WO2016116473A1 - Émulsion huile/huile contenant des microparticules comprenant au moins deux matériaux différents, chacun étant organique ou minéral - Google Patents

Émulsion huile/huile contenant des microparticules comprenant au moins deux matériaux différents, chacun étant organique ou minéral Download PDF

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Publication number
WO2016116473A1
WO2016116473A1 PCT/EP2016/051056 EP2016051056W WO2016116473A1 WO 2016116473 A1 WO2016116473 A1 WO 2016116473A1 EP 2016051056 W EP2016051056 W EP 2016051056W WO 2016116473 A1 WO2016116473 A1 WO 2016116473A1
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Prior art keywords
oil
chosen
volatile
oils
oily phase
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PCT/EP2016/051056
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English (en)
Inventor
Léonora HENAULT-MEZAIZE
Cécile TOULOUZAN
Florence Levy
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L'oreal
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Publication of WO2016116473A1 publication Critical patent/WO2016116473A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/025—Explicitly spheroidal or spherical shape
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/621—Coated by inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/624—Coated by macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/651—The particulate/core comprising inorganic material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/654—The particulate/core comprising macromolecular material

Definitions

  • Oil/oil emulsion containing microparticles comprising at least two different materials, each being organic or mineral
  • the present invention relates to the field of cosmetic compositions based on oil/oil (O/O) emulsions.
  • 0/0 emulsions are generally stabilized with gelling agents or even emulsifying surfactants and/or (co)polymers.
  • patent application WO 2009/150 852 is directed towards an oil-in- oil cosmetic composition comprising a hydrocarbon-based non- volatile oil, a silicone nonvolatile oil and a fatty acid ester of dextrin; said application does not describe O/O emulsions of Pickering type.
  • the authors of the present invention have used O/O emulsions of Pickering type stabilized with solid particles, which particles, furthermore, are not nanoparticles.
  • the emulsions according to the invention comprise two different immiscible oily phases, one forming the continuous phase and the other forming the dispersed phase, and particular solid particles for stabilizing the emulsion by positioning themselves at the interface of the dispersed and continuous phases.
  • the solid particles Once positioned at the interface, the solid particles "block" the dispersed phase, which leads to stabilization of the emulsion.
  • the O/O emulsion thus formed is stable for several weeks.
  • the emulsion according to the invention also makes it possible to dispense with the use, as stabilizers, of compounds of surfactant type, especially synthetic surfactants, and/or of gelling agents, since some of these agents may present toxicity risks to the environment depending on the amounts used.
  • the oils used for forming the two phases may be judiciously chosen as a function of the intended use of the final product and of the desired properties.
  • a first subject of the invention is directed towards an oil/oil (O/O) emulsion comprising at least:
  • first oily phase comprising at least a first non-volatile oil chosen from silicone oils, hydrocarbon-based oils and fluoro oils,
  • a second oily phase comprising at least a second non-volatile or volatile oil, which is immiscible with the first oil(s), at 25°C, and
  • room temperature is intended to denote a temperature of about 25°C, for example ranging from 18 to 25°C. It is set at atmospheric pressure (i.e. a pressure of 1.013 x 10 5 Pa).
  • compositions and/or emulsions according to the invention comprise a physiologically acceptable medium, i.e. a non-toxic medium that can be applied to human skin, and which is of pleasant appearance, odour and feel.
  • a physiologically acceptable medium i.e. a non-toxic medium that can be applied to human skin, and which is of pleasant appearance, odour and feel.
  • the composition according to the invention is a solid composition.
  • the composition according to the invention is a liquid composition.
  • it is a cosmetic composition for caring for and/or making up the skin, and more particularly facial skin, or alternatively a composition for treating keratin fibres.
  • skin is intended to denote all of the skin of the body, including the lips, and preferably the skin of the face, the neck and the neckline, and also the lips.
  • the term "keratin fibres" more particularly means the hair.
  • the composition according to the invention is a composition chosen from lip makeup products, antisun products, deodorants, care products and fragrances.
  • the cosmetic composition of the invention may also contain adjuvants that are common in cosmetics, such as lipophilic gelling agents, preserving agents, fragrances, fillers, UV-screening agents, which are especially lipophilic, bactericides, odour absorbers, dyestuffs, plant extracts, antioxidants and nonionic, anionic, cationic or amphoteric surfactants.
  • adjuvants that are common in cosmetics, such as lipophilic gelling agents, preserving agents, fragrances, fillers, UV-screening agents, which are especially lipophilic, bactericides, odour absorbers, dyestuffs, plant extracts, antioxidants and nonionic, anionic, cationic or amphoteric surfactants.
  • these various adjuvants are those conventionally used in the field under consideration, for example from 0.01 to 20% of the total weight of the composition. Depending on their nature, these adjuvants may be introduced into the first oily phase and/or into the second oily phase.
  • the invention is directed towards the use of solid microparticles having at least one curved part whose radius of curvature is not infinite, the largest dimension of which is at least 0.15 ⁇ and comprising at least two different materials, each mineral or organic, for stabilizing an O/O emulsion comprising at least a first oily phase comprising at least a first non-volatile oil chosen from silicone oils, hydrocarbon-based oils and fluoro oils, and at least a second oily phase comprising at least a second volatile or non-volatile oil that is immiscible with the first oil(s) at 25°C.
  • the solid microparticles that may be used for stabilizing the O/O emulsion according to the invention thus have at least one curved part whose radius of curvature is not infinite.
  • the term "radius of curvature” does not cover the "infinity” value " ⁇ "; thus, the microparticles used according to the invention are not in the form of platelets or leaflets.
  • the solid microparticles in accordance with the invention may be filled or hollow. They may also be smooth or rough.
  • the largest dimension of the composite microparticles of the invention is preferably, on average, between 0.15 and 100 ⁇ , more particularly between 0.2 and 50 ⁇ , more particularly from 0.4 to 30 ⁇ , preferably between 0.5 and 20 ⁇ ; or even from 1 to 10 ⁇ , for example from 2 to 7 ⁇ .
  • the largest dimension of the particles which corresponds to a mean dimension on 50% by volume of the particles, may be determined using a laser diffraction granulometer (e.g. Mastersizer 2000 from the company Malvern).
  • the solid microparticles contain at least two curved parts.
  • the solid microparticles that may be used in the present invention comprise several curvatures.
  • the term "several curvatures” means curvatures of different radius.
  • the solid microparticles that may be used in the present invention comprise at least one concave part and at least one convex part.
  • microparticles in accordance with this variant have a form chosen from forms of "bowl”, “golf ball” and “polytope” type.
  • the solid microparticles that may be used in the present invention comprise only one curvature.
  • only one curvature means that when the microparticle comprises several curves, these curves have curvatures of the same radius.
  • They may thus be chosen from hemispherical, fusiform microparticles, for example of "rugby ball” type.
  • the solid microparticles in accordance with the invention are spherical.
  • spherical means that the particle has a sphericity index, i.e. the ratio between its smallest diameter and its largest diameter, of between 0.8 and 1.
  • the largest dimension of said microparticles corresponds more particularly to the "mean particle diameter".
  • This mean diameter may be indicated on 50% by volume of the particles (D[0,5]) obtained using a laser diffraction granulometer (e.g. Mastersizer 2000 from the company Malvern).
  • the solid microparticles may have various structures.
  • the arrangement of the at least two materials included in the microparticles may vary.
  • one subject of the invention is an oil/oil (O/O) emulsion according to any one of the attached claims, in which (i) the microparticles comprise a core comprising at least a first material; said core being covered at the surface, continuously or discontinuously, with an envelope comprising at least a second material different from the first, or alternatively (ii) at least a second material is dispersed in a matrix of at least a first material different from the second material(s).
  • the composite particles in accordance with the invention comprise a core comprising at least a first material; said core being covered at the surface, continuously or discontinuously, with an envelope (or shell) comprising at least a second material different from the first.
  • the envelope may comprise particles of the second material(s).
  • the composite particles in accordance with the invention comprise a core comprising at least a first material covered with an envelope
  • the composite particles in accordance with the invention comprise a core comprising at least a first material covered with an envelope
  • the envelope Preferentially, from 10% to 90%, more particularly from 10% to 70% and even more particularly from 30% to 50% of the surface of the core is covered with the envelope.
  • the weight ratio of the first material(s) i.e. the material(s) constituting the core of the particles or the matrix
  • the weight of the second material(s) ranges from 70/30 to 99.9/0.1, more preferentially from 80/20 to 99/1 and even more particularly from 90/10 to 99/1.
  • microparticles according to the invention are moreover such that a stable emulsion is obtained by using 5% of microparticles in a mixture comprising 47.5% of castor oil (castor oil Codex, sold by Interchimie) and 47.5% of polydimethylsiloxane oil (Dow Corning® 200 Fluid 100 cSt, sold by Dow Corning) with at least one of the following two procedures, each performed at 20°C and atmospheric pressure: 1) Rayneri blender (LG335 rotor/stator emulsifying machine; Reference B00141638 from the company VMI Rayneri; rotor diameter 25 mm - stator height 30 mm); process performed with 80 g of mixture, for 5 minutes at 1 150 rpm with only the oils, then for 5 minutes at 1150 rpm with the oils and the microparticles.
  • castor oil castor oil Codex, sold by Interchimie
  • polydimethylsiloxane oil Dow Corning® 200 Fluid 100 cSt, sold by Dow Corning
  • stable emulsion is intended to denote emulsions for which at least 50% by volume of dispersed phase remains in the form of drops, more particularly at least 70% by volume, preferably at least 80% by volume, after 24 hours at 20°C and atmospheric pressure.
  • the materials constituting the microparticles according to the invention are more particularly chosen from hydrocarbon-based and silicone polymers, or from mineral compounds; the microparticles comprising at least two different materials; the microparticles being satisfactory for obtaining a stable emulsion as described previously.
  • the materials included in the composition of the composite particles according to the invention may be chosen from the following compounds, in particular on condition that at least two different materials are present and that the particles satisfy the conditions for obtaining a stable emulsion indicated previously:
  • polysaccharides in particular natural polysaccharides or polysaccharides of natural origin
  • polyamides (v) polyamides, (v) copolymers of styrene and of (meth)acrylic acid or a (Ci-C2o)alkyl ester thereof under the INCI name: Styrene/ Acrylates Copolymer, polystyrene,
  • mineral particles chosen more particularly from metal oxides, silicates, glass particles, silica, calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, hydroxyapatite, boron nitride, and alkali metal sulfates and phosphates; bismuth oxychloride,
  • polyethylene polyethylene (meth)acrylate, polypropylene, polytetrafluoroethylene (Teflon®), polyurethanes; expanded hollow particles of vinylidene chloride and acrylonitrile polymer, and
  • polysaccharides in particular natural polysaccharides or polysaccharides of natural origin
  • mineral particles chosen more particularly from metal oxides, silicates, glass particles, silica, calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate and hydroxyapatite,
  • polyethylene polyethylene (meth)acrylate, polypropylene, polytetrafluoroethylene (Teflon®), polyurethanes; expanded hollow particles of vinylidene chloride and acrylonitrile polymer, and
  • polyorganosilsesquioxanes more particularly polymethylsilsesquioxanes
  • crosslinked or non-crosslinked poly(meth)acrylate polymers
  • silica for example fumed silicas
  • the solid microparticles in accordance with the invention may comprise a core comprising at least one polyorganosilsesquioxane.
  • the microparticles are in the form of microspheres.
  • a polyorganosilsesquioxane is more particularly a resin which is composed of trifunctional organosiloxane units represented by the following formula
  • R 2 is a substituted or unsubstituted monovalent hydrocarbon-based group containing 1 to 20 carbon atoms, illustrated by alkyl groups such as methyl, ethyl, propyl and butyl, aryl groups such as phenyl and tolyl groups, alkenyl groups such as vinyl and allyl, and aralkyl groups such as 2-phenylethyl and 2-phenylpropyl groups, and also substituted hydrocarbon-based groups obtained by replacing some or all of the hydrogen atoms in the hydrocarbon-based groups mentioned above with substituents, for example halogen atoms, epoxy groups, an amino group, a mercapto group and (meth)acryloxy, such as chloromethyl and 3,3,3-trifluoropropyl groups.
  • alkyl groups such as methyl, ethyl, propyl and butyl
  • aryl groups such as phenyl and tolyl groups
  • alkenyl groups such as vinyl and allyl
  • At least 50 mol% of the groups denoted by R 2 in the polyorganosilsesquioxane are methyl groups; more particularly at least 60%, especially at least 80%, for example at least 90%.
  • the microparticles comprise a core comprising or even formed from polymethylsilsesquioxane.
  • the microparticles bear a coating or shell on the core comprising at least one cationic polymer.
  • the cationic polymer comprises units derived from (meth)acrylamide or from (meth)acrylic acid and cyclic units derived from dialkyldiallylammonium; the alkyl group, which is optionally hydroxylated, more particularly comprising from 1 to 6 carbon atoms.
  • the cationic polymer comprises units derived from (meth)acrylamide and cyclic units derived from dialkyldiallylammonium; the alkyl group, which is optionally hydroxylated, more particularly comprising from 1 to 6 carbon atoms.
  • Said coating may also comprise at least one compound chosen from esters of a saturated or unsaturated C6-C24 fatty acid and of glycerol, the compound preferably being polyoxyalkylenated, and also silicone derivatives thereof. More particularly, mention may be made of PEG-7 glyceryl cocoate and the methylsilanol derivative Tri-PEG-8 glyceryl cocoate.
  • the particles according to this first variant may have a mean diameter of between 0.5 ⁇ and 20 ⁇ , preferably between 1 ⁇ and 10 ⁇ and preferably between 2 ⁇ and 7 ⁇ .
  • microspheres tospearl AQ® as sold by the company Momentive, designated by the following INCI name: polymethylsilsesquioxane (and) Polyquaternium-7 (and) PEG-7 Glyceryl Cocoate (and) Methylsilanol Tri-PEG-8 Glyceryl Cocoate.
  • the solid microparticles in accordance with the invention may be multilayer spherical composite particles.
  • a core comprising at least one material A with a refractive index ranging from 1.3 to 1.8;
  • At least one layer covering said core comprising at least one material B with a refractive index ranging from 1.9 to 3.1 ;
  • iii) preferably, at least a second layer covering the material B, comprising at least one material C with a refractive index ranging from 1.3 to 1.8.
  • n refractive index
  • the refractive index n, of a transparent medium is defined by the ratio between the speed of propagation of light in a vacuum, c and its speed in this medium vi .
  • the refractive index of a substance is measured relative to air.
  • the refractive index n depends on the wavelength ⁇ of the incident light, and on the temperature at which the measurement is carried out.
  • the refractive index is a complex number, the imaginary part of which gives an account of the attenuation of the wave.
  • the refractive index in particular intervenes in the Snell-Descartes laws, which involve the ratio of the refractive indices.
  • the refractive indices according to the invention are measured at room temperature (20-25°C) by means of a refractometer, most of the models of which take a measurement of the limiting angle of refraction. This method is described in "Cours de Physique Generale Optique” ["Course in General Optical Physics”] by G. Bruhat (pages 12 to 14, sixth edition, published by Masson).
  • the various layers of the spherical composite particles according to the invention are generally concentric.
  • the spherical composite particles in accordance with the invention are preferably characterized by a mean diameter of less than 50 ⁇ , more particularly between 0.5 and 20 ⁇ , and preferably less than or equal to 10 ⁇ .
  • the mineral materials A and C with a refractive index of 1.3-1.8 may be chosen from the group formed by silica, calcium carbonate and aluminium oxide, and mixtures thereof.
  • the mineral material B with a refractive index of 1.9-3.1 may be chosen from metal oxides, most particularly with zirconium and titanium oxides.
  • the layer based on the material B represents from 1% to 50% by weight and more preferentially from 5% to 30% by weight relative to the total weight of the spherical composite particle.
  • the layer based on the material C represents from 1% to 30% by weight and more preferentially from 2% to 10% by weight relative to the total weight of the spherical composite particle.
  • the solid microparticles in accordance with the invention may be composite particles comprising a matrix that may comprise one or more organic and/or mineral materials and an additional mineral material different from the organic and/or mineral materials included in the matrix.
  • the additional mineral material is generally chosen from metal oxides.
  • the matrix is essentially formed from an organic and/or mineral material.
  • the mineral materials that may be used in the matrix according to the third variant of the present invention are chosen from the group formed by mica, synthetic mica, talc, sericite, boron nitride, glass, calcium carbonate, barium sulfate, hydroxyapatite, silica, silicate, magnesium sulfate, magnesium carbonate, magnesium trisilicate, aluminium oxide, aluminium silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clays and synthetic clays and mixtures thereof.
  • the organic materials that may be used to form the matrix are chosen from the group formed by poly(meth)acrylates, polyamides, silicones, polyurethanes, polyethylenes, polypropylenes, polystyrenes, polyhydroxyalkanoates, polycaprolactams, poly(butylene succinate)s, polysaccharides, polypeptides, polyvinyl alcohols, polyvinyl resins, fluoropolymers, polyesters and polyethers, and mixtures thereof.
  • the additional mineral materials that may be used in the composite particle may be chosen from metal oxides.
  • these metal oxides are chosen from titanium dioxide Ti0 2 , zinc oxide ZnO and iron oxide FeO.
  • These metal oxides are in the form of particles with a mean size generally less than 200 run.
  • metal oxides may also be in the form of layers, preferably multilayers with a mean thickness generally less than 200 nm.
  • the additional mineral material is Ti0 2 .
  • the Ti0 2 particles used have a mean size of less than or equal to lOO nm.
  • the composite particles that may be used according to the invention are preferably spherical.
  • the mean size of the composite particles which are advantageously spherical, is more particularly between 0.15 ⁇ and 30 ⁇ , preferably between 0.2 ⁇ and 20 ⁇ , more preferably between 0.3 ⁇ and 10 ⁇ , advantageously between 0.5 ⁇ and 10 ⁇ , for example between 1 and 10 ⁇ .
  • the composite particles according to this third variant of the invention may be in various forms.
  • the composite particles contain a matrix comprising an organic and/or mineral material, in which are included particles of additional mineral material.
  • the additional mineral material is then said to be dispersed in the matrix.
  • the composite particles are formed from a matrix comprising an organic and/or mineral material, in which are included particles of additional mineral material.
  • the matrix has inclusions and particles of additional mineral material are placed in the inclusions of the matrix.
  • the composite particles are spherical and have inclusions in which are placed particles of additional mineral material.
  • composite particles corresponding to this variant mention may be made of the products Sunsil TIN 50 and Sunsil TIN 40 sold by the company Sunjin Chemical. These spherical composite particles with a mean size between 2 and 7 ⁇ are formed from T1O2 encapsulated in a silica matrix.
  • the composite particles contain a matrix made of an organic and/or mineral material, covered with a layer of additional mineral material connected to the matrix by means of a binder.
  • the mean thickness of the layer of additional mineral material is generally about ten nanometres.
  • the mean thickness of the layer of additional mineral material is advantageously between 1 and 200 nm and preferably between 10 and 200 nm.
  • the matrix may also be formed from one or more organic or mineral materials. There may then be a continuous phase of materials, such as an alloy, i.e. a continuous phase in which the materials can no longer be separated, or a discontinuous phase of materials, for example formed from an organic or mineral material covered with a layer of another different organic or mineral material.
  • a continuous phase of materials such as an alloy, i.e. a continuous phase in which the materials can no longer be separated, or a discontinuous phase of materials, for example formed from an organic or mineral material covered with a layer of another different organic or mineral material.
  • the weight ratio of the matrix to the additional mineral material is generally between 100: 1 and 100:500.
  • the composite particles may furthermore be covered with an additional coating, in particular chosen from biodegradable or biocompatible materials, lipid materials, for instance surfactants or emulsifiers, polymers, and oxides.
  • the additional mineral material used in the composite particle is Ti0 2 or a mixture of Ti0 2 and ZnO.
  • the matrix of the composite particle contains, and preferably is formed from, a material or a mixture of materials chosen from:
  • the solid microparticles in accordance with the invention may denote silicone elastomer powder coated with a silicone resin.
  • These microparticles may be of spherical or amorphous form, and preferably of spherical form.
  • the elastomeric organopolysiloxane is crosslinked and may be obtained via a crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and of diorganopolysiloxane containing ethylenically unsaturated groups bonded to silicon, especially in the presence of a platinum catalyst; or via a dehydrogenation crosslinking condensation reaction between a diorganopolysiloxane containing hydroxyl end groups and a diorganopolysiloxane containing at least one hydrogen bonded to silicon, especially in the presence of an organotin; or via a crosslinking condensation reaction of a diorganopolysiloxane containing hydroxyl end groups and of a hydrolysable organopolysilane; or via thermal crosslinking of organopolysiloxane, especially in the presence of an organoperoxide catalyst; or via crosslinking of organopolysiloxane by high-energy radiation
  • the crosslinked organopolysiloxane elastomer is obtained by a crosslinking addition reaction (A2) of a diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B2) of a diorganopolysiloxane containing at least two ethylenically unsaturated groups bonded to silicon, especially in the presence (C2) of a platinum catalyst, for instance as described in patent application EP-A-295 886.
  • A2 crosslinking addition reaction
  • B2 of a diorganopolysiloxane containing at least two hydrogens each bonded to a silicon
  • C2 platinum catalyst
  • the organopolysiloxane may be obtained by reaction of dimethylpolysiloxane bearing dimethylvinylsiloxy end groups and of methylhydrogenopolysiloxane bearing trimethylsiloxy end groups, in the presence of a platinum catalyst.
  • Compound (A2) is the base reagent for the formation of elastomeric organopolysiloxane and the crosslinking is performed by an addition reaction of compound (A2) with compound (B2) in the presence of the catalyst (C2).
  • Compound (A2) is advantageously a diorganopolysiloxane containing at least two lower (for example of C2-C4) alkenyl groups; the lower alkenyl group may be chosen from vinyl, allyl and propenyl groups. These lower alkenyl groups may be located at any position on the organopolysiloxane molecule but are preferably located at the ends of the organopolysiloxane molecule.
  • the organopolysiloxane (A2) may have a branched chain, linear chain, cyclic or network structure, but the linear chain structure is preferred.
  • Compound (A2) may have a viscosity ranging from the liquid state to the gum state.
  • compound (A2) has a viscosity of at least 100 centistokes at 25°C.
  • the organopolysiloxanes (A2) may be chosen from methylvinylsiloxanes, methylvinylsiloxane-dimethylsiloxane copolymers, dimethylpolysiloxanes bearing dimethylvinylsiloxy end groups, dimethylsiloxane-methylphenylsiloxane copolymers bearing dimethylvinylsiloxy end groups, dimethylsiloxane-diphenylsiloxane- methylvinylsiloxane copolymers bearing dimethylvinylsiloxy end groups, dimethylsiloxane-methylvinylsiloxane copolymers bearing trimethylsiloxy end groups, dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers bearing trimethylsiloxy end groups, methyl(3,3,3-trifluoropropyl)polysiloxanes bearing dimethylvinylsiloxy end groups,
  • Compound (B2) is in particular an organopolysiloxane containing at least two hydrogens bonded to silicon in each molecule and is thus the crosslinking agent for compound (A2).
  • Compound (B2) may be in any molecular structure, especially in a linear chain, branched chain or cyclic structure.
  • Compound (B2) may have a viscosity at 25°C ranging from 1 to 50 000 centistokes, especially so as to be miscible with compound (A).
  • compound (B2) it is advantageous for compound (B2) to be added in an amount such that the molecular ratio between the total amount of hydrogen atoms bonded to silicon in compound (B2) and the total amount of all the ethylenically unsaturated groups in compound (A2) is in the range from 1/1 to 20/1.
  • Compound (B2) may be chosen from trimethylsiloxy-terminated methylhydrogenopolysiloxanes, trimethylsiloxy-terminated dimethylsiloxane/methylhydrosiloxane copolymers and dimethylsiloxane/methylhydrosiloxane cyclic copolymers.
  • Compound (C2) is the catalyst for the crosslinking reaction, and is especially chloroplatinic acid, chloroplatinic acid-olefm complexes, chloroplatinic acid- alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black and platinum on a support.
  • the catalyst (C2) is preferably added in an amount of from 0.1 to 1000 parts by weight and better still from 1 to 100 parts by weight, as clean platinum metal, per 1000 parts by weight of the total amount of compounds (A2) and (B2).
  • organic groups may be bonded to silicon in the organopolysiloxanes (A2) and (B2) described previously, for instance alkyl groups such as methyl, ethyl, propyl, butyl or octyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl or 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl or xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon-based groups such as an epoxy group, a carboxylate ester group or a mercapto group.
  • alkyl groups such as methyl, ethyl, propyl, butyl or octyl
  • substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl or 3,3,3-trifluoropropyl
  • aryl groups such as phenyl, tolyl or x
  • the elastomeric organopolysiloxane powder is non- emulsifying.
  • non-emulsifying defines organopolysiloxane elastomers that do not contain a hydrophilic chain, such as polyoxyalkylene or polyglycerol units.
  • Spherical elastomeric organopolysiloxanes are especially described in patent applications JP-A-61-194 009, EP-A-242 219, EP-A-285 886 and EP-A-765 656.
  • the elastomeric organopolysiloxane powder is coated with silicone resin.
  • the silicone resin may be a silsesquioxane resin, as described, for example, in patent US 5 538 793.
  • Such elastomer powders coated with silicone resin are sold especially under the names KSP-lOO, KSP-101, KSP-102, KSP-103, KSP-104 and KSP-105 by the company Shin-Etsu.
  • the elastomeric organopolysiloxanes in the form of spherical powders may be powders of a hybrid silicone functionalized with fluoroalkyl groups, sold especially under the name KSP-200 by the company Shin-Etsu; powders of a hybrid silicone functionalized with phenyl groups, sold especially under the name KSP-300 by the company Shin-Etsu.
  • the elastomeric organopolysiloxane particles may have a JIS-A hardness of less than or equal to 80 (especially ranging from 5 to 80) and preferably less than or equal to 65 (especially ranging from 5 to 65).
  • the JIS-A hardness is measured according to the method JIS K 6301 (1995) established by the Japanese Industrial Standards Committee.
  • the elastomeric organopolysiloxane particles may have a mean size ranging from 0.5 to 20 ⁇ , for example from 1 to 10 ⁇ and especially from 2 to 7 ⁇ .
  • the particles according to the invention may also be chosen from composite materials comprising microspheres of a first material, a plurality of particles of a second material, different from the first, which may be organic or mineral, and covering the first, and a residue of coupling agent that is reactive with the first and second materials; such that the particles of the second material are covalently linked to said microspheres.
  • the first material is chosen from polymers of the type such as polyethylene, methyl methacrylate, Nylon, an ethylene (meth)acrylate copolymer, polyurethane and polyvinylidene copolymers.
  • the second material which is more particularly mineral, is preferably chosen from pigments, talc, silica, sericites and titanium mica.
  • the coupling agent is chosen from aluminates, titanates and zirconates, and also from organo functional silanes.
  • the coupling agent is chosen from titanates, such as mono(Ci-C2o)alkoxy isostearyl titanate.
  • the particles which are preferably spherical, preferably have a mean size of between 0.2 and 50 ⁇ and more particularly between 0.4 and 30 ⁇ .
  • the silicone elastomer used in the present invention is chosen from Dimethicone Crosspolymer (INCI name), Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone /Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone Crosspolymer-3 (INCI name).
  • organopolysiloxane powders coated with silsesquioxane resin that may advantageously be used according to the invention, mention may especially be made of the organopolysiloxane elastomers having the INCI name Vinyl Dimethicone/Methicone Silsesquioxane Crosspolymer, such as those sold under the commercial reference KSP-100 from the company Shin-Etsu.
  • amylose and amylopectin vary as a function of the botanical origin of the starches. On average, a sample of native starch consists of about 25% amylose and 75% amylopectin. Occasionally, phytoglycogen is present (between 0%> and 20% of the starch), which is an analogue of amylopectin but branched every 10 to 15 glucose residues.
  • the botanical origin of the starch molecules used in the present invention may be cereals or tubers.
  • the starches are chosen, for example, from corn starch, rice starch, tapioca starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch and pea starch.
  • the native starches are represented, for example, by the products sold under the names C*AmilogelTM, Cargill GelTM, C* GelTM, Cargill GumTM, DryGelTM and C*Pharm GelTM by the company Cargill, under the name Corn Starch by the company Roquette, and under the name Tapioca Pure by the company National Starch.
  • modified starches used in the composition of the invention may be modified via one or more of the following reactions: pregelatinization, degradation (acid hydrolysis, oxidation, dextrinization), substitution (esterification, etherification), crosslinking (esterification), bleaching. More particularly, these reactions can be carried out in the following way:
  • Ci-C 6 acyl acetyl
  • Ci-C 6 hydroxyalkyl hydroxyethyl or hydroxypropyl
  • carboxymethyl or octenylsuccinic in particular Ci-C 6 acyl (acetyl), Ci-C 6 hydroxyalkyl (hydroxyethyl or hydroxypropyl), carboxymethyl or octenylsuccinic.
  • Monostarch phosphates (of the type St-0-PO-(OX) 2 ), distarch phosphates (of the type St-O-PO-(OX)-O-St) or even tristarch phosphates (of the type St-0-PO-(0-St) 2 ) or mixtures thereof may especially be obtained by crosslinking with phosphorus compounds.
  • X especially denotes alkali metals (for example sodium or potassium), alkaline-earth metals (for example calcium or magnesium), ammonium salts, amine salts, for instance those of monoethanolamine, diethanolamine, triethanolamine, 3-amino-l,2- propanediol, or ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine or citrulline.
  • alkali metals for example sodium or potassium
  • alkaline-earth metals for example calcium or magnesium
  • ammonium salts for instance those of monoethanolamine, diethanolamine, triethanolamine, 3-amino-l,2- propanediol, or ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine or citrulline.
  • the phosphorus compounds can, for example, be sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate.
  • the starch molecules may be derived from any plant source of starch, especially such as corn, potato, oat, rice, tapioca, sorghum, barley or wheat. It is also possible to use the starch hydrolysates mentioned above.
  • the modified starches are represented, for example, by the products sold under the names C*Tex-Instant (pregelatinized adipate), C*StabiT ex-Instant (pregelatinized phosphate), C*PolarT ex-Instant (pregelatinized hydroxypropyl), C*Set (acid hydrolysis, oxidation), C*size (oxidation), C*BatterCrisp (oxidation), C*DrySet (dextrinization), C*TexTM (acetyl distarch adipate), C*PolarTexTM (hydroxypropyl distarch phosphate), C* StabiTexTM (distarch phosphate, acetyl distarch phosphate) by the company Cargill, by distarch phosphates or compounds rich in distarch phosphate such as the product sold under the references Prejel VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate) or Prejel TK1 (gelatinized cas
  • oxidized starches use will be made especially of those sold under the name C*size from the company Cargill.
  • the porosity of celluloses may be determined by their specific surface area ranging from 0.05 m 2 /g to 1500 m 2 /g, more preferentially from 0.1 m 2 /g to 1000 m 2 /g and even more preferentially from 0.2 m 2 /g to 500 m 2 /g according to the BET method.
  • the cellulose esters result from the reaction of a few free hydroxyl functions of said rings with a carboxylic acid containing from 1 to 4 carbon atoms.
  • the cellulose esters are chosen from cellulose acetates, cellulose propionates, cellulose butyrates, cellulose isobutyrates, cellulose acetobutyrates and cellulose acetopropionates, and mixtures thereof.
  • These cellulose esters may have a weight-average molecular weight ranging from 3000 to 1 000 000, preferably from 10 000 to 500 000 and more preferentially from 15 000 to 300 000.
  • the cellulose ethers are preferably chosen from cellulose alkyl ethers with a
  • C1 -C4 alkyl group such as cellulose methyl ether, cellulose propyl ether, cellulose isopropyl ether, cellulose butyl ether and cellulose isobutyl ether.
  • These cellulose ethers may have a weight-average molecular weight ranging from 3000 to 1 000 000, preferably from 10 000 to 500 000 and more preferentially from 15 000 to 300 000.
  • core particles chosen from spherical cellulose particles mention may be made of the following commercial products sold by the company Daito Kasei in Japan:
  • the products Cellulobeads USF® and Cellulobeads D-5® are preferential, more particularly the product Cellulobeads USF®.
  • the polyamide particles used in the invention may be those sold under the name Orgasol by the company Atochem. The process for obtaining these particles is the one described, for example, in document FR 2 619 385 or in document EP 303 530. These polyamide particles are moreover known according to their various physicochemical properties under the name polyamide 12 (INCI name: Nylon- 12) or polyamide 6 (INCI name: Nylon-6). The particles used in the invention may also be those sold under the name SP500® by the company Kobo.
  • polymethylsilsesquioxanes which are obtained by hydrolysis and condensation of methyltrimethoxysilane such as the products sold under the trade names AEC Silicone Resin Spheres® (A & E Connock (Perfumery & Cosmetics) Ltd.), Belsil PMS MK® (Wacker Chemie AG), Granpowder BUI 9® (Grant Industries, Inc.), Gransil PSQ® (Grant Industries, Inc.), Gransil PSQ-W® (Grant Industries, Inc.), KMP-590® (Shin-Etsu Chemical Co.), KMP-599® (Shin-Etsu Chemical Co.), MSP-K050® (Nikko Jamaica Corporation), SilDerm SQ® (Active Concepts LLC), SilForm Flexible Resin® (Momentive Performance Materials), SilPearl 508® (Koda Corporation), Si-Tec PMS® (Ashland Inc.), Tospearl 2000® Tospearl 120A®
  • metal oxides such as zirconium oxides, cerium oxides, iron oxides and titanium oxides
  • - silicates such as talc, clays and kaolin
  • silica particles mention may be made of hollow spherical silica particles such as the products sold under the trade names Silica Beads SB 700® and Silica Beads SB 700 from the company Maprecos, and Sunspheres H-33® and Sunspheres H- 51® from the company Asahi Glass.
  • polymethylsilsesquioxanes such as those mentioned previously
  • crosslinked or non-crosslinked poly(meth)acrylate polymers such as those mentioned previously
  • the fumed silicas may be hydrophilic or lipophilic.
  • the hydrophilic fumed silicas are obtained by pyrolysis of silicon tetrachloride (SiC14) in a continuous flame at 1000°C in the presence of hydrogen and oxygen.
  • SiC14 silicon tetrachloride
  • the fumed silicas of hydrophilic nature that may be used according to the present invention, mention may especially be made of those sold by the company Degussa or Evonik Degussa under the trade names Aerosil® 90, 130, 150, 200, 300 and 380 or alternatively by the company Cabot under the name Carbosil H5.
  • the lipophilic fumed silicas may be hydrophobic-surface-treated fumed silicas. This is because it is possible to chemically modify the surface of the silica, by chemical reaction generating a reduction in the number of silanol groups present at the surface of the silica. It is especially possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.
  • the hydrophobic groups may be:
  • Silicas thus treated are named "silica silylate” according to the CTFA (8th edition, 2000). 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 thus treated are known as "silica dimethyl silylate" according to the CTFA (8th edition, 2000). 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.
  • Such coated or uncoated metal oxide particles are described in particular in patent application EP-A-0 518 773.
  • Commercial pigments that may be mentioned include the products sold by the companies Sachtleben Pigments, Tayca, Merck and Degussa.
  • the metal oxide particles may be coated or uncoated. They have a mean elementary particle size of less than or equal to 0.5 ⁇ , more preferentially between 0.005 and 0.5 ⁇ , even more preferentially between 0.01 and 0.2 ⁇ , better still between 0.01 and 0.1 ⁇ and more particularly between 0.015 and 0.05 ⁇ .
  • the coated particles are particles that have undergone one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (of titanium or aluminium), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
  • compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (of titanium or aluminium), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
  • coated particles are more particularly titanium oxides that have been coated:
  • alumina and aluminium stearate such as the products Microtitanium Dioxide MT 100 T®, MT 100 TX®, MT 100 Z® and MT-01® from the company Tayca, the products Solaveil CT-10 W® and Solaveil CT 100® from the company Uniqema and the product Eusolex T-AVO® from the company Merck, - with silica, alumina and alginic acid, such as the product MT-100 AQ® from the company Tayca,
  • the uncoated titanium oxide particles are sold, for example, by the company Tayca under the trade names Microtitanium Dioxide MT 500 B or Microtitanium Dioxide MT 600 B®, by the company Degussa under the name P 25, by the company Wackherr under the name Transparent titanium oxide PW®, by the company Miyoshi Kasei under the name UFTR®, by the company Tomen under the name ITS® and by the company Tioxide under the name Tioveil AQ®.
  • the materials constituting the particles B mention may also be made of poly-P-alanine powders, polyethylene powders; tetrafluoroethylene (Teflon®) powders, polyurea powders; polyurethane powders such as the copolymer of hexamethylene diisocyanate and of trimethylol sold under the name Plastic Powder D-400® by Toshiki; hollow expanded particles of vinylidene chloride and acrylonitrile polymer, such as the product sold under the name Expancel® by the company Expancel.
  • the composite particles are chosen from:
  • a mechanochemical melting process consists of a process in which mechanical power such as a compression force, a friction force or shear is exerted on a plurality of elements, bringing about the melting of said elements.
  • the hybridizer process was developed in the 1980s.
  • the hybridizer process is a type of mechanochemical melting process in which strong mechanical power is applied to a plurality of particles in order to bring about a mechanochemical reaction so as to form composite particles.
  • the hybridizer process may be performed using a hybridization system sold under the trade name Nara Machinery, in which at least two types of particles, generally core particles and fine particles, are introduced into a hybridizer equipped with a high- speed rotor having a plurality of blades in a dry chamber, the particles are dispersed in the chamber and mechanical and thermal energy (compression, friction and shear) are exerted on the particles for a short period of time such as from 1 to 10 minutes and preferably from 1 to 5 minutes.
  • a short period of time such as from 1 to 10 minutes and preferably from 1 to 5 minutes.
  • mineral particles chosen more particularly from metal oxides, silicates, glass particles, silica, calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate and hydroxyapatite, and
  • polyethylene polyethylene (meth)acrylate, polypropylene, polytetrafluoroethylene (Teflon®), polyurethanes; expanded hollow particles of vinylidene chloride and acrylonitrile polymer, and
  • the materials that can constitute the shell (or dispersed material) of the microparticles mention may be made of:
  • microspheres comprising a core comprising at least one polyorganosiloxane, especially a polymethylsilsesquioxane, said core being covered with a cationic polymer, especially a Polyquaternium,
  • multilayer composite spherical particles comprising:
  • At least one layer covering said core comprising at least one material B with a refractive index ranging from 1.9 to 3.1;
  • the emulsion according to the invention comprises two oily phases, a first oily phase comprising at least a first oil chosen from silicone oils, hydrocarbon-based oils and fluoro oils, and a second oily phase comprising at least a second oil that is immiscible with the first oil(s), at room temperature and at atmospheric pressure (760 mmHg/1.013 x 10 5 Pa).
  • first oily phase comprising at least a first oil chosen from silicone oils, hydrocarbon-based oils and fluoro oils
  • second oily phase comprising at least a second oil that is immiscible with the first oil(s), at room temperature and at atmospheric pressure (760 mmHg/1.013 x 10 5 Pa).
  • the term "immiscible oils” means that the mixing of these two oils does not lead to a homogeneous one-phase solution. Said mixing is performed with the same weight amount of each oil.
  • oil means a compound whose maximum viscosity is 200 000 cPs (200 Pa.s) at 25°C.
  • At least one of the oils is chosen from water-immiscible compounds (mixing performed with the same weight amount of water).
  • the oil(s) are chosen from water- immiscible compounds.
  • the viscosity is measured at 25°C ⁇ 0.5°C using a Haake RS600 controlled- stress rheometer from the company Thermo Rheo equipped with a spindle of cone/plate geometry with a diameter of between 2 cm and 6 cm and an angle of between 1° and 2°, the choice of the spindle depending on the viscosity to be measured (the more fluid the formulation, the greater the diameter of the chosen cone and the smaller the angle).
  • the measurement is performed by applying on the oil sample a logarithmic ramp of shear gradient ⁇ ' ranging from 10 "3 s "1 to 1000 s "1 for a duration of 5 minutes.
  • the value under consideration is that of the viscosity at 500 s "1 , whether it is measured at this gradient or extrapolated by the plot if no experimental point corresponds to this value.
  • oils are said to be "immiscible" when mixing them leads to a separation of phases according to the following protocols:
  • the two oils to be evaluated are introduced (5 g/5 g) at room temperature into a conical-tipped plastic centrifuge tube (ref. Corning® 15mL PET Centrifuge Tubes, Rack Packed with Plug Seal Cap, Sterile (Product #430055), which is placed in a Vortex Genie 2 machine. Stirring is performed at speed 10 for 10 seconds, followed by manual inversion of the tube before replacing it in the Vortex machine. This cycle is repeated three times in succession. The mixture is then left to stand at room temperature for 48 hours.
  • a conical-tipped plastic centrifuge tube ref. Corning® 15mL PET Centrifuge Tubes, Rack Packed with Plug Seal Cap, Sterile (Product #430055)
  • Stirring is performed at speed 10 for 10 seconds, followed by manual inversion of the tube before replacing it in the Vortex machine. This cycle is repeated three times in succession. The mixture is then left to stand at room temperature for 48 hours.
  • the mixture of the two oils (5 g/5 g) is placed in an oven at 50°C for 30 minutes before performing the three stirring cycles described previously.
  • the mixture is observed using a phase-contrast microscope, at room temperature (about 25°C). If a continuous phase and a dispersed phase in the form of drops are observed, the phases are said to be "separated" and the oils are considered as immiscible.
  • the O/O emulsion according to the invention comprises at least a first oily phase containing at least one non-volatile oil, and a second oily phase containing at least one volatile or non- volatile oil.
  • the first and second oily phases each contain at least one nonvolatile oil.
  • non- volatile refers to an oil whose vapour pressure at room temperature (25°C) and atmospheric pressure is non-zero and is less than 10 "3 mmHg (0.13 Pa).
  • volatile oil means an oil which has a non-zero vapour pressure, at room temperature (25°C) and atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa, preferably ranging from 1.3 Pa to 13 000 Pa and preferentially ranging from 1.3 Pa to 1300 Pa.
  • a preferred embodiment of the invention concerns an oil/oil emulsion in which said first non-volatile oil or second oil, preferably said first oil, is chosen from silicone oils and fluoro oils, or mixtures thereof, and more particularly from non-volatile non-phenyl silicone oils; non-volatile phenyl silicone oils, optionally bearing at least one dimethicone fragment; fluoro oils; or mixtures thereof.
  • the first oily phase comprises at least a first non-volatile oil chosen from silicone oils, fluoro oils and hydrocarbon-based oils, or mixtures thereof, and more particularly, in accordance with a first embodiment, from non-phenyl non- volatile silicone oils; phenyl non-volatile silicone oils, optionally bearing at least one dimethicone fragment; fluoro oils; or mixtures thereof.
  • a first non-volatile oil chosen from silicone oils, fluoro oils and hydrocarbon-based oils, or mixtures thereof, and more particularly, in accordance with a first embodiment, from non-phenyl non- volatile silicone oils; phenyl non-volatile silicone oils, optionally bearing at least one dimethicone fragment; fluoro oils; or mixtures thereof.
  • the first oily phase comprises at least a first hydrocarbon-based oil.
  • This first oily phase may be the continuous phase or the dispersed phase.
  • silicon oil means an oil containing at least one silicon atom, and in particular containing Si-0 groups.
  • polar hydrocarbon-based oil means an oil formed essentially from, or even constituted by, carbon and hydrogen atoms, and also heteroatoms such as oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms.
  • fluoro oil means an oil containing at least one fluorine atom.
  • Non-volatile non-phenyl silicone oils are non-volatile non-phenyl silicone oils
  • 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.
  • these oils may be chosen from the following non- volatile non- phenyl silicone oils:
  • - PDMSs 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,
  • the non- volatile non-phenyl silicone oil is preferably chosen from non- volatile dimethicone oils.
  • these non-volatile non-phenylated silicone oils are chosen from polydimethylsiloxanes; alkyl dimethicones and also PDMSs comprising at least one aliphatic group, in particular C2-C24 alkyl groups and/or at least one functional group such as hydroxyl, thiol and/or amine groups.
  • Pvi , P 2, P 5 and Re 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, a vinyl radical, an amine radical or a hydroxyl radical
  • X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or an amine radical,
  • 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 5 and X represent a methyl group
  • p and n are such that the viscosity is 60 000 cSt (54 000 mPa.s), 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,
  • phenyl silicone oils may be chosen from those which also bear at least one dimethicone fragment, or from those which do not bear any.
  • the groups R which are monovalent or divalent, represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl.
  • 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. Mixtures of different phenylorganopolysiloxane compounds described above can be used.
  • Examples that may be mentioned include mixtures of triphenyl-, tetraphenyl- or pentaphenyl-organopolysiloxanes.
  • 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: l,3,5-trimethyl-l,l,3,5,5-pentaphenyltrisiloxane; INCI name: trimethylpentaphenyltrisiloxane), or the tetramethyltetraphenyltrisiloxane sold under the reference Dow Corning 554 Cosmetic Fluid by Dow Corning may also be used.
  • - Ri to Rio independently of each other, are saturated or unsaturated, linear, cyclic or branched, preferably saturated or unsaturated, linear or branched, C1-C30 hydrocarbon-based radicals,
  • 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.
  • Ri to Rio independently of each other, represent a linear or branched C1-C30 alkyl radical, preferably C1-C20 and more particularly C1-C16 alkyl, or a monocyclic or polycyclic C 6 -Ci4 and in particular C10-C13 aryl radical, or an aralkyl radical, the alkyl part of which is preferably C1-C3 alkyl.
  • Ri to Rio 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 Rio may in particular be identical, and in addition may be a methyl radical.
  • phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding to formula (VI) below, and mixtures thereof:
  • - Ri to Re independently of each other, are saturated or unsaturated, linear, cyclic or branched, preferably saturated or unsaturated, linear or branched, C1-C30 hydrocarbon-based radicals, a preferably C 6 -Ci4 aryl radical or an aralkyl radical, the alkyl part of which is C1-C3 alkyl,
  • 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 R5 independently of each other, represent a C1-C30, preferably C1-C20 and in particular C1-C16, alkyl radical, or a C 6 -Ci4 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 5 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 Re 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
  • Ri to Re are methyl radicals.
  • the silicone oil is preferably chosen from a diphenyl dimethicone such as KF-54 from Shin-Etsu, KF54HV from Shin-Etsu, KF-50- 300CS from Shin-Etsu, KF-53 from Shin-Etsu or KF-50- lOOCS from Shin-Etsu.
  • phenyl silicone oils optionally bearing at least one dimethicone fragment correspond more particularly to formula (VII) below:
  • 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.
  • Use may be made, for example, of trimethylsiloxyphenyl dimethicone, sold in particular under the reference Belsil PDM 1000 by the company Wacker.
  • 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 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
  • R independently of each other, represent a saturated or unsaturated, linear, cyclic or branched, preferably saturated or unsaturated, linear or branched, C1-C30 hydrocarbon-based radical; more particularly, R represent a C1-C30 alkyl radical, an aryl radical, preferably a C 6 -Ci4 aryl radical, or an aralkyl radical, the alkyl part of which is Ci- C 3 alkyl,
  • n are, independently of each other, integers between 0 and 100, with the proviso that the sum n+m is between 1 and 100.
  • R independently of each other, represent a linear or branched Ci- C 3 o and in particular a C1-C20, in particular C1-C16 alkyl radical, a monocyclic or polycyclic C 6 -Ci4, and in particular Cio-Ci 3 , aryl radical, or an aralkyl radical of which preferably the aryl part is C 6 aryl and the alkyl part is Ci-C 3 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.
  • n 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.
  • a phenyl silicone oil of formula (VIII) with a viscosity at 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 70663 V30 oil from Rhone-Poulenc
  • phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding to the following formula, and mixtures thereof:
  • Ri, R 2 , Rs and Re 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 C 6 -Ci 4 ), with the proviso that at least one of R 3 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 of less than 200 000 g/mol, preferably less than 150 000 g/mol and more preferably less than 100 000 g/mol. f) and a mixture thereof.
  • the first non-volatile oil is chosen from fluoro oils.
  • the fluoro oils that may be used according to the invention may be chosen from 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 first fluoro oil according to the invention is chosen from perfluoro oils.
  • perfluoro oils that may be used in the invention, mention may be made of perfluorodecalins and perfluoroperhydrophenanthrenes.
  • the fluoro oil is chosen from perfluoroperhydrophenanthrenes, and in particular 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.
  • the first oily phase comprises at least one first non- volatile oil chosen from the non-phenyl oils of formula (I), the phenyl oils of formula (II), especially (III), of formula (V), in particular (VI) or (VII), and also mixtures thereof.
  • a second embodiment consists in using, as first oil phase, at least one hydrocarbon-based oil, chosen in particular from non-volatile oils comprising not more than one free hydroxyl group or not comprising any, or from non- volatile oils comprising at least two free hydroxyl groups, or from apolar hydrocarbon- based non- volatile oils, or mixtures thereof.
  • the second oily phase comprises at least one second non-volatile or volatile oil, which is immiscible with the first oil, at room temperature.
  • the second oily phase comprises at least one second non-volatile oil, which is immiscible with the first oil(s), at room temperature.
  • This second oily phase may be the continuous phase or the dispersed phase.
  • the second oil(s) may advantageously be chosen from polar hydrocarbon- based non-volatile oils, in particular chosen from non-volatile oils comprising not more than one free hydroxyl group or not comprising any, or from non-volatile oils comprising at least two free hydroxyl groups, or from apolar hydrocarbon-based non-volatile oils, or mixtures thereof.
  • the second oil(s) are chosen from silicone oils that are immiscible with the first oil(s).
  • the non-volatile silicone oils listed in the context of the definition of the first oily phase may be used as oil(s) of the second oily phase. Their description will not be repeated in this part of the text and reference may be made thereto, most particularly for the preferred silicones. 1. Polar non-volatile hydrocarbon-based oils
  • polar hydrocarbon-based oil means an oil formed essentially from, or even constituted by, carbon and hydrogen atoms, and also heteroatoms such as oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms.
  • It may thus contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
  • hydrocarbon-based non-volatile polar oil may be chosen from the list of oils below, and mixtures thereof: a) non-volatile oils comprising not more than one free hydroxyl group or not comprising any
  • the second oil(s) may be chosen from non-volatile hydrocarbon-based oils comprising not more than one free hydroxyl group, or not comprising any.
  • oils of this type mention may be made of: i) Ester oils
  • Hydrocarbon-based plant oils such as liquid triglycerides of fatty acids containing from 4 to 40 carbon atoms and more particularly from 4 to 24 carbon atoms.
  • Examples that may be mentioned include heptanoic or octanoic acid triglycerides, jojoba oil, sesame oil and ximenia seed oil, or mixtures thereof.
  • Synthetic glycerides such as those of capric/caprylic acids, Cis-36 acid triglyceride (Dub TGI 24 from Stearinerie Dubois).
  • Monoesters or diesters obtained from a saturated or unsaturated, aromatic or non-aromatic mono carboxy lie or dicarboxylic fatty acid, in particular comprising from 4 to 40 and in particular from 4 to 24 carbon atoms, optionally comprising a free hydroxyl, on the one hand, and from a saturated or unsaturated, aromatic or non-aromatic monoalcohol or polyol, comprising from 2 to 40 and in particular from 3 to 24 carbon atoms, on the other hand; the number of carbon atoms (excluding the carbonyl group) being at least 12 and preferably at least 16, the ester comprising at most one free hydroxyl, if it contains any.
  • - Fatty acid monoesters and diesters in particular of C4-C22 and preferably C 6 - C22, and especially of octanoic acid, heptanoic acid, lanolic acid, oleic acid, lauric acid or stearic acid, and of C3-C6 glycol, for instance propylene glycol dioctanoate, propylene glycol monoisostearate or neopentyl glycol diheptanoate, are also suitable for use.
  • Hydroxylated monoesters and diesters preferably with a total carbon number ranging from 20 to 70, for instance isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate or diisostearyl malate.
  • Rl represents a C5-C21 alkyl group
  • R 2 , R3 and R 4 which may be identical or different, represent a C1-C4 alkyl group
  • R3 possibly being a hydrogen atom.
  • Pentaerythritol esters of C6-C22 fatty monoacids or diacids for instance the mixture of esters of pentaerythritol and of isostearic, capric, caprylic and adipic acids
  • oils comprising three ester functions, of a monohydroxylated acid comprising three carboxylic functions, and of a C 2 - C4 monoalcohol, in particular triethyl citrate.
  • the second oil(s) may be chosen from non-volatile hydrocarbon-based oils comprising at least two free hydroxyl groups and preferably at least three free hydroxyl groups.
  • oils examples include:
  • hydrocarbon-based plant oils such as liquid triglycerides of fatty acids containing from 4 to 40 carbon atoms and comprising at least two free hydroxyl groups and advantageously at least three free hydroxyl groups, for instance castor oil;
  • h represents an integer ranging from 1 to 9
  • polyesters obtained by condensation of an unsaturated fatty acid dimer and/or trimer and of diol in particular such as of dilinoleic acid and of 1,4-butanediol.
  • an unsaturated fatty acid dimer and/or trimer and of diol in particular such as of dilinoleic acid and of 1,4-butanediol.
  • oils may be of plant, mineral or synthetic origin.
  • the O/O emulsion according to the invention may also comprise, as oil(s) present in the second oily phase, at least one volatile silicone or hydrocarbon-based oil.
  • volatile silicone oils that may be used in the invention, mention may be made of linear or cyclic silicone oils with a viscosity at room temperature of less than 8 cSt and especially containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms.
  • volatile silicone oils that may be used in the invention, mention may be made especially of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
  • isododecane Permethyl 99 A
  • Cs-Ci6 isoparaffms such as Isopar L, E, G or H, or mixtures thereof, optionally combined with decamethyltetrasiloxane or with cyclop entasiloxane.
  • the emulsion according to the invention more particularly comprises from 5% to 95% by weight and preferably from 30%> to 70%> by weight of the oil(s) of the first oily phase, relative to the weight of the emulsion.
  • the O/O emulsion comprises a first oily phase containing at least a first oil chosen from non-phenyl nonvolatile silicone oils or phenyl non-volatile silicone oils bearing at least one dimethicone fragment, and a second oily phase containing at least a second oil chosen from non- volatile hydrocarbon-based oils comprising not more than one free hydroxyl group or not comprising any.
  • non-phenyl non-volatile silicone oils they may preferably be chosen from the silicone oils of formula ( ⁇ ).
  • non- volatile phenyl silicone oils comprising at least one dimethicone fragment
  • they may be chosen from the compounds of formula (I) with radicals R such that the silicone is phenylated and comprises at least one dimethicone fragment
  • radicals R such that the silicone is phenylated and comprises at least one dimethicone fragment
  • IV with radicals R such that the silicone is phenylated and comprises at least one dimethicone fragment
  • IV with non-zero p, in particular (VI) with non-zero p and especially the variants (A) and (B);
  • the O/O emulsion comprises a first oily phase containing at least a first oil chosen from non-volatile silicone oils and a second oily phase containing at least a second oil chosen from non- volatile hydrocarbon- based oils comprising at least two free hydroxyl groups and preferably at least three free hydroxyl groups. More particularly, said non-volatile hydrocarbon-based oils comprise at least one carboxylic ester group. Non-volatile hydrocarbon-based oils comprising three ester functions, of a monohydroxylated acid comprising three carboxylic functions and of a C2-C4 monoalcohol, are also suitable in this variant, as second oil(s).
  • the O/O emulsion comprises a first oily phase containing at least a first oil chosen from phenyl nonvolatile silicone oils not bearing a dimethicone fragment, and a second oily phase containing at least a second oil chosen from non-volatile hydrocarbon-based oils comprising at least two free hydroxyl groups and preferably at least three free hydroxyl groups, or from non-volatile apolar hydrocarbon-based oils and even more particularly at least a second oil chosen from non- volatile hydrocarbon-based oils comprising at least two free hydroxyl groups, and preferably at least three free hydroxyl groups.
  • the apolar non- volatile oil(s) are chosen from hydrogenated or non-hydrogenated polydecenes and hydrogenated or non-hydrogenated polybutenes, and mixtures thereof.
  • the second non- volatile apolar oil(s) are preferably chosen from hydrogenated or non-hydrogenated polydecenes, hydrogenated or non-hydrogenated polybutenes and hydrogenated or non-hydrogenated polyisobutenes, or mixtures thereof.
  • the O/O emulsion comprises a first oily phase comprising at least one non-phenyl non- volatile silicone oil and a second oily phase containing at least one phenyl non-volatile silicone oil optionally bearing a dimethicone fragment, or at least one volatile silicone oil.
  • the O/O emulsion comprises a first oily phase comprising at least one non-volatile phenyl silicone oil not bearing a dimethicone fragment, and a second oily phase containing at least one nonvolatile phenyl silicone oil bearing at least one dimethicone fragment, or at least one volatile silicone oil.
  • the first non- volatile phenyl silicone oil(s) not bearing a dimethicone fragment are chosen from the compounds of formula (II).
  • the second non- volatile silicone oil(s) bearing at least one dimethicone fragment they are advantageously chosen from the oils i) of formula (VI), more particularly B) with, for example, the silicones of formula (VII).
  • the O/O emulsion may comprise at least one volatile oil. More particularly, the first oily phase and/or the second oily phase may comprise at least one volatile oil. It should be noted that the second oily phase may comprise only volatile oils. Reference may be made to that which has been detailed previously regarding the nature of these oils.
  • the O/O emulsion according to the present invention comprises at least one structuring agent chosen from waxes, pasty compounds, polymeric thickeners and mineral thickeners, and mixtures thereof.
  • the structuring agent may be incorporated into one and/or the other of the oily phases of the O/O emulsion according to the invention.
  • the structuring agent is present in the continuous oily phase of the emulsion.
  • the structuring agent is more particularly chosen as a function of the oil(s) into which it is incorporated.
  • the emulsion according to the invention may comprise at least one wax.
  • the wax is chosen such that it is compatible with the oil into which it is incorporated.
  • use is preferably made of at least one wax which, when it is mixed with at least one oil (first oil(s) or second oil(s)) (wax/oil proportion: 10/90; 10 g sample) at a temperature greater than or equal to the melting point of said wax, leads to the production of a homogeneous mixture.
  • 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.
  • 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, 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.
  • 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 compressive force, measured at 20°C using the texture analyser sold under the name ⁇ - ⁇ 2 ⁇ by the company Rheo, equipped with a stainless-steel cylinder with a diameter of 2 mm, travelling at a measuring speed of 0.1 mm/second, and penetrating the wax to a penetration depth of 0.3 mm.
  • the waxes may be hydrocarbon-based waxes, silicone 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 wax means a wax whose solubility parameter 5a at 25°C as defined below is equal to 0 (J/cm 3 )1 ⁇ 2.
  • the apolar waxes are in particular hydrocarbon-based waxes formed solely from carbon and hydrogen atoms, and free of heteroatoms such as N, O, Si and P.
  • apolar wax means a wax that is formed solely from apolar wax, rather than a mixture also comprising other types of waxes that are not apolar waxes.
  • hydrocarbon-based waxes for instance microcrystalline waxes, paraffin waxes, ozokerite, polymethylene waxes, polyethylene waxes and microwaxes, especially polyethylene waxes.
  • Polyethylene waxes that may be mentioned include Performalene 500-L Polyethylene and Performalene 400 Polyethylene sold by New Phase Technologies, and Asensa SC 211 sold by Honeywell.
  • Cirebelle 108 sold by Cirebelle.
  • Ozokerite Wax SP 1020 P An ozokerite that may be mentioned is Ozokerite Wax SP 1020 P.
  • microwaxes that may be used in the O/O emulsions according to the invention as apolar wax
  • Polar wax such as those sold under the names Micropoly 200®, 220®, 220L® and 250S® by the company Micro Powders.
  • polar wax means a wax whose solubility parameter 5a at 25°C is other than 0 (J/cm 3 )1 ⁇ 2.
  • polar wax means a wax whose chemical structure is formed essentially from, or even constituted by, carbon and hydrogen atoms, and comprising at least one highly electronegative heteroatom such as an oxygen, nitrogen, silicon or phosphorus atom.
  • silicon wax means an oil comprising at least one silicon atom, especially comprising Si-0 groups.
  • 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 oils may also be hydroxylated.
  • alcohol wax means a wax comprising at least one alcohol function, i.e. comprising at least one free hydroxy 1 (OH) group.
  • ester wax The following may especially be used as ester wax:
  • waxes of formula R1COOR2 in which Rl 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.
  • Rl 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.
  • 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®, Hydroxypoly ester K 82 P®, Kester Wa
  • 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.
  • the C4-C30 aliphatic group is linear and unsaturated.
  • total esters means that all the hydroxyl functions of glycerol are esterified.
  • Examples that may be mentioned include trihydroxystearine (or glyceryl trihydroxystearate), tristearine (or glyceryl tristearate) and tribehenine (or glyceryl tribehenate), alone or as a mixture.
  • trihydroxystearine or glyceryl trihydroxystearate
  • tristearine or glyceryl tristearate
  • tribehenine or glyceryl tribehenate
  • suitable compounds mention may be made of triesters of glycerol and of 12-hydroxystearic acid, or hydrogenated castor oil, for instance Thixcin R and Thixcin E sold by Elementis Specialties.
  • the polar wax may be an alcohol wax.
  • silicon wax means an oil comprising at least one silicon atom, and in particular comprising Si-0 groups.
  • the silicone waxes that may be used may also be alkyl or alkoxy dimethicones, and also (C2o-C 6 o)alkyl dimethicones, in particular (C3o-C4 5 )alkyl dimethicones, such as the silicone wax sold under the name SF-1642 by the company GE-Bayer Silicones or C30-45 alkyldimethylsilyl polypropylsilsesquioxane under the name SW-8005 ® C30 Resin Wax sold by the company Dow Corning. Mention may also be made of silicone waxes obtained by esterification with a (poly)alkoxylated silicone, such as silicone beeswax, silicone candelilla wax or silicone carnauba wax.
  • the content of wax(es) is preferably between 0.1% and 20%, preferentially 0.5% and 15% and more particularly 1% and 10% by weight relative to the total weight of the oil(s) into which they are incorporated.
  • the emulsion according to the invention may comprise at least one compound that is pasty at 25°C and atmospheric pressure.
  • At least one pasty compound which, when it is mixed with at least one oil (first oil(s) or second oil(s)) (pasty compound/oil proportion: 10/90; 10 g sample) at a temperature greater than or equal to the melting point of said pasty compound, leads to the production of a homogeneous mixture.
  • the term "pasty” refers to a compound that undergoes a reversible solid/liquid change of state, having anisotropic crystalline organization in the solid state, 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 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 of the pasty compound is the heat consumed by the compound in order to pass 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 of the pasty compound is the amount of energy required to make the pasty compound change from the solid state to the liquid state. It is expressed in J/g.
  • 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 2°C, formed from a liquid fraction and a solid fraction.
  • 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 is more particularly chosen as a function of the oil(s) into which it is incorporated.
  • At least one pasty compound which, when it is mixed with at least one oil (first oil(s) or second oil(s)) (pasty compound/oil proportion: 25/75; 10 g sample) at a temperature greater than or equal to the melting point of said wax until a homogeneous mixture is obtained, which is then allowed to cool to 20°C, does not reveal any oil phase separation greater than 20% by volume, more particularly 10% by volume.
  • the pasty compound may in particular be chosen from synthetic pasty compounds and fatty substances of plant origin.
  • 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 C2-C4 polyalkylene glycol pentaerythrityl ethers, fatty alcohol ethers of sugars, and mixtures thereof.
  • C2-C4 polyalkylene glycol pentaerythrityl ethers fatty alcohol ethers of sugars, and mixtures thereof.
  • polyethylene glycol pentaerythrityl ether comprising 5 oxy ethylene units (5 OE)
  • CTFA name PEG-5 Pentaerythrityl Ether
  • polypropylene glycol pentaerythrityl ether comprising five oxypropylene (5 OP) units CTFA name: PPG-5 Pentaerythrityl Ether
  • 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 pentaery
  • linear or branched oligomers which are homopolymers or copolymers of alkyl (meth)acrylates preferably containing a C8-C30 alkyl group,
  • oligomers which are homopolymers and copolymers of vinyl esters containing C8-C30 alkyl groups, and
  • oligomers which are homopolymers and copolymers of vinyl ethers containing C8-C30 alkyl groups,
  • liposoluble poly ethers resulting from polyetherification between one or more C2-C100 and preferably C2-C50 diols,
  • liposoluble polyethers that are particularly considered are copolymers of ethylene oxide and/or of propylene oxide with C6-C30 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 the following are especially considered:
  • - esters of a glycerol oligomer especially diglycerol esters, 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 Cremer Oleo,
  • esters of diol dimer and of diacid dimer where appropriate esterified on the free alcohol or acid function(s) thereof 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/isostearyl/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 Sahara), murumuru butter (Rain Forest RF3710 from the company Beraca Sahara), cocoa butter; 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 product sold under the reference Cegesoft® HF 52 from BASF (INCI name Hydrogenated Vegetable Oil), the trans-isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the commercial reference Iso-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 HCISV-L sold by Nisshin Oillio,
  • the pasty compounds that are suitable for use in the invention are chosen from hydrocarbon-based compounds and comprise, besides carbon and hydrogen atoms, at least oxygen atoms.
  • the pasty compounds therefore do not comprise any silicon atoms or any fluorine atoms.
  • the pasty compound(s) are chosen from lanolin and derivatives thereof, esters of glycerol oligomers, butters of plant origin, totally or partially hydrogenated plant oils, and hydrogenated castor oil esters, or mixtures thereof.
  • the content of pasty compound(s) is preferably between 0.1% and 30%> by weight, preferentially 0.5%> and 20% by weight and more particularly 1% and 10% by weight relative to the total weight of the oil(s) into which they are incorporated.
  • organopolysiloxane elastomers examples include organopolysiloxane elastomers, semi-crystalline polymers, hydrocarbon-based polyamides, silicone polyamides and dextrin esters, and also mixtures thereof.
  • the polymeric thickener is chosen such that it is compatible with the oil into which it is incorporated.
  • polymeric thickener which, when it is mixed with at least one oil (first oil(s) or second oil(s)) (polymeric thickener/oil proportion: 10/90; 10 g sample) at a temperature greater than or equal to the melting point of said polymeric thickener, leads to the production of a homogeneous mixture.
  • first oil(s) or second oil(s) polymeric thickener/oil proportion: 10/90; 10 g sample
  • the choice of the polymeric thickener may advantageously be made as a function of the nature of the oils present. For example, if the oil is hydrocarbon-based, it may be advantageous to choose a hydrocarbon-based polymeric thickener, and if the oil is silicone-based, it may be advantageous to choose a silicone polymeric thickener.
  • the content of polymeric thickener(s), expressed as solids more particularly ranges from 0.1% to 40%> by weight, preferably from 0.1% to 20% by weight and even more preferentially from 0.1% to 10% by weight relative to the total weight of the oil(s) into which they are incorporated.
  • the organopolysiloxane elastomer that may be used as polymeric thickener also has the advantage of giving the composition according to the invention good application properties. It affords a very soft feel and a matt effect after application, which is advantageous especially for application to the skin, in particular for foundation compositions. It may also allow efficient filling of the hollows present on keratin materials.
  • organopolysiloxane elastomer or "silicone elastomer” means a supple, deformable organopolysiloxane with viscoelastic properties and especially with the consistency of a sponge or a supple sphere. Its modulus of elasticity is such that this material withstands deformation and has limited stretchability and contractability. This material is capable of regaining its original shape after stretching.
  • the organopolysiloxane elastomer may be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and of diorganopolysiloxane containing ethylenically unsaturated groups bonded to silicon, especially in the presence of a platinum catalyst; or by dehydrogenation crosslinking condensation reaction between a diorganopolysiloxane containing hydroxyl end groups and a diorganopolysiloxane containing at least one hydrogen bonded to silicon, especially in the presence of an organotin; or by crosslinking condensation reaction of a diorganopolysiloxane containing hydroxyl end groups and of a hydrolysable organopolysilane; or by thermal crosslinking of organopolysiloxane, especially in the presence of an organoperoxide catalyst; or by crosslinking of organopolysiloxane via high- energy radiation such as gamma rays
  • the organopolysiloxane elastomer is obtained by crosslinking addition reaction (A) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B) of diorganopolysiloxane containing at least two ethylenically unsaturated groups bonded to silicon, especially in the presence (C) of a platinum catalyst, as described, for instance, in patent application EP-A-295 886.
  • the organopolysiloxane elastomer may be obtained by reaction of dimethylpolysiloxane bearing dimethylvinylsiloxy end groups and of methylhydrogenopolysiloxane bearing trimethylsiloxy end groups, in the presence of a platinum catalyst.
  • Compound (A) is the base reagent for the formation of organopolysiloxane elastomer, and the crosslinking is performed by addition reaction of compound (A) with compound (B) in the presence of the catalyst (C).
  • Compound (A) is in particular an organopolysiloxane containing at least two hydrogen atoms bonded to different silicon atoms in each molecule.
  • Compound (A) may have any molecular structure, in particular a linear-chain or branched-chain structure or a cyclic structure.
  • Compound (A) may have a viscosity at 25°C ranging from 1 to 50 000 centistokes, especially so as to be readily miscible with compound (B).
  • the organic groups bonded to the silicon atoms of compound (A) may be alkyl groups such as methyl, ethyl, propyl, butyl, octyl; substituted alkyl groups such as 2- phenylethyl, 2-phenylpropyl or 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl, xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon-based groups such as an epoxy group, a carboxylate ester group or a mercapto group.
  • alkyl groups such as methyl, ethyl, propyl, butyl, octyl
  • substituted alkyl groups such as 2- phenylethyl, 2-phenylpropyl or 3,3,3-trifluoropropyl
  • aryl groups such as phenyl, tolyl, xylyl
  • substituted aryl groups
  • Compound (A) may thus be chosen from trimethylsiloxy-terminated methylhydrogenopolysiloxanes, trimethylsiloxy-terminated dimethylsiloxane/methyl- hydrogenosiloxane copolymers, and dimethylsiloxane/methylhydrogenosiloxane cyclic copolymers.
  • Compound (B) is advantageously a diorganopolysiloxane containing at least two lower alkenyl groups (for example C2-C4); the lower alkenyl group may be chosen from vinyl, allyl and propenyl groups. These lower alkenyl groups may be located at any position on the organopolysiloxane molecule but are preferably located at the ends of the organopolysiloxane molecule.
  • the organopolysiloxane (B) may have a branched-chain, linear-chain, cyclic or network structure but the linear-chain structure is preferred.
  • Compound (B) may have a viscosity ranging from the liquid state to the gum state. Preferably, compound (B) has a viscosity of at least 100 centistokes at 25°C.
  • the other organic groups bonded to the silicon atoms in compound (B) may be alkyl groups such as methyl, ethyl, propyl, butyl or octyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl or 3,3,3- trifluoropropyl; aryl groups such as phenyl, tolyl or xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon-based groups such as an epoxy group, a carboxylate ester group or a mercapto group.
  • alkyl groups such as methyl, ethyl, propyl, butyl or octyl
  • substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl or 3,3,3- trifluoropropyl
  • aryl groups such as phenyl, tolyl or xylyl
  • substituted aryl groups such
  • the organopolysiloxanes (B) may be chosen from methylvinylpolysiloxanes, methylvinylsiloxane-dimethylsiloxane copolymers, dimethylpolysiloxanes bearing dimethylvinylsiloxy end groups, dimethylsiloxane-methylphenylsiloxane copolymers bearing dimethylvinylsiloxy end groups, dimethylsiloxane-diphenylsiloxane- methylvinylsiloxane copolymers bearing dimethylvinylsiloxy end groups, dimethylsiloxane-methylvinylsiloxane copolymers bearing trimethylsiloxy end groups, dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers bearing trimethylsiloxy end groups, methyl(3,3,3-trifluoropropyl)polysiloxanes bearing dimethylvinylsiloxy end
  • the elastomeric organopolysiloxane may be obtained via reaction of dimethylvinylsiloxy-terminated dimethylpolysiloxane and of trimethylsiloxy-terminated methylhydrogenopolysiloxane, in the presence of a platinum catalyst.
  • the sum of the number of ethylenic groups per molecule of compound (B) and of the number of hydrogen atoms bonded to silicon atoms per molecule of compound (A) is at least 5.
  • compound (A) is added in an amount such that the molecular ratio of the total amount of hydrogen atoms bonded to silicon atoms in compound (A) to the total amount of all the ethylenically unsaturated groups in compound (B) is within the range from 1.5/1 to 20/1.
  • Compound (C) is the catalyst for the crosslinking reaction, and is especially chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid- alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black and platinum on a support.
  • Catalyst (C) is preferably added in an amount of from 0.1 to 1000 parts by weight and better still from 1 to 100 parts by weight, as clean platinum metal, per 1000 parts by weight of the total amount of compounds (A) and (B).
  • the elastomer is advantageously a non-emulsifying elastomer.
  • non-emulsifying defines organopolysiloxane elastomers not containing any hydrophilic chains, and in particular not containing any polyoxyalkylene units (especially polyoxy ethylene or polyoxypropylene) or any polyglyceryl units.
  • the O/O emulsion comprises an organopolysiloxane elastomer free of polyoxyalkylene units and of polyglyceryl units.
  • the silicone elastomer used in the present invention is chosen from Dimethicone Crosspolymer (INCI name), Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone /Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone Crosspolymer-3 (INCI name).
  • the organopolysiloxane elastomer particles may be conveyed in the form of a gel formed from an elastomeric organopolysiloxane included in at least one hydrocarbon- based oil and/or one silicone oil. In these gels, the organopolysiloxane particles are often non-spherical particles.
  • Non-emulsifying elastomers are described especially in patents EP 242 219, EP 285 886 and EP 765 656 and in patent application JP-A-61-194009, the content of which is incorporated by way of reference.
  • the silicone elastomer is generally in the form of a gel, a paste or a powder, but advantageously in the form of a gel in which the silicone elastomer is dispersed in a linear silicone oil (dimethicone) or cyclic silicone oil (e.g.: cyclopentasiloxane), advantageously in a linear silicone oil.
  • a linear silicone oil dimethicone
  • cyclic silicone oil e.g.: cyclopentasiloxane
  • Non-emulsifying elastomers that may be used more particularly include those sold under the names KSG-6, KSG-15, KSG-16, KSG-18, KSG-41, KSG-42, KSG-43 and KSG-44 by the company Shin-Etsu, DC9040 and DC9041 by the company Dow Corning, and SFE 839 by the company General Electric.
  • a gel of silicone elastomer dispersed in a silicone oil chosen from a non-exhaustive list comprising cyclopentadimethylsiloxane, dimethicones, dimethylsiloxanes, methyl trimethicone, phenyl methicone, phenyl dimethicone, phenyl trimethicone and cyclomethicone, preferably a linear silicone oil chosen from polydimethylsiloxanes (PDMSs) or dimethicones with a viscosity at 25°C ranging from 1 to 500 cSt, optionally modified with optionally fluorinated aliphatic groups, or with functional groups such as hydroxyl, thiol and/or amine groups.
  • a silicone oil chosen from a non-exhaustive list comprising cyclopentadimethylsiloxane, dimethicones, dimethylsiloxanes, methyl trimethicone, phenyl methicone,
  • dimethicone (and) dimethicone crosspolymer such as DC9041 from the company Dow Corning
  • dimethicone/vinyl dimethicone crosspolymer (and) dimethicone such as
  • KSG-6 and KSG-16 from the company Shin-Etsu;
  • the O/O emulsion according to the invention comprises at least one crosslinked silicone elastomer having the INCI name "dimethicone (and) dimethicone crosspolymer", preferably with a dimethicone having a viscosity ranging from 1 to 100 cSt, in particular from 1 to 10 cSt at 25°C, such as the mixture of polydimethylsiloxane crosslinked with hexadiene/polydimethylsiloxane (5 cSt) sold under the name DC 9041 by the company Dow Corning.
  • organopolysiloxane elastomer particles may also be used in powder form: mention may be made of the powders sold under the names Dow Corning 9505 Powder and Dow Corning 9506 Powder by the company Dow Corning, these powders having the INCI name: dimethicone/vinyl dimethicone crosspolymer.
  • the organopolysiloxane powder may also be coated with silsesquioxane resin, as described, for example, in patent US 5 538 793.
  • silsesquioxane resin as described, for example, in patent US 5 538 793.
  • Such elastomeric powders are sold under the names KSP-lOO, KSP-101, KSP-102, KSP-103, KSP-104 and KSP-105 by the company Shin-Etsu, and have the INCI name: vinyl dimethicone/methicone silsesquioxane crosspolymer.
  • the O/O emulsion according to the invention may comprise at least one semi- crystalline polymer.
  • the semi-crystalline polymer has an organic structure, and a melting point of greater than or equal to 30°C.
  • the term "semi-crystalline polymer” means polymers comprising a crystallizable portion and an amorphous portion and having a first- order reversible change of phase temperature, in particular of melting point (solid-liquid transition).
  • the crystallizable part is either a side chain (or pendent chain) or a block in the backbone.
  • the crystallizable portion of the semi-crystalline polymer is a block of the polymer backbone
  • this crystallizable block has a chemical nature different than that of the amorphous blocks; in this case, the semi-crystalline polymer is a block copolymer, for example of the diblock, triblock or multiblock type.
  • the semicrystalline polymer may be a homopolymer or a copolymer.
  • the melting point of the semicrystalline polymer is preferably less than 150°C.
  • the melting point of the semi-crystalline polymer is preferably greater than or equal to 30°C and less than 100°C. More preferably, the melting point of the semi- crystalline polymer is preferably greater than or equal to 30°C and less than 70°C.
  • the semi-crystalline polymer(s) according to the invention are solid at room temperature (25°C) and atmospheric pressure (760 mmHg), with a melting point of greater than or equal to 30°C.
  • the melting point values correspond to the melting point measured using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name DSC 30 by the company Mettler, with a temperature rise of 5°C or 10°C per minute. (The melting point under consideration is the point corresponding to the temperature of the most endothermic peak of the thermogram).
  • the semi-crystalline polymer(s) according to the invention preferably have a melting point that is higher than the temperature of the keratin support intended to receive said composition, in particular the skin or the lips.
  • crystallizable chain or block means a chain or block which, if it were alone, would change from the amorphous state to the crystalline state reversibly, depending on whether the temperature is above or below the melting point.
  • a chain is a group of atoms, which are 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 polymer backbone of the semi-crystalline polymers is soluble in the oily phase at a temperature above their melting point.
  • the crystallizable blocks or chains of the semi-crystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%.
  • the semi-crystalline polymers containing crystallizable side chains are homopolymers or copolymers.
  • the semi-crystalline polymers of the invention bearing crystallizable blocks are block or multiblock copolymers. They may be obtained by polymerizing a monomer bearing reactive (or ethylenic) double bonds or by polycondensation. When the polymers of the invention are polymers bearing crystallizable side chains, these side chains are advantageously in random or statistical form.
  • the semicrystalline polymers of the invention are of synthetic origin.
  • the semi-crystalline polymer is chosen from:
  • the semi-crystalline polymers that may be used in the invention may be chosen in particular from: - block copolymers of polyolefms of controlled crystallization, the monomers of which are described in EP-A-0 951 897,
  • - acrylate/silicone copolymers such as copolymers of acrylic acid and of stearyl acrylate bearing polydimethylsiloxane grafts, copolymers of stearyl methacrylate bearing polydimethylsiloxane grafts, copolymers of acrylic acid and of stearyl methacrylate bearing polydimethylsiloxane grafts, copolymers of methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and stearyl methacrylate bearing polydimethylsiloxane grafts. Mention may be made in particular of the copolymers sold by the company Shin-Etsu under the names KP-561 (CTFA name: acrylates/dimethicone),
  • polyamide means a compound containing at least two, preferably at least three and better still ten amide repeating units.
  • hydrocarbon-based polyamide means a polyamide formed essentially of, indeed even constituted by, carbon and hydrogen atoms, and optionally of oxygen or nitrogen atoms, and not comprising any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
  • the term "functionalized chain” means an alkyl chain comprising one or more functional groups or reagents chosen especially from hydroxyl, ether, ester, oxyalkylene and polyoxyalkylene groups.
  • this polyamide of the emulsion according to the invention has a weight-average molecular mass of less than 100 000 g/mol, especially ranging from 1000 to 100 000 g/mol, in particular ranging from 1000 to 50 000 g/mol, more particularly ranging from 1000 to 30 000 g/mol, preferably from 2000 to 20 000 g/mol and better still from 2000 to 10 000 g/mol.
  • This polyamide is insoluble in water, especially at 25°C.
  • the polyamide is a compound (i), namely a hydrocarbon-based polyamide, in particular a non-silicone polyamide, of formula (la) below:
  • n denotes a whole number of amide units such that the number of ester groups represents from 10% to 50% of the total number of ester and amide groups
  • Ri is, independently in each case, an alkyl or alkenyl group containing at least 4 carbon atoms and in particular from 4 to 24 carbon atoms
  • R 2 represents, independently in each case, a C 4 to C 42 hydrocarbon-based group, on condition that 50%> of the groups R 2 represent a C30 to C 42 hydrocarbon-based group
  • R3 represents, independently in each case, an organic group containing at least 2 carbon atoms, hydrogen atoms and optionally one or more oxygen or nitrogen atoms
  • R 4 represents, independently in each case, a hydrogen atom, a Ci to Cio alkyl group or a direct bond to R3 or to another R 4 , such that the nitrogen atom to which R3 and R 4 are both attached forms part of a heterocyclic structure defined by R4NR3, with at least 50%> of the groups R 4 representing a hydrogen atom.
  • the optionally functionalized terminal fatty chains are terminal chains linked to the last heteroatom, in this case nitrogen, of the polyamide backbone.
  • the ester groups of formula (I), which form part of the terminal and/or pendent fatty chains represent from 15% to 40% of the total number of ester and amide groups and better still from 20%> to 35%.
  • n advantageously represents an integer ranging from 1 to 5 and better still greater than 2.
  • Ri is a C 12 to C22 and preferably C 16 to C22 alkyl group.
  • R2 may be a C10 to C42 hydrocarbon-based, preferably alkylene, group.
  • R2 is a divalent radical derived from acid dimer.
  • At least 50% and better still at least 75% of the groups R2 are groups containing from 30 to 42 carbon atoms.
  • the other groups R2 are C 4 to C19 and even C 4 to C12 hydrogen-containing groups.
  • R3 represents a C2 to C36 hydrocarbon- based group or a polyoxyalkylene group and R 4 represents a hydrogen atom.
  • R3 represents a C2 to C12, preferably C 2 , hydrocarbon-based group.
  • the hydrocarbon-based groups may be linear, cyclic or branched, and saturated or unsaturated groups.
  • the alkyl and alkylene groups may be linear or branched, and saturated or unsaturated groups.
  • the hydrocarbon-based polyamide of formula (la) is such that n is an integer ranging from 1 to 5, preferably greater than 2, Ri is a C12 to C22 and preferably Ci6 to C22 alkyl group, R2 is a C10 to C42 hydrocarbon-based group, preferably a divalent radical derived from acid dimer, R3 represents a C2 to C12, preferably C 2 , hydrocarbon- based group, and R 4 represents a hydrogen atom.
  • the polyamides of formula (la) are in the form of mixtures of polyamides, these mixtures also possibly containing a synthetic product corresponding to a compound of formula (la) in which n is 0, i.e. a diester.
  • hydrocarbon-based polyamides of formula (la) that may be used in the emulsions according to the invention, mention may be made of the commercial products sold by the company Arizona Chemical under the names Uniclear 80 and Uniclear 100, the INCI name of which is ethylenediamine/stearyl dimer dilinoleate copolymer, or Uniclear 80 V, Uniclear 100 V and Uniclear 100 VG, the INCI name of which is ethylenediamine/stearyl dimer tallate copolymer. They are sold, respectively, in the form of a gel at 80% active material in a mineral oil and at 100% active material. They have a softening point of from 88 to 94°C.
  • Hydrocarbon-based polyamides that may also be mentioned include polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and a diamine, including compounds containing more than two carbonyl groups and two amine groups, the carbonyl and amine groups of adjacent individual units being condensed in the form of an amide bond.
  • These polyamide resins are especially the products sold under the brand name Versamid® by the companies General Mills, Inc. and Henkel Corp., (Versamid 930, 744 or 1655) or by the company Olin Mathieson Chemical Corp., under the brand name Onamid®, especially Onamid S or C.
  • These resins have a weight-average molecular mass ranging from 6000 to 9000 g/mol.
  • polyamide resins such as those disclosed in patents US-A-5 783 657 and US-A-5 998 570.
  • the polyamide advantageously has a softening point of greater than 65°C, which may be up to 190°C. It preferably has a softening point ranging from 70°C to 130°C and better still from 80°C to 105°C.
  • the polyamide used is Uniclear 100 VG, the INCI name of which is ethylenediamine/stearyl dimer tallate copolymer.
  • the silicone polyamides are preferably solid at room temperature (25°C) and atmospheric pressure (760 mrnHg).
  • the silicone polyamides may be more particularly polymers comprising at least one unit corresponding to the general formula I:
  • G' represents C(O) when G represents -C(0)-NH-Y-NH-
  • G' represents -NH- when G represents -NH-C(0)-Y-C(0)-
  • R 4 , R 5 , R 6 and R 7 which may be identical or different, represent a group chosen from:
  • Ci to C 4 o hydrocarbon- based groups possibly containing in their chain one or more oxygen, sulfur and/or nitrogen atoms, and which may be partially or totally substituted with fluorine atoms,
  • Cio aryl groups optionally substituted with one or more Ci to C 4 alkyl groups,
  • the groups X which may be identical or different, represent a linear or branched Ci to C30 alkylenediyl group, possibly containing in its chain one or more oxygen and/or nitrogen atoms,
  • Y is a saturated or unsaturated Ci to C50 linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene divalent group, which may comprise one or more oxygen, sulfur and/or nitrogen atoms, and/or may bear as substituent one of the following atoms or groups of atoms: fluorine, hydroxyl, C3 to Cs cycloalkyl, Ci to C 4 o alkyl, C5 to Cio aryl, phenyl optionally substituted with one to three Ci to C3 alkyl, Ci to C3 hydroxyalkyl and Ci to C 6 aminoalkyl groups, or
  • Y represents a group corresponding to the formula:
  • T represents a linear or branched, saturated or unsaturated, C3 to C 24 trivalent tetravalent hydrocarbon-based group optionally substituted with a polyorganosiloxane chain, and possibly containing one or more atoms chosen from O, N and S, or T represents a trivalent atom chosen from N, P and Al, and
  • R 8 represents a linear or branched C1-C50 alkyl group or a polyorganosiloxane chain, possibly comprising one or more ester, amide, urethane, thiocarbamate, urea, thiourea and/or sulfonamide groups, which may possibly be linked to another chain of the polymer;
  • - n is an integer ranging from 2 to 500 and preferably from 2 to 200
  • m is an integer ranging from 1 to 1000, preferably from 1 to 700 and better still from 6 to 200.
  • 80% of the groups R 4 , R 5 , R 6 and R 7 of the polymer are preferably chosen from methyl, ethyl, phenyl and 3,3,3- trifluoropropyl groups. According to another embodiment, 80% of the groups R 4 , R 5 , R 6 and R 7 of the polymer are methyl groups.
  • Y may represent various divalent groups, furthermore optionally comprising one or two free valencies to establish bonds with other units of the polymer or copolymer.
  • Y represents a group chosen from:
  • Ci to C20 alkylene groups comprising from 1 to 5 amide groups
  • Ci to C20 alkylene groups comprising one or more substituents chosen from hydroxyl, C3 to Cs cycloalkane, Ci to C3 hydroxyalkyl and Ci to C 6 aminoalkyl groups,
  • the silicone polymer may be a homopolymer, i.e. a polymer comprising several identical units, of formula (I).
  • a polymer consisting of a copolymer comprising several different units of formula (I), i.e. a polymer in which at least one of the groups R 4 , R 5 , R 6 , R 7 , X, G, G', Y, m and n is different in one of the units.
  • a silicone polyamide furthermore comprising at least one hydrocarbon-based unit comprising two groups capable of establishing hydrogen interactions, chosen from ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and biguanidino groups, and combinations thereof.
  • copolymers may be block polymers or grafted polymers.
  • the alkylene group representing X or Y may optionally contain in its alkylene part at least one of the following components:
  • alkylene groups may also be substituted with at least one component chosen from the group formed by:
  • Y may also represent:
  • a, b and c are, independently, integers ranging from 1 to 10
  • R 13 is a hydrogen atom or a group such as those defined for R 4 , R 5 , R 6 and R 7 .
  • R 4 , R 5 , R 6 and R 7 preferably represent, independently, a linear or branched Ci to C 4 o alkyl group, preferably a CH 3 , C2H5, n-C 3 H 7 or isopropyl group, a polyorganosiloxane chain or a phenyl group optionally substituted with one to three methyl or ethyl groups.
  • the silicone polyamide com rises at least one unit of formula (III) or (IV):
  • m ranges from 1 to 700, in particular from 15 to 500 and especially from 50 to 200, and n ranges in particular from 1 to 500, preferably from 1 to 100 and better still from 4 to 25,
  • - X is preferably a linear or branched alkylene chain containing from 1 to 30 carbon atoms, in particular 1 to 20 carbon atoms, especially from 5 to 15 carbon atoms and more particularly 10 carbon atoms, and
  • - Y is preferably an alkylene chain that is linear or branched, or which may comprise rings and/or unsaturations, containing from 1 to 40 carbon atoms, in particular 1 to 20 carbon atoms and better still from 2 to 6 carbon atoms, in particular 6 carbon atoms.
  • the alkylene group representing X or Y may optionally contain in its alkylene portion at least one of the following components:
  • alkylene groups may also be substituted with at least one component chosen from the group consisting of:
  • Y may also represent:
  • R represents a polyorganosiloxane chain and T represents a group of formula: 13
  • a, b and c are, independently, integers ranging from 1 to 10
  • R 13 is a hydrogen atom or a group such as those defined for R 4 , R 5 , R 6 and R 7 .
  • R 4 , R 5 , R 6 and R 7 preferably represent, independently, a linear or branched Ci to C 4 o alkyl group, preferably a CH 3 , C2H5, n-C 3 H7 or isopropyl group, a polyorganosiloxane chain or a phenyl group optionally substituted with one to three methyl or ethyl groups.
  • the polymer may comprise identical or different units of formula (III) or (IV).
  • the polymer may be a polyamide containing several units of formula (III) or (IV) of different lengths, i.e. a polyamide corresponding to formula (V):
  • X, Y, n and R 4 to R 7 have the meanings given above, mi and m 2 , which are different, are chosen in the range from 1 to 1000, and p is an integer ranging from 2 to 300.
  • the units may be structured to form either a block copolymer, or a random copolymer or an alternating copolymer.
  • the units may be not only of different lengths, but also of different chemical structures, for example containing different groups Y.
  • the polymer may correspond to formula VI:
  • the various units may be structured to form either a block copolymer, or a random copolymer or an alternating copolymer.
  • the silicone polyamide may also be formed from a grafted copolymer.
  • the polyamide containing silicone units may be grafted and optionally crosslinked with silicone chains containing amide groups.
  • Such polymers may be synthesized with trifunctional amines.
  • the polymer may comprise at least one unit of formula (VII):
  • X 1 and X 2 which are identical or different, have the meaning given for X in formula (I)
  • n is as defined in formula (I)
  • Y and T are as defined in formula (I)
  • R 14 to R 21 are groups chosen from the same group as R 4 to R 7
  • mi and m 2 are numbers in the range from 1 to 1000
  • p is an integer ranging from 2 to 500.
  • R is a hydrogen atom or a group chosen from the groups defined for R 4 to R 7
  • R 23 , R 24 and R 25 are, independently, linear or branched alkylene groups, and more preferably correspond to the formula:
  • - mi and m2 be in the range from 15 to 500 and better still from 15 to 45,
  • - Xi and X2 represent -(CH 2 ) 10 -
  • - Y represent -CH2-.
  • polyamides containing a grafted silicone unit of formula (VII) may be copolymerized with polyamide-silicones of formula (II) to form block copolymers, alternating copolymers or random copolymers.
  • the weight percentage of grafted silicone units (VII) in the copolymer may range from 0.5% to 30% by weight.
  • the siloxane units may be in the main chain or backbone of the polymer, but they may also be present in grafted or pendent chains.
  • the siloxane units may be in the form of segments as described above.
  • the siloxane units may appear individually or in segments.
  • a copolymer comprising units of formula (III) or (IV) and hydrocarbon-based polyamide units.
  • the polyamide-silicone units may be located at the ends of the hydrocarbon-based polyamide.
  • the silicone polyamide comprises units of formula III.
  • silicone polyamides examples include the compounds sold by the company Dow Corning under the names DC 2-8179 (DP 100) and DC 2-8178 (DP 15), the INCI name of which is Nylon-61 1/dimethicone copolymer, i.e. Nylon-61 1/dimethicone copolymers.
  • the emulsion used according to the invention comprises at least one polydimethylsiloxane block polymer of general formula (I) with an m value of about 100.
  • the value "m” corresponds to the degree of polymerization of the silicone portion of the polymer.
  • the emulsion according to the invention comprises at least one polymer comprising at least one unit of formula (III) in which m ranges from 50 to 200, in particular from 75 to 150 and is preferably about 100.
  • the silicone polymers and/or copolymers used in the emulsion of the invention advantageously have a temperature of transition from the solid state to the liquid state ranging from 45°C to 190°C. Preferably, they have a temperature of transition from the solid state to the liquid state ranging from 70 to 130°C and better still from 80°C to 105°C.
  • the 0/0 emulsion preferably comprises at least one preferably C12-C24 and in particular C 14 -C 18 fatty acid ester of dextrin, or mixtures thereof.
  • the dextrin ester is an ester of dextrin and of a C 12 -C 18 and in particular C 14 -C 18 fatty acid.
  • the dextrin ester is chosen from dextrin myristate and/or dextrin palmitate, and mixtures thereof.
  • the dextrin ester is dextrin palmitate.
  • This product may be chosen, for example, from those sold under the names Rheopearl TL ® , Rheopearl KL ® and Rheopearl ® KL2 by the company Chiba Flour Milling.
  • the mineral thickeners that are suitable for use in the present invention, mention may be made of modified clays, and silicas, alone or as a mixture.
  • the content of mineral thickener is advantageously between 0.1% and 20%> and preferably from 0.1 % to 10% by weight relative to the total weight of the oil(s) into which they are incorporated.
  • the 0/0 emulsion according to the invention may comprise at least one lipophilic clay.
  • They may be chosen from bentonites, in particular hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites and vermiculites. They are preferably chosen from hectorites.
  • Hectorites modified with a Cio to C22 ammonium chloride such as hectorite modified with distearyldimethylammonium chloride, for instance the product sold under the name Bentone 38V ® by the company Elementis or bentone gel in isododecane sold under the name Bentone Gel ISD V ® (87% isododecane/ 10% disteardimonium hectorite/3% propylene carbonate) by the company Elementis, are preferably used as lipophilic clays.
  • Lipophilic clay may especially be present in a content ranging from 0.1% to 15% by weight, in particular from 0.5% to 10% and more particularly from 1% to 10% by weight relative to the total weight of the oil(s) into which they are incorporated.
  • the O/O emulsion according to the invention may also comprise, as thickener, a fumed silica or silica aerogel particles. a) Fumed silica
  • Fumed silica which has undergone a hydrophobic surface treatment is most particularly suitable for use in the invention. This is because it is possible to chemically modify the surface of the silica, by chemical reaction generating a reduction in the number of silanol groups present at the surface of the silica. It is especially possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.
  • the hydrophobic groups may be:
  • Silicas thus treated are known as "Silica silylate” according to the CTFA (8th edition, 2000). 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 thus treated are known as "silica dimethyl silylate" according to the CTFA (8th edition, 2000). 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 fumed silicas may be present in an O/O emulsion according to the present invention in a content of between 0.1% and 40% by weight, more particularly between 1% and 15% by weight and even more particularly between 2% and 10% by weight relative to the total weight of the oil(s) into which they are incorporated.
  • the O/O emulsion according to the invention may also comprise, as mineral thickener, 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 used in the present invention have a specific surface area per unit mass (SM) 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 ⁇ .
  • SM specific surface area per unit mass
  • D[0.5] volume- mean diameter
  • the hydrophobic silica aerogel particles used in the present invention have a size expressed as volume-mean diameter (D[0.5]) ranging from 1 to 30 ⁇ , preferably from 5 to 25 ⁇ , better still from 5 to 20 ⁇ and even better still from 5 to 15 ⁇ .
  • D[0.5] volume-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 and corresponding 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 of mass (SM) ranging from 600 to 800 m 2 /g.
  • the silica aerogel particles used in the present invention may advantageously have a tapped density p ranging from 0.02 g/cm 3 to 0.10 g/cm 3 , preferably from 0.03 g/cm 3 to 0.08 g/cm 3 and in particular ranging from 0.05 g/cm 3 to 0.08 g/cm 3 .
  • this density known as the tapped density, may be assessed according to the following protocol:
  • the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of volume SV ranging from 5 to 60 m 2 /cm 3 , preferably from 10 to 50 m 2 /cm 3 and better still from 15 to 40 m 2 /cm 3 .
  • the hydrophobic silica aerogel particles according to the invention have an oil-absorbing capacity, measured at the wet point, ranging from 5 to 18 ml/g, preferably from 6 to 15 ml/g and better still from 8 to 12 ml/g.
  • the absorbing capacity measured at the wet point, noted Wp corresponds to the amount of oil that needs to be added to 100 g of particles in order to obtain a homogeneous paste.
  • wet point method the method for determining the oil uptake of a powder described in standard NF T 30-022. It corresponds to the amount of oil adsorbed onto the available surface of the powder and/or absorbed by the powder by measurement of the wet point, described below:
  • the oil uptake corresponds to the ratio Vs/m.
  • the aerogels used according to the present invention are hydrophobic silica aerogels, preferably of silyl silica (INCI name: silica silylate).
  • hydrophobic silica means any silica whose surface is treated with silylating agents, for example halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups Si-Rn, for example trimethylsilyl groups.
  • silylating agents for example halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes
  • Use will preferably be made of hydrophobic silica aerogel particles surface- modified with trimethylsilyl groups, preferably of the INCI name Silica silylate.
  • hydrophobic silica aerogels that may be used in the invention, examples that may be mentioned include the aerogel sold under the name VM-2260 or VM-2270 (INCI name: Silica silylate), by the company Dow Corning, 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.
  • 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 m 2 /g.
  • the hydrophobic silica aerogel particles are present in the O/O emulsion according to the invention in a solids content ranging from 0.1% to 8% by weight, preferably from 0.2%> to 5% by weight and preferably from 0.2%> to 3% by weight relative to the total weight of the oil(s) into which they are incorporated.
  • the emulsion comprises at least one structuring agent chosen from waxes and pasty compounds, and mixtures thereof.
  • the O/O emulsion comprises:
  • first oily phase containing at least a first oil chosen from non- volatile phenyl or non-phenyl silicone oils
  • a second oily phase containing at least a second oil chosen from non-volatile hydrocarbon-based oils, in particular comprising at least two free hydroxyl groups, preferably at least three free hydroxyl groups, and
  • a pasty compound chosen from lanolin and derivatives thereof, esters of glycerol oligomers, butters of plant origin, totally or partially hydrogenated plant oils, and hydrogenated castor oil esters, or mixtures thereof, and more particularly castor oil esters.
  • the present invention is also directed towards processes for preparing the emulsion according to the invention.
  • the first oily phase is prepared in a first stage, and the second oily phase is prepared in a second stage.
  • the process for preparing the emulsion may be continued, for example, according to the variants described below.
  • the process for preparing the emulsion comprises the following steps, in this order:
  • the first oily phase and the second oily phase are mixed together.
  • the emulsification of these two oily phases leads to the creation of an interface, and more particularly a dispersion of one of the oily phases in the other oily phase.
  • the solid microparticles are added to the emulsion formed and the mixture is then agitated, either by means of a combination of shear forces or by ultrasonication.
  • the process for preparing the emulsion is such that the solid microparticles are introduced into the first oily phase or into the second oily phase.
  • the process comprises the following steps, in this order:
  • the microparticles are first introduced into one of the two oily phases, and a combination of shear forces or ultrasonication is then applied, so as to obtain a homogeneous dispersion of said microparticles in said oily phase.
  • the other oily phase is then added.
  • the process for preparing the emulsion comprises the following steps, in this order: - simultaneous introduction of the solid microparticles, the first oily phase and the second oily phase,
  • the emulsion is obtained by mixing the solid microparticles and the two oily phases with vigorous stirring.
  • the oily phases comprise at least one structuring agent and/or at least one thickener
  • these agents are added to the oily phase into which each must be incorporated before the actual emulsification.
  • the mixing preferably takes place at a temperature greater than or equal to the melting point of the structuring compound if it is present and the homogenization is advantageously performed at a temperature greater than or equal to this melting point.
  • Emulsification takes place by subjecting the mixture of the two oily phases and the solid microparticles to a combination of shear forces or ultrasonication, to obtain homogeneity thereof.
  • homogeneity of an emulsion is intended to denote an emulsion in which the drops of inner phases are uniformly dispersed in the continuous or outer oily phase.
  • the drops of dispersed phases in the emulsion may be very fine, in particular ranging from 0.1 to 10 ⁇ , or may be coarser, in particular ranging from 10 ⁇ to 1 cm.
  • a person skilled in the art may choose the conditions and the device that are the best suited for obtaining the combination of forces necessary for obtaining the targeted type of emulsion, especially for obtaining the targeted droplet size.
  • This combination of forces may be obtained by subjecting the first and second oily phases or the emulsion to manual shaking or to mechanical stirring with a blender such as a Moritz, Rayneri or Ultra-Turrax blender, or alternatively by ultrasonic homogenization.
  • a blender such as a Moritz, Rayneri or Ultra-Turrax blender, or alternatively by ultrasonic homogenization.
  • the speed of blending or stirring for obtaining a homogeneous phase or emulsion may depend on various factors such as its composition or its volume.
  • the various stirring parameters, especially the speed may be determined by a person skilled in the art on the basis of his general knowledge and, where appropriate, by means of a few routine tests.
  • this operation is performed at a temperature between 10 and 50°C;
  • Sonicator XL machine from Misonix Incorporated for 1 minute to 1 minute 5 seconds with a power of 165 W.
  • the emulsions are prepared by ultrasonication in two steps:
  • the power applied is that specified in the table below for each emulsion.
  • Example 1 Emulsions prepared using methylsilsesquioxane resin microbead particles
  • microbeads used are sold under the name Tospearl AQ by the company Momentive. They have a mean diameter of 5 ⁇ .
  • Castor oil (g/100 g) 47.5 47.5 47.5 47.5 (Codex sold by Interchimie)
  • Triethyl citrate (g/100 g)
  • Pentaerythrityl tetraisostearate (g/lOOg)
  • Ultrasonication power (watts)/ 165W 165W 165W 165W 165W 165W 165W 165W 165W 165W 165W 165W 165W time (seconds) (35s+30s) (35s+30s) (35s+30s) (35s+30s) (35s+30s) (35s+30s) (35s+30s) (35s+30s) (35s+30s)
  • Example 2 Emulsions prepared using titanium oxide particles encapsulated in silica microspheres
  • Sunjin Chemical They have a mean diameter of between 2 and 7 ⁇ .
  • Triethyl citrate (g/100 g)
  • Pentaerythrityl tetraisostearate (g/lOOg)
  • Example 3 Emulsions prepared using crosslinked polydimethylsiloxane gum particles coated with silsesquioxane resin
  • Triethyl citrate (g/100 g)
  • Pentaerythrityl tetraisostearate (g/lOOg)
  • Example 4 Emulsions prepared using a talc/ethylene-methacrylate copolymer mixture coated with isopropyl triisostearyl titanate
  • the particles used are sold under the name SPCAT-12 by the company Kobo. They have a mean diameter of 5 ⁇ .

Abstract

La présente invention concerne une émulsion huile/huile (H/H) comprenant au moins : - une première phase huileuse comprenant au moins une première huile non volatile choisie parmi les huiles de silicone, les huiles à base d'hydrocarbure et les huiles fluorées, - une seconde phase huileuse comprenant au moins une seconde huile non volatile ou volatile, qui n'est pas miscible avec la ou les première(s) huile(s), à 25 °C, et des microparticules solides présentant au moins une partie courbe dont le rayon de courbure n'est pas infini, dont la dimension la plus importante est au moins 0,15 µm, et comprenant au moins deux matériaux différents, chacun minéral ou organique. L'invention concerne également une composition cosmétique comprenant, dans un milieu physiologiquement acceptable, au moins une émulsion huile/huile selon l'invention, ainsi que l'utilisation de microparticules solides ayant au moins une partie incurvée dont le rayon de courbure n'est pas infini, dont la dimension la plus importante est au moins 0,15 µm, et comprenant au moins deux matériaux différents, chacun étant minéral ou organique, pour stabiliser une émulsion H/H.
PCT/EP2016/051056 2015-01-21 2016-01-20 Émulsion huile/huile contenant des microparticules comprenant au moins deux matériaux différents, chacun étant organique ou minéral WO2016116473A1 (fr)

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FR1550478A FR3031674B1 (fr) 2015-01-21 2015-01-21 Emulsion huile / huile renfermant des microparticules comprenant au moins deux materiaux differents, chacun organique ou inorganique
FR1550478 2015-01-21

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FR3095758A1 (fr) 2019-05-06 2020-11-13 L'oreal Emulsion huile-dans-huile avec au moins un oxyde métallique enrobé hydrophobe et au moins deux huiles immiscibles comprenant une huile hydrocarbonée polaire non volatile et une huile siliconée non volatile
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JPWO2018216443A1 (ja) * 2017-05-24 2020-03-26 ダウ・東レ株式会社 固体シリコーン材料、それを用いてなる積層体および発光デバイス
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US20210251851A1 (en) * 2018-10-30 2021-08-19 Cosmax, Inc. Ether/ester composite polyurethane foam cosmetic
FR3095758A1 (fr) 2019-05-06 2020-11-13 L'oreal Emulsion huile-dans-huile avec au moins un oxyde métallique enrobé hydrophobe et au moins deux huiles immiscibles comprenant une huile hydrocarbonée polaire non volatile et une huile siliconée non volatile

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