O-Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot. The hydrophobic fumed silica in particular has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm.
The composition according to the invention may also comprise at least silica aerogel particles.
Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air.
They are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, the one most commonly used being supercritical C02. This type of drying makes it possible to avoid shrinkage of the pores and of the material. The sol-gel process and the various drying processes are described in detail in Brinker CJ., and Scherer G.W., Sol-Gel Science: New York: Academic Press, 1990.
The hydrophobic silica aerogel particles that are suitable for use in the invention have a specific surface area per unit mass (SM) ranging from 500 to 1500 m2/g, preferably from 600 to 1200 m2/g and better still from 600 to 800 m2/g, and a size expressed as the volume-mean diameter (D[0.5]) ranging from 1 to 1500 μπι, better still from 1 to 1000 μηι, preferably from 1 to 100 μηι, in particular from 1 to 30 μπι, more preferably from 5 to 25 μηι, better still from 5 to 20 μπι and even better still from 5 to 15 μηη.
According to an advantageous embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit mass (SM) ranging from 600 to 800 m2/g and a size expressed as volume-mean diameter (D[0.5]) ranging from 5 to 20 μιτι and better still from 5 to 15 μιη.
The specific surface area per unit mass may 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, which corresponds to international standard ISO 5794/1 (appendix D). The BET specific surface area corresponds to the total specific surface area of the particles under consideration.
The sizes of the silica aerogel particles may be measured by static light scattering using a commercial particle size analyser such as the MasterSizer 2000 machine from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non- spherical particles, an "effective" particle diameter. This theory is especially described in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957.
According to a preferred embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit volume Sv ranging from 5 to 60 m2/cm3, preferably from 10 to 50 m2/cm3 and better still from 15 to 40 m2/cm3.
The aerogels used according to the present invention are hydrophobic silica aerogels preferably of silyl silica (I NCI name silica silylate).
As regards the preparation of the hydrophobic silica aerogel particles surface-modified by silylation, reference may be made to US 7 470 725. Hydrophobic silica aerogel particles surface-modified with trimethylsilyl groups will preferably be used.
As hydrophobic silica aerogels that may be used in the invention, examples that may be mentioned include the aerogel sold under the name VM-2260 (INCI name: Silica silylate), by the company Dow Coming, the particles of which have a mean size of about 1000 microns and a specific surface area per unit of mass ranging from 600 to 800 m2/g.
Mention may also be made of the aerogels sold by the company Cabot under the references Aerogel TLD 201 , Aerogel OGD 201 , Aerogel TLD 203, Enova® Aerogel MT 1 100 and Enova Aerogel MT 1200.
Use will preferably be made of the aerogel sold under the name VM-2270 (INCI name:
Silica silylate) by the company Dow Corning, the particles of which have an average size ranging from 5-15 microns and a specific surface area per unit of mass ranging from 600 to 800 m2/g.
Preferably, the mineral thickeners are chosen from organophilic clays, in particular modified hectorites; hydrophobic-treated fumed silica; hydrophobic silica aerogels, or mixtures thereof, and even more precisely at least one organophilic modified clay or at least one hydrophobic modified silica, in particular an organophilic modified clay.
More particularly, if the composition contains any, the content of mineral thickener(s) represents from 0.2 to 2% by weight, expressed as active material, preferably 0.5 to 1.8% by weight, relative to the total weight of the composition.
The term "filler" should be understood as meaning colourless or white solid particles of any shape, which are in a form that is insoluble and dispersed in the medium of the composition. They are different from the dyestuffs and make it possible especially to thicken the lipophilic phase of the composition according to the invention.
Among the fillers that may be used in the compositions according to the invention, mention may be made of silica, kaolin, bentone, starch, lauroyllysine, and fumed silica particles, optionally hydrophilically treated, and mixtures thereof.
A composition used according to the invention may comprise one or more fillers in a content ranging from 0.1 % to 15% by weight and in particular from 1 % to 10% by weight relative to the total weight of the composition.
DEVICE
The composition according to the invention may be conditioned in any type of device that is common for fluid cosmetic compositions intended especially to be applied to the lips.
It may thus be envisaged to use devices containing a container comprising an applicator equipped with a ball (roll-on), a container of dispensing pen type, terminated with an end provided with at least one orifice through which the composition may be expelled, or alternatively terminated with a felt or with a partially or fully flocked tip, or with a brush; a container comprising a dip applicator, for instance a brush. Such devices may or may not be provided with a mechanism for dispensing the composition making it possible to expel said composition from the container to the application member, or to the support. It should be noted that this mechanism may advantageously comprise a means for metering out the composition.
According to a particularly advantageous embodiment of the invention, the composition is packaged in a container and is applied by means of an application member having a porous application surface.
The application member may be entirely porous, i.e. the composition may cross from an internal surface of the application member to an external surface of the application member, or vice versa.
The application member may in particular consist of one or more open-cell or semi- open-cell foams.
Thus, the application member may be made up of one of at least two portions of foam, of different compressibilities, which can be adhesively bonded together.
The foam may be non-crosslinked or preferentially crosslinked.
Still preferentially, the foam(s) are elastically compressible. The term "elastically compressible" is intended to mean that, starting from a position deformed by a pressure exerted on its surface, the foam returns to its initial shape when the pressure is released.
With such materials, the releasing of the composition on the surface to be treated takes place either by capillary action on contact with the lips, or by expulsion of the composition, from the pores of the applicator, in response to a slight deformation (by pressure) of said applicator on the surface to be treated.
The application member may have a cylindrical shape and may have a circular cross section. As a variant, the application member may have any other shape, for example conical, flattened-cone, nose-cone or prism shape, and can have an oval, rectangular or polygonal cross section. It may also comprise a bevelled portion and/or a concave portion forming a hollow on the application surface. The application member may be symmetrical or asymmetrical relative to a longitudinal plane of said application member.
The visible part of the application member may have a cross section which falls within a circle advantageously having a diameter of between 2 mm and 20 mm, and preferably between 5 mm and 15 mm. The visible part of the application member, in the non- compressed position, may be between 2 mm and 20 mm in height.
The application member may consist of several different materials, in particular of a stack of foams having different characteristics.
By way of example, the application member may consist of one or more foams chosen from polyether, polyester, polyurethane, polyester-polyurethane, NBR (natural butadiene rubber), SBR (synthetic butadiene rubber) or PVC (polyvinyl chloride) foams, or mixtures thereof, and quite particularly polyester-polyurethane, in particular the product S90 from Crest Foam Industries. The density of the foam(s) forming the application member, measured according to standard ASTM D 3574-05, may advantageously be between 0.02 g.cm 3 and 0.05 g.cm"3, for example 0.03 g.cm"3. This density makes it possible to release an appropriate amount of impregnated composition.
The average number of pores or cells of the foam(s) may advantageously be between
25 and 50 pores per centimetre, for example equal to 35 pores per centimetre. The average pore size may advantageously be between 0.2 mm and 0.5 mm. It should be noted that the evaluation of the average number of pores is conventionally carried out visually by counting. Preferably, the cells or pores communicate with one another omnidirectionally.
The hardness of the application surface of the applicator member, measured by means of an F-type durometer from Asker, may advantageously be between 10 Asker F and 70 Asker F.
At least one part of the surface of the application member may be covered with a flock, in particular based on polyamide, rayon, cotton, viscose or nylon fibres. The flock contributes to creating a store of product, immediately in the neighbourhood of the application surface. In addition, it makes it possible to impart more softness on application, in particular when the application member is made of wide-cell foam. Furthermore, the flock may contribute to the homogenization of the spreading of the composition to form a thin film.
The flock may consist of a mixture of fibres of various lengths and/or nature and/or diameters.
The length of the fibres may advantageously be between 0.2 mm and 1 mm, for example equal to 0.75 mm.
The fibre count grading unit may advantageously be between 0.3 dtex and 3.3 dtex, for example equal to 1.7 dtex.
As a variant, the application surface can be covered with a permeable coating of textile, perforated plastic or felt type.
In accordance with one advantageous variant of the invention, the device comprises a composition-dispensing mechanism which makes it possible to expel said composition from the container to the application member.
According to this variant, said dispensing mechanism advantageously comprises a composition-metering means.
Application devices that are particularly suited to this composition will be described with reference to the appended drawings, in which:
- Figure 1 is a sectional view of an application device according to a first embodiment;
- Figure 2 is an exploded view of an application device according to a second embodiment;
- Figure 3 is a sectional view of the device of Figure 2.
According to a first embodiment represented in Figure 1 , the device 1 comprises a cylindrical polypropylene body 2 having a longitudinal axis X. The body 2 denotes a first housing 3 (container), delimited by a cylindrical skirt 19, a first end 18 of which is open, and a second end of which, opposite the first, is closed by a transverse wall 16 comprising passages which emerge to form a grille 42. The transverse wall 16 separates the first housing 3 from a second housing 6, located above the first housing 3.
The upper housing 6 has a bottom 7, in the shape of a hemisphere, into which the passages forming the grille 42 emerge. One end of the housing 6, opposite the bottom 7, forms a free edge 8 delimiting an opening 9. The external surface of the housing 6 comprises a screw thread 10 intended to cooperate with a corresponding screw thread 11 provided for on the internal surface of a skirt 12 of a stopper 13. As a variant, the stopper is reversibly snap-fastened onto the external surface of the housing 6.
The stopper 13 is rigidly connected to an applicator 14 correspondingly made to match the hemispherical profile defined by the bottom 7 of the housing 6. The application member 14 may be adhesively bonded, welded or crimped onto the cap 13.
The application member consists of an open-cell polyurethane foam. The density of the foam forming the application member, measured according to standard ASTM D 3574-05, is advantageously between 0.02 g.cm"3 and 0.05 g.cm"3, for example equal to 0.03 g.cm"3.
According to one preferred variant, at least one part of the surface 14 of the application member is covered with a flock 15, in particular based on rayon, cotton, viscose or nylon fibres. The length of the fibres is advantageously between 0.2 mm and 1 mm, for example 0.75 mm. The fibre count grading unit is advantageously between 0.3 dtex and 3.3 dtex, for example equal to 1.7 dtex.
The application member 14 is proportioned relative to the housing 6 such that, when the stopper 13 is in the closed position, at least one portion of the application surface of the application member 14 is in contact with the bottom 7.
The application member 14 is proportioned such that, in this position, it is not appreciably axially compressed.
The composition of the invention is here referred to as product P. This product P is contained inside the housing 3 forming a container, the open end 18 of the housing 3 being closed via a dispensing mechanism 30. The latter is mounted by clip-fastening onto the body 2 of the housing 3, after filling with the product P inside the housing 3 through its open end 18. The mechanism 30 comprises an actuating wheel 31 mounted to rotate freely with respect to the body 2, via a bulge/groove arrangement. The wheel 31 is rigidly connected to a threaded rod 32 capable of axially driving a threaded piston 33, incapable of rotating inside the container, for example by virtue of a rib/notch assembly which prevents the piston from rotating inside the container. The mechanism may also comprise a metering means, such as a ratchet system, capable of periodically generating an audible sound, so as to inform the user of the amount of product dispensed.
As a variant, the mechanism associated with the first housing, for causing the product to exit, may be different; for example, the walls of the body 2 may be deformable in order to apply, by crimping, an overpressure in the container so as to expel the product through the grille. To use this device, the user turns the actuating wheel through half or one turn, with the cap 13 in the closed position over the opening 9 of the housing 6, so as to cause a corresponding amount of product P to pass from the container to the applicator 14 contained in the housing 6, via the passage of the grille 42. The product is taken up by the applicator 14, in particular by capillary action. All that then remains is for the cap 13 to be unscrewed so that the application member can be extracted therefrom and for the product P to be applied by moving the application surface of the application member 14 over lips, in order to deposit the product impregnated in the application member.
According to a variant which is not illustrated, the application member 14 is axially oversized with respect to the housing 6. Thus, after having applied all the product contained on the application member 14, it is possible to reload the latter, without having to rescrew the cap fully onto the device 1 , simply by introducing the application member 14 into the housing 6 through the opening 9, and picking up either residual product resulting from the previous actuating of the wheel 31 , or product resulting from a further actuating of the wheel 31 , in the absence of the application member 14.
According to a second embodiment represented in Figures 2 and 3, the device is in the form of an applicator bottle for a product P, and comprises mainly a container or reservoir 1 10 consisting of a body 11 1 , one end of which is closed by a bottom 1 12. The other end of the reservoir 1 10 is surmounted by an application head which comprises an intermediate element 130 intended for mounting the head on the reservoir and an application member 120 housed in the intermediate element.
The intermediate element 130 comprises, on its external surface, means 132 (of screw thread or snap-fitting bead type) for enabling the removable mounting of a stopper 140 capable of covering the application member 120.
As a variant, a dispensing mechanism can be combined with the reservoir, for example a piston mechanism as previously described, or flexible walls making it possible to generate an overpressure in the reservoir in order to expel the product. Likewise, a ball 160 can be placed inside the reservoir so as to homogenize the product in order to facilitate the flow thereof and/or to facilitate the conveying thereof to the application member.
The internal wall of the intermediate element 130 defines a cylindrical internal housing 133 which rotates about an axis X. This housing 133 comprises a side wall 134 and a planar transverse wall 135 constituting the bottom of the housing. A fitting skirt 136 extends the side wall beyond the transverse wall, on the opposite side from the opening 131 of the intermediate element. The fitting skirt 136 is attached, by snap-fitting, onto the body of the reservoir, at the top of which a radial projection 1 14 is provided for, on the opposite side from the bottom 1 12.
This snap-fitting system can of course be replaced with any other system of attachment, in particular a screw attachment system. A sealing skirt 137 is advantageously provided for on the transverse wall 135 of the housing so as to come into leaktight contact with the inside of the reservoir. The body 1 1 1 of the reservoir, the intermediate element 130 and also the stopper 140 are made of rigid material, for example of polyethylene. It is obvious that these three independent elements can each be made of a different material. It is thus possible to envisage using a flexible material for at least one part of the reservoir.
The housing 133 communicates with the inside of the reservoir via a passage 139 which passes through a shaft 1 15 extending along the axis of the housing. The shaft is made up of a single part with the transverse wall 135 from which it extends to a free end, located inside the housing 133. The shaft has a circular internal cross section, which is constant throughout its axial height, whereas its external cross section decreases to the free end.
The diameter of the shaft is chosen according to the product contained in the reservoir, in such a way that the product coming from the reservoir can flow in the shaft, for example by simply shaking the assembly.
The application member 120 is mounted inside the housing 133 around the shaft 1 15. The application member is in the form of a block of porous material(s), at least one part of which is elastically compressible.
According to one preferred embodiment, the application member is made up of a block of open-cell foam, in particular a block of polyurethane foam. Alternatively, the application member 120 may be made up of an axial succession of at least two portions of foam, of different compressibilities, which can be adhesively bonded together.
According to the example represented, the application member has a cylindrical shape and has a circular cross section. It is obvious that the application member can have any other shape, and can have any other cross section.
The application member 120 has a side wall 121 , one end 122 of which constitutes a dome-shaped application surface.
Where appropriate, the application surface 122 can be covered with a flock. In this case, the flock may consist of hairs of various diameters and/or of various natures and/or of various heights, or of a mixture of such hairs.
On the opposite side from this application surface 122, the application member ends with a second open end 124 which comes into contact with the transverse wall 135 of the housing. The end 124 can be permanently attached to the intermediate element 130. Advantageously, this end is removably attached so as to make it possible to easily remove the application member in order, for example, to clean it. To this effect, the end 124 of the application member is covered with a permanent adhesive, for example an acrylic adhesive, which adheres more to the application member than to the wall 135.
A portion 123 of the side wall located on the side of the open end 124 acts as a support for the application member. The portion 123 acting as a support for the application member is separated from the rest of the application member by an annular groove 150 which defines a zone of smaller cross section. The annular groove 150 provided for on the periphery of the application member enables the zone of smaller cross section to have a greater compressibility than the rest of the application member. Thus, when a pressure is exerted on the application surface, the maximum compression of the zone of smaller cross section is obtained before obtaining the maximum compression of the application member.
When the application member is mounted in the housing 133, it occupies approximately the entire housing, the application member having a shape approximately complementary to the shape of the housing. The application member 120 has in particular an axial recess 125, the shape of which is adjusted so that the application member comes to press against the wall of the shaft, without being substantially laterally compressed by said shaft. Alternatively, the side wall of the application member can be at a distance from the shaft. When the application member is in the relaxed position, the axial recess 125 has an axial height which is substantially greater than the axial height of the shaft 115 so as to define an internal cavity inside the application member, between an internal surface 126 located facing the shaft and the free end of the shaft. The portion 127 of the application member located above the cavity has an axial thickness which is smaller than the thickness of the lateral edge 121 of the application member, measured perpendicular to the axis X. The cavity can thus constitute a store of product in proximity to the application surface, it being possible for the product to come into contact with the application member only in the cavity.
Typically, the application member has a diameter of between 2 mm and 20 mm, and preferably between 5 mm and 15 mm. Its height, in the non-compressed position, can range between 2 mm and 20 mm.
Generally, the application member 120 comprises pores or open cells which have an average size of between 0.3 mm and 0.5 mm. Preferably, the pores or cells communicate with one another omnidirectionally.
In order to use the application assembly according to the invention, the user shakes the packaging and application assembly in order to bring the product into the shaft and into the application member. As a variant, the user actuates a dispensing mechanism in order to bring the product to the application member. Product is then kept inside the block of foam 120 of the application member by capillary action. All that is then needed is to bring the application member 120 into contact with the area to be treated; a slight pressure can be applied so as to place the product present in the cells of the foam in proximity to the application surface 122. Product is then spread by passing the application surface 122 over the support to be treated, by simple capillary contact, so as to draw the product in the form of a film, under the action of the affinity of the product that is exerted between the application surface and the support to be treated, without the slightest pressure being appreciably exerted on the application assembly.
In the detailed description above, reference was made to preferred embodiments of the invention. It is obvious that variants can be introduced therein without departing from the spirit of the invention as claimed hereinafter.
In particular, the shape of the applicator may be different from the shape illustrated with reference to the embodiments that have just been described. Generally, the shape of the applicator is chosen according to the area to be treated. For example, in the case of an applicator for the lips, an applicator approximately in the shape of a cone, a nose-cone or a hemisphere will more particularly be used, the applicator optionally comprising a bevelled face.
Likewise, the applicator can be dissociated from a container containing the product without a dispensing mechanism. The device is then used by dipping the applicator in the container and then by applying the product to the lips by means of the applicator.
The examples below are presented as non-limiting illustrations from the field of the invention.
EXAMPLE 1
The following composition is prepared (the contents are expressed as weight of starting material).
Figure imgf000071_0001
Pentaerythrityl tetraisostearate (Crodamol PTIS-LQ sold by Croda) 4.5
1 ,3-Butylene glycol 6.0
Magnesium sulfate 0.7
F Preserving agent qs
Glycerol 2.0
Water qs
Acrylates/polytrimethylsiloxy methacrylate copolymer (sold under the
G name Dow Corning FA 4002 ID Silicone Acrylate by Dow Corning, as a 10.0 40% by weight mixture in isododecane)
H Ethanol 5.0
Ground pigmentary material (phase E) is prepared by dispersing the pigments in the pentaerythrityl tetraisostearate using an Exakt three-roll machine (at least 3 treatments).
The gel C is prepared by mixing the ingredients with a TM DAC 150.1 speed mixer from Hauschild, at 3500 rpm for 3 minutes.
Phase A, B, the ground material E and the gel C are stirred using a Moritz rotor-stator for 20 minutes at 70°C. Phase D is then added.
Phase F is prepared by mixing with magnetic stirring in a beaker.
It is added to the preceding mixture with stirring using the Moritz rotor-stator. After 10 minutes, the formulation is cooled to 30°C with continued stirring. Phase G and then phase H are then successively added, after homogenization.
The composition obtained is homogeneous and stable. There is no leaching or sedimentation after treatment in a centrifuge (900*g for 1 hour).
After one week, it does not undergo any phase separation at room temperature or in an oven at 45°C.
Devices used for the application:
Pack 1 : application member consisting of S90NR foam from the company Crest Foam Industries, covered with a flock from the company ERZI Flock Technik (0.75 mm; 1.7 dtex). Pack 2: applicator for compositions of lip gloss type (flexible flocked applicator 14030; GEKA GmbH).
Very thin, homogeneous and comfortable deposits are obtained, with a moisturizing sensation on application and without any dragging when the lips are slid one over the other, after 10 minutes, 30 minutes and 1 hour of drying. The deposits migrate little and are sparingly tacky/non-tacky. When the poly C10-30 alkyl acrylate is replaced with dextrin palmitate, the composition obtained is homogeneous and stable, without leaching or sedimentation after treatment in a centrifuge (900g for 1 hour).
After one week, it does not undergo any phase separation at room temperature, or in an oven at 45°C.
Very thin, homogeneous, sparingly tacky/non-tacky and sparingly migrating deposits are obtained. However, they are drier and less comfortable than in the case of the composition in accordance with the invention, with a dragging sensation when the lips are slid one over the other, this being the case 10 minutes after application.
EXAMPLES 2-3
The following compositions are prepared (the contents are expressed as weight of starting material).
Figure imgf000073_0001
Materials)
Disteardimonium hectorite (sold under the name
1 .6 1.6
Bentone 38 VCG by Elementis)
Dodecamethylpentasiloxane (sold under the name
c Xiameter PMX-200 Silicone Fluid 2CS: sold by 8.75 8.75
Dow Corning)
Propylene carbonate (sold under the name Jeffsol
0.48 0.48
propylene carbonate by Huntsman)
Bis-behenyl/isostearyl/phytosteryl dimer dilinoleyl
D dimer dilinoleate (Plandool G7 sold by Nippon Fine 2.5 2.5
Chemical)
Dyestuffs 1 .5 1.5
E Pentaerythrityl tetraisostearate (Crodamol PTIS-LQ
4.5 4.5
sold by Croda)
1 ,3-Butylene glycol 6.0 6.0
Magnesium sulfate 0.7 0.7
F Preserving agent qs qs
Glycerol 2.0 2.0
Water qs qs
Acrylates/polytrimethylsiloxy methacrylate
copolymer (sold under the name Dow Corning FA
G 10.0 10.0
4002 ID Silicone Acrylate by Dow Corning, as a
40% by weight mixture in isododecane)
H Ethanol 5.0 5.0
Ground pigmentary material (phase E) is prepared by dispersing the pigments in the pentaerythrityl tetraisostearate using an Exakt three-roll machine (at least 3 treatments).
The gel C is prepared by mixing the ingredients with a TM DAC 150.1 speed mixer from Hauschild, at 3500 rpm for 3 minutes.
Phase A, B, the ground material E and the gel C are stirred using a Moritz rotor-stator for 20 minutes at 70°C. Phase D is then added.
Phase F is prepared by mixing with magnetic stirring in a beaker.
It is added to the preceding mixture with stirring using the Moritz rotor-stator. After 10 minutes, the formulation is cooled to 30°C with continued stirring. Phase G and then phase H are then successively added, after homogenization.
The compositions obtained are homogeneous and stable. There is no leaching or sedimentation after treatment in the centrifuge (900g for 1 hour).
After one week, they do not undergo any phase separation at room temperature or in an oven at 45°C. Devices used for the application:
Pack 1 : application member consisting of S90NR foam from the company Crest Foam Industries, covered with a flock from the company ERZI Flock Technik (0.75 mm; 1 .7 dtex).
Pack 2: applicator for compositions of lip gloss type (flexible flocked applicator 14030;
GEKA GmbH).
Very thin, homogeneous and comfortable deposits are obtained, with a moisturizing sensation on application and without any dragging when the lips are slid one over the other, after 10 minutes, 30 minutes and 1 hour of drying. The deposits migrate little and are sparingly tacky/non-tacky.
When the wax is replaced with dextrin palmitate, the composition obtained is homogeneous and stable, without leaching or sedimentation after treatment in a centrifuge (900*g for 1 hour).
After one week, it does not undergo any phase separation at room temperature, or in an oven at 45°C.
Very thin, homogeneous, sparingly tacky/non-tacky and sparingly migrating deposits are obtained. However, they are drier and less comfortable than in the case of the composition in accordance with the invention, with a dragging sensation when the lips are slid one over the other, this being the case 10 minutes after application.

Claims

1 . Composition for making up and/or caring for in particular the lips, in the form of an emulsion comprising:
a. at least one film-forming polymer chosen from vinyl polymers comprising at least one carbosiloxane dendrimer-based unit,
b. at least one non-volatile oil,
c. at least one silicone gum,
d. at least one semi-crystalline polymer or at least one wax,
e. water.
2. Composition according to Claim 1 , in which the vinyl polymer comprises at least one carbosiloxane dendrimer-based unit of general formula:
Figure imgf000076_0001
in which:
R1 represents an aryl group containing from 5 to 10 carbon atoms or an alkyl containing from 1 to 10 carbon atoms;
X1 represents a silylalkyi group which, when i = 1 , is represented by formula (II):
Figure imgf000076_0002
in which:
. R1 is as defined above in formula (I),
. R2 represents an alkylene radical containing from 2 to 10 carbon atoms,
. R3 represents an alkyl group containing from 1 to 10 carbon atoms,
. Xl+1 is chosen from: a hydrogen atom, an alkyl group containing from 1 to 10 carbon atoms, an aryl group containing from 5 to 10 carbon atoms and a silylalkyi group defined above of formula (II) with i = i + 1 ,
. i is an integer from 1 to 10 which represents the generation of said silylalkyi group, and . a' is an integer from 0 to 3;
Y represents a radical-polymerizable organic group chosen from:
. organic groups containing a methacrylic group or an acrylic group, said organic groups being represented by the formulae:
Figure imgf000076_0003
in which:
* R4 represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms; and
* R5 represents an alkylene group containing from 1 to 10 carbon atoms; and
. organic groups containing a styryl group of formula:
Figure imgf000077_0001
in which:
* R6 represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms;
* R7 represents an alkyl group containing from 1 to 10 carbon atoms;
* R8 represents an alkylene group containing from 1 to 10 carbon atoms;
* b is an integer from 0 to 4; and
* c is 0 or 1 , such that if c is 0, -(R8)c- represents a bond.
3. Composition according to either of claim 1 and 2, in which the carbosiloxane dendrimer is represented by the formula:
Figure imgf000077_0002
in which:
Y, R1, R2, R3, are as defined in the preceding claim;
a1, a2 and aJ correspond to the definition of a' according to the preceding claim and
R12 represents a hydrogen atom, an aryl group containing from 5 to 10 carbon atoms or an alkyl group containing from 1 to 10 carbon atoms.
4. Composition according to any one of Claims 1 , to 3, in which the carbosiloxane dendrimer is represented by one of the following formulae:
CH, CH, CH,
I 3 I 3
H2C=C— C— O— C3H6— Si- -o— si— α,ΗΛ— si- Ό— Si -CH
I
CH, CH,
CH, CH,
I 3
H2C=CH-C— O— C3H6— Si†0— Si— C2H— Si- -Si-CH
o CH, CH,
/3
5. Composition according to any one of the preceding claims, in which the film-forming polymer chosen from vinyl polymers comprising at least one carbosiloxane dendrimer-based unit, the INCI name of which is Acrylates/polytrimethylsiloxy methacrylate copolymer.
6. Composition according to any one of the preceding claims, in which the film-forming polymer chosen from vinyl polymers comprising at least one carbosiloxane dendrimer-based unit is present in an active material content ranging from 0.5% to 20% by weight, in particular from 1 % to 15% by weight, more particularly from 1.5% to 10% by weight and preferably from 3% to 5% by weight, relative to the total weight of the composition.
7. Composition according to any one of the preceding claims, characterized in that the non-volatile oil(s) are chosen from non-volatile phenyl or non-phenyl silicone oils; non-volatile fluoro oils; non-volatile polar or apolar hydrocarbon-based oils, or mixtures thereof; and preferably from non-volatile phenyl silicone oils, from non-volatile polar or apolar hydrocarbon-based oils, and also mixtures thereof.
8. Composition according to any one of the preceding claims, characterized in that the content of non-volatile oil(s) represents at least 5% by weight, more particularly from 5 to 30% by weight, even more particularly from 10 to 20% by weight, relative to the total weight of the composition.
9. Composition according to any one of the preceding claims, characterized in that it comprises at least one volatile oil chosen from hydrocarbon-based or silicone volatile oils, and in particular chosen from Cs-Ci6 branched alkanes, linear alkanes and linear or cyclic silicones.
10. Composition according to any one of the preceding claims, characterized in that it comprises at least one non-volatile oil chosen from non-volatile phenyl silicone oils not comprising any dimethicone fragments.
1 1. Composition according to any one of the preceding claims, characterized in that the silicone gum has the following formula:
Figure imgf000078_0002
Figure imgf000078_0001
in which: - R7, R8, R1 1 and R12 are identical or different, and each is chosen from alkyl radicals comprising from 1 to 6 carbon atoms,
- R9 and R10 are identical or different, and each is chosen from an alkyl radical comprising from 1 to 6 carbon atoms, an aryl radical, a hydroxyl radical, a vinyl radical, preferably with an alkyl radical comprising from 1 to 6 carbon atoms, a hydroxyl radical;
- X is chosen from an alkyl radical comprising from 1 to 6 carbon atoms, a hydroxyl radical, a vinyl radical, preferably with an alkyl radical comprising from 1 to 6 carbon atoms, a hydroxyl radical;
- n and p are chosen so as to give the silicone gum a molecular mass of greater than or equal to 400 000 g/mol, and in particular may each take values ranging from 0 to 5000, given that n and p are not simultaneously zero.
12. Composition according to any one of the preceding claims, characterized in that the silicone gum is a polydimethylsiloxane gum optionally comprising at least one aryl radical, a dimethiconol gum, or mixtures thereof, and preferably a dimethiconol gum.
13. Composition according to any one of the preceding claims, in which the silicone gum is present in an active material content ranging from 0.1 to 10% by weight, preferably from 0.2 to 8% by weight, in particular from 0.3 to 6% by weight, and more, relative to the total weight of the composition.
14. Composition according to any one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from a group comprising homopolymers and copolymers resulting from the polymerization of at least one monomer bearing crystallizable chains, these chains being chosen from alkyl chains comprising at least 11 carbon atoms and not more than 40 carbon atoms.
15. Composition according to any one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from homopolymers obtained by polymerization of a monomer chosen from C14-C24 alkyl acrylates and C14-C24 alkyl methacrylates and from copolymers obtained by copolymerization of a monomer chosen from C14-C24 alkyl acrylates and C14-C24 alkyl methacrylates, with a hydrophilic monomer.
16. Composition according to any one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from the polymers whose INCI name is: Poly C10-C30
Alkyl Acrylate.
17. Composition according to any one of the preceding claims, characterized in that the content of semi-crystalline polymer ranges from 0.5 to 3% by weight, preferably from 0.5 to 2% by weight, relative to the total weight of the composition.
18. Composition according to any one of Claims 1 to 13, characterized in that the wax is chosen from apolar hydrocarbon-based waxes, from polar hydrocarbon-based or silicone waxes, and also a mixture thereof.
19. Composition according to the preceding claim, characterized in that the composition comprises at least one polar silicone wax, or at least one polar hydrocarbon-based wax such as waxes of animal or plant origin, optionally obtained by catalytic hydrogenation of animal or plant oils; alcohol waxes; and also mixtures thereof.
20. Composition according to any one of claims 18 or 19, characterized in that the wax content ranges from 0.5 to 5% by weight, preferably from 0.5 to 2% by weight, relative to the total weight of the composition.
21. Composition according to any one of the preceding claims, characterized in that the pasty compound(s) are chosen from hydrocarbon-based compounds, in particular from lanolin and derivatives thereof, petroleum jelly, polyol ethers, vinyl polymers, liposoluble polyethers resulting from polyetherification between one or more C2-C100 diols, esters and polyesters, butters of plant origin, totally or partially hydrogenated plant oils, esters of hydrogenated castor oil, and mixtures thereof.
22. Composition according to any one of the preceding claims, in which the pasty compound is present in a content of greater than 0.5% by weight, preferably in a content ranging from 2% to 20% by weight and in particular from 2% to 15% by weight relative to the total weight of the composition.
23. Composition according to any one of the preceding claims, characterized in that it comprises at least one surfactant chosen from nonionic or anionic, hydrocarbon-based or silicone surfactants, preferably from nonionic hydrocarbon-based surfactants, silicone surfactants particularly chosen from dimethicone copolyols, and alkyl dimethicone copolyols, and mixtures thereof.
24. Composition according to any one of the preceding claims, in which the composition comprises a water content of from 20% to 65% by weight and more preferentially from 25% to 55% by weight relative to the total weight of the composition.
25. Composition characterized in that the composition comprises at least one saturated or unsaturated, linear or branched C2-C8 and preferably C3-C6 polyol that is liquid at room temperature (25°C), comprising from 2 to 6 hydroxyl groups.
26. Composition according to any one of the preceding claims, characterized in that the composition is in the form of a water-in-oil emulsion and is preferably liquid.
27. Process for making up and/or caring for the lips, comprising the application to said lips of a composition according to any one of the preceding claims.
28. Device comprising a container (3; 1 10) in which is stored the composition according to any one of Claims 1 to 25 and comprising an application member with a porous application surface (14; 120).
29. Device according to the preceding claim, characterized in that it comprises a composition-dispensing mechanism (30) for expelling said composition from the container to the application member.
PCT/EP2017/057122 2016-03-31 2017-03-24 Aqueous emulsion comprising a silicone-based dendritic polymer, a silicone gum and a semi-crystalline polymer or a wax and treatment of the lips WO2017167667A1 (en)

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FR1652846A FR3049458B1 (en) 2016-03-31 2016-03-31 AQUEOUS EMULSION COMPRISING A SILICONE DENDRITIC POLYMER, A SILICONE GUM AND A SEMI-CRYSTALLINE POLYMER, AND A METHOD OF TREATING THE LIP USING THE SAME
FR1652845A FR3049457B1 (en) 2016-03-31 2016-03-31 AQUEOUS EMULSION COMPRISING A SILICONE DENDRITIC POLYMER, A SILICONE GUM AND A SEMI-CRYSTALLINE POLYMER, AND A METHOD OF TREATING THE LIP USING THE SAME

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