WO2013190100A2 - Matt-effect composition comprising hydrophobic aerogel particles and expanded polymer particles - Google Patents

Matt-effect composition comprising hydrophobic aerogel particles and expanded polymer particles Download PDF

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Publication number
WO2013190100A2
WO2013190100A2 PCT/EP2013/063017 EP2013063017W WO2013190100A2 WO 2013190100 A2 WO2013190100 A2 WO 2013190100A2 EP 2013063017 W EP2013063017 W EP 2013063017W WO 2013190100 A2 WO2013190100 A2 WO 2013190100A2
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particles
composition according
weight
composition
ranging
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PCT/EP2013/063017
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French (fr)
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WO2013190100A3 (en
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Patricia Pierre
Eric Lheureux
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L'oreal
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Publication of WO2013190100A3 publication Critical patent/WO2013190100A3/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25Silicon; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241Containing particulates characterized by their shape and/or structure
    • A61K8/0279Porous; Hollow
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/008Preparations for oily skin

Definitions

  • the present invention relates to the field of caring for and/or making up keratin materials, and in particular the skin.
  • the invention relates to a cosmetic and/or dermatological composition
  • a cosmetic and/or dermatological composition comprising, in a physiologically acceptable medium, at least hydrophobic aerogel particles, at least expanded copolymer particles and at least one sebum-absorbing particle.
  • the invention also relates to a process for caring for and/or making up the skin, comprising the topical application of the composition to the skin.
  • the invention also relates to a cosmetic process for making the skin matt and/or for reducing its sheen, comprising the topical application to the said skin of the abovementioned composition.
  • the shininess of the skin is a problem essentially affecting adolescents, but which may also appear in adulthood as a result especially of an overproduction of androgens, or as a result of external factors such as pollution.
  • the shininess of the skin may also be associated with sweat resulting from physical activity or weather conditions.
  • the sheen of the skin may be due to the combination of the two phenomena (sebum and sweat).
  • Shiny skin also generally gives rise to poorer staying power of the makeup, which thus has a tendency to become degraded in the course of the day.
  • an efficient means for rapidly reducing unsightly sheen areas consists in using "soft-focus" fillers.
  • fillers that absorb sebum and perspiration is also a means for prolonging the mattness over time. It is known practice to use perlite (FR 2 881 643), fumed fillers (EP 1 637 186) or fibres as matting agents. However, these fillers may afford adverse results, especially pilling on the skin and/or a sensation of unclean skin. It is thus sought to limit the filler content.
  • the need remains for matting cosmetic compositions which have good cosmetic properties, and which in particular afford an efficient (strong), immediate and/or long-lasting matting effect.
  • the Applicant has discovered that this need can be satisfied by combining several particular fillers and especially a) at least hydrophobic aerogel particles, b) at least expanded copolymer particles, and c) at least matting particles different from the particles a) and b).
  • the composition thus obtained makes it possible to improve the mattness of the skin in a remanent manner.
  • the skin is thus durably rendered matt. What is more, the performance of the combination of the three types of particles is greater than that of each of the particles taken in isolation.
  • the compositions according to the invention can also make it possible to reduce the perception of skin defects at the surface of the skin and in particular to mask wrinkles and pores and/or to hide coloured defects of the skin, namely red blotches or blemishes.
  • a subject of the present invention is thus a cosmetic and/or dermatological composition
  • a cosmetic and/or dermatological composition comprising, in a physiologically acceptable medium:
  • the composition comprising at least one aqueous phase, the hydrophobic aerogel particles having a specific surface area per unit of mass ranging from 200 to 1500 m 2 /g and preferably a size, expressed as volume-mean diameter (D[0.5]), of less than 1500 ⁇ .
  • Aerogels are ultra-light porous materials.
  • the first aerogels were made by Kristler in 1932. They are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, the one most commonly used being supercritical CO2. This type of drying makes it possible to avoid shrinkage of the pores and of the material.
  • Other types of drying also make it possible to obtain porous materials starting from gel, namely cryodesiccation, which consists in solidifying the gel at low temperature and in then subliming the solvent, and drying by evaporation. The materials thus obtained are referred to respectively as cryogels and xerogels.
  • the sol-gel process and the various drying operations are described in detail in Brinker C.J. and Scherer G.W., Sol-Gel Science, New York, Academic Press, 1990.
  • the aerogel particles in accordance with the present invention are hydrophobic aerogel particles.
  • hydrophobic aerogel particle means any particle of the aerogel type having a water absorption capacity at the wet point of less than 0.1 ml/g, i.e. less than 10 g of water per 100 g of particle.
  • the wet point corresponds to the amount of water that needs to be added to 1 g of particle in order to obtain a homogeneous paste. This method is derived directly from the method for determining the oil uptake of a powder as described in standard NF T 30-022.
  • wet point weight expressed in grams per 100 g of product corresponding to the production of a homogeneous paste during the addition of a solvent to a powder.
  • the wet point is measured according to the following protocol:
  • the glass plate is placed on the balance and 1 g of aerogel is weighed out.
  • the beaker containing the solvent and the liquid sampling pipette is placed on the balance.
  • the solvent is gradually added to the powder, the whole being regularly blended (every 3 to 4 drops) with the spatula.
  • the mass of solvent required to reach the wet point is noted. The average of three tests will be determined.
  • the hydrophobic aerogels used according to the present invention may be organic, mineral or hybrid organic-mineral.
  • the organic aerogels may be based on resins from among the following: polyurethanes, resorcinol-formaldehyde, polyfurfuranol, cresol-formaldehyde, phenol-furfuranol, polybutadiene, melamine-formaldehyde, phenol-furfural, polyimides, polyacrylates, polymethacrylates, polyolefins, polystyrenes, polyacrylonitriles, phenol-formaldehyde, polyvinyl alcohol, dialdehydes, polycyanurates, epoxys, celluloses, cellulose derivatives, chitosan, agar, agarose, alginate, starches, and mixtures thereof.
  • resins from among the following: polyurethanes, resorcinol-formaldehyde, polyfurfuranol, cresol-formaldehyde, phenol-furfuranol, polybutadiene, melamine-formal
  • Aerogels based on organic-mineral hybrids for example silica-PMMA, silica- chitosan and silica-polyether, are also envisaged.
  • Patent applications US 2005/0 192 366 and WO 2007/126 410 describe such organic-mineral hybrid materials.
  • the hydrophobic aerogel particles used in the present invention have a specific surface area per unit of mass (SM) ranging from 200 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 volume-mean diameter (D[0.5]), of less than 1500 ⁇ and preferably ranging 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 surface area per unit of mass
  • the specific surface area per unit of mass can be determined by the nitrogen absorption method, known as the BET (Brunauer-Emmett-Teller) method, described in the Journal of the American Chemical Society, Vol. 60, page 309, February 1938, and corresponding to international standard ISO 5794/1 (appendix D).
  • the BET specific surface area corresponds to the total specific surface area of the particles under consideration.
  • the sizes of the aerogel particles according to the invention can be measured by static light scattering using a commercial particle size analyzer such as the MasterSizer 2000 machine from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter. This theory is described in particular in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957.
  • the hydrophobic 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 and a size, expressed as volume-mean diameter (D[0.5]), ranging from 5 to 20 ⁇ and better still from 5 to 15 ⁇ .
  • SM surface area per unit of mass
  • D[0.5] volume-mean diameter
  • the hydrophobic aerogel particles used in the present invention can advantageously exhibit a tapped density ranging from 0.02 g/cm 3 to 0.10 g/cm 3 and preferably from 0.02 g/cm 3 to 0.08 g/cm 3 .
  • this density can be assessed according to the following protocol, known as the tapped density protocol:
  • the hydrophobic 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 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 absorption capacity measured at the wet point corresponds to the amount of oil that needs to be added to 100 g of particles in order to obtain a homogeneous paste. It is measured according to the "wet point" method or method of determination of 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 aerogel particles used are mineral and are more particularly hydrophobic silica aerogel particles having the properties stated previously.
  • Silica aerogels are porous materials obtained by replacing (especially 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 CO2. This type of drying makes it possible to avoid shrinkage of the pores and of the material.
  • the sol-gel process and the various drying operations are described in detail in Brinker C.J. and Scherer G.W., Sol-Gel Science, New York, Academic Press, 1990.
  • hydrophobic silica aerogels used according to the present invention are preferably silylated silica aerogels (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, 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
  • hydrophobic silica aerogels that may be used in the invention, examples that may be mentioned include the aerogel sold under the name VM-2260 (INCI name: Silica silylate), by the company Dow 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.
  • Aerogel TLD 201 Mention may also be made of the aerogels sold by Cabot under the references Aerogel TLD 201 , Aerogel OGD 201 and Aerogel TLD 203, Enova® Aerogel MT 1 100 and Enova Aerogel MT 1200.
  • Aerogel MT 1 100 (INCI name: Silica silylate) by the company Cabot, the particles of which have a mean size ranging from 2 to 25 microns and a specific surface area per unit of mass ranging from 600 to 800 m 2 /g.
  • the hydrophobic aerogel particles represent from 0.1 % to 30% by weight, preferably from 0.5% to 20% by weight, better still from 1 % to 10% by weight and more preferably from 1 .5% to 5% by weight, relative to the total weight of the composition.
  • Expanded polymer particles are different from aerogel particles a) and c).
  • the expanded copolymer particles have a density of less than 0.1 , especially less than 0.09, better still less than 0.06 and even better still less than 0.04.
  • a gas may especially be air, nitrogen, isobutane or isopentane.
  • the particles are in the form of beads. It is, however, possible to use particles in the form of fibres or needles.
  • These particles may be made of various inert materials that do not react chemically with the medium; in particular, these particles do not react with the oils, the surfactants, the water or the various other constituents of the composition, such as the active agents.
  • the acrylic monomer is, for example, a methyl or ethyl acrylate or methacrylate.
  • the styrene monomer is, for example, a-methylstyrene or styrene.
  • the particles are deformable hollow particles of an expanded copolymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and (meth)acrylate or styrene monomer. It is possible, for example, to use a polymer containing 0-60% of units derived from vinylidene chloride, 20-90% of units derived from acrylonitrile and 0-50% of units derived from an acrylic or styrene monomer, the sum of the percentages (by weight) being equal to 100%.
  • the acrylic monomer may be methyl or ethyl (meth)acrylate.
  • the styrene monomer may be styrene or a-methylstyrene.
  • the particles used in the present invention are hollow particles of an expanded copolymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and methyl methacrylate. These particles may be dry or hydrated.
  • the mass per unit volume of these particles is chosen in the range from 15 to 200 kg/m 3 , better still from 40 to 120 kg/m 3 and even better still from 60 to 80 kg/m 3 .
  • the particles that may be used in the invention are, for example, microspheres of expanded terpolymer of vinylidene chloride, acrylonitrile and methyl methacrylate, sold under the brand name Expancel by the company Nobel Casco and in particular under the references 551 DE 12 (particle size D(0.5) of about 12 ⁇ and mass per unit volume of about 40 kg/m 3 ), 551 DE 20 (particle size D(0.5) of about 15 to 25 ⁇ and mass per unit volume of about 60 kg/m 3 ), 551 DE 50 (particle size D(0.5) of about 40 ⁇ ), 461 DE 50 and 642 WE 50 of about 50 ⁇ of particle size D(0.5), 551 DE 80 (particle size D(0.5) of about 50 to 80 ⁇ ).
  • particles of this same expanded terpolymer with a particle size D(0.5) of about 18 ⁇ and a mass per unit volume of about 60 to 80 kg/m 3 (Expancel EL23) or with a particle size D(0.5) of about 34 ⁇ and a mass per unit volume of about 20 kg/m 3 .
  • Expancel particles 551 DE 40 d42 (particle size D(0.5) of approximately 30 to 50 ⁇ and density of approximately 42 kg/m 3 ), 551 DE 80 d42 (particle size D(0.5) of approximately 50 to 80 ⁇ and density of approximately 42 kg/m 3 ), 461 DE 20 d70 (particle size D(0.5) of approximately 15 to 25 ⁇ and density of approximately 70 kg/m 3 ), 461 DE 40 d25 (particle size D(0.5) of approximately 35 to 55 ⁇ and density of approximately 25 kg/m 3 ), 461 DE 40 d60 (particle size D(0.5) of approximately 20 to 40 ⁇ and density of approximately 60 kg/m 3 ), 461 DET 40 d25 (particle size D(0.5) of approximately 35 to 55 ⁇ and density of approximately 25 kg/m 3 ), 051 DE 40 d60 (particle size D(0.5) of approximately 20 to 40 ⁇ and density of approximately 60 kg/m 3 ), 091 DE 40 d30 (p
  • particles of a polymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and methyl methacrylate in unexpanded form, for instance those sold under the brand name Expancel with the reference 551 DU 10 (particle size D(0.5) of about 10 ⁇ ) or 461 DU 15 (particle size D(0.5) of about 15 ⁇ ).
  • the expanded copolymer particles are present in the compositions according to the invention in concentrations ranging from 0.01 % to 5% by weight and preferably from 0.05% to 2% by weight relative to the total weight of the composition.
  • Sebum-absorbing particles are different from the particles a) and b).
  • the composition according to the invention comprises a particle that absorbs sebum, in particular having a different sebum uptake from the two types of particle a) and b).
  • the sebum-absorbing particles have a sebum uptake of greater than or equal to 10 ml/100 g, especially greater than or equal to 20 ml/100 g and in particular greater than or equal to 30 ml/100 g.
  • the term "sebum-absorbing particle” means a powder that is capable of absorbing and/or adsorbing sebum. Generally, this type of particle is in the form of a powder of particles having sebum uptake.
  • the sebum uptake corresponds to the amount of sebum absorbed and/or adsorbed by the particle. It is measured according to the wet point method described below.
  • the sebum-absorbing particle may have a BET specific surface area of greater than or equal to 200 m 2 /g, preferably greater than 350 m 2 /g and preferentially greater than 500 m 2 /g, and especially less than 2000 m 2 /g.
  • the BET specific surface area is determined according to the BET (Brunauer- Emmett-Teller) method described in the Journal of the American Chemical Society, Vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (appendix D).
  • the BET specific surface area corresponds to the total specific surface area (thus including micropores) of the particle and especially of the powder.
  • the sebum-absorbing particles may be a mineral powder or an organic powder.
  • the particle or particles of one or more mineral compounds used in the cosmetic composition may have different shapes, for example sphere-shaped, full or hollow, glitter, needles or platelets and preferably they are approximately spherical.
  • the sebum-absorbing particles may be chosen from:
  • - powders of acrylic polymers especially of polymethyl methacrylate, poly(methyl methacrylate/ethylene glycol dimethacrylate), poly(allyl methacrylate/ethylene glycol dimethacrylate), ethylene glycol dimethacrylate/lauryl methacrylate copolymer;
  • the sebum-absorbing particle may be a powder coated with a hydrophobic treatment agent.
  • the hydrophobic treatment agent may be chosen from fatty acids, for instance stearic acid; metal soaps, for instance aluminium dimyristate, the aluminium salt of hydrogenated tallow glutamate; amino acids; N-acylamino acids or salts thereof; lecithin, isopropyl triisostearyl titanate, waxes, and mixtures thereof.
  • the N-acylamino acids may comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group.
  • the salts of these compounds may be the aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts.
  • the amino acid may be, for example, lysine, glutamic acid or alanine.
  • alkyl mentioned in the compounds cited above especially denotes an alkyl group containing from 1 to 30 carbon atoms and preferably containing from 5 to 16 carbon atoms.
  • the silicas that can be used may be natural and untreated. Mention may thus be made of the silicas sold under the names Sillitin N85, Sillitin N87, Sillitin N82, Sillitin N85 and Sillitin V88 by the company Hoffmann Mineral.
  • They may be fumed silicas.
  • the fumed silicas can be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process makes it possible especially to obtain hydrophilic silicas which contain a large number of silanol groups at their surface. It is possible to chemically modify the surface of said silica via a chemical reaction which brings about a reduction in the number of silanol groups. It is possible in particular to substitute silanol groups with hydrophobic groups; a hydrophobic silica is then obtained.
  • hydrophobic groups can be:
  • Silica powders that may more particularly be mentioned include:
  • Acrylic polymer powders that may be mentioned include:
  • the silicone elastomers are especially elastomeric partially or completely crosslinked organopolysiloxanes, having three-dimensional structure, such as those sold under the names KSG6 ® , KSG16 ® and KSG18 ® by Shin-Etsu, Trefil E-505C ® and Trefil E-506C ® by Dow Corning, Gransil SR-CYC ® , SR DMF10 ® , SR-DC556 ® , SR 5CYC gel ® , SR DMF 10 gel ® and SR DC 556 gel ® by Grant Industries, SF 1204 ® and JK 1 13 ® by General Electric.
  • Silicone elastomer powders that may be mentioned include the powders sold under the names Trefil® Powder E-505C and Trefil® Powder E-506C by Dow Corning.
  • silicone powder gum beads of crosslinked polydimethylsiloxane coated with silsesquioxane resin may be mentioned, especially sold under the name KSP100 by Shin-Etsu, silicone resin powders in the form of rugby balls such as especially the product sold under the name NLK-602 by Takemoto.
  • Perlite is a natural glass of volcanic origin, shiny light-grey or black in colour, which results from the rapid cooling of lava and which is provided in the form of small particles resembling pearls when it is heated beyond 800°C.
  • the perlite particles used according to the invention are especially commercially available from World Minerals Europe under the trade name Perlite P1430, Perlite P2550 or Perlite P2040. These particles are sold as mattifying agents for paints. They are presented in the form of a white powder having a crystalline silica content below 0.1 % by weight.
  • the perlite particles according to the invention have a particle size distribution such that at least 50% of the particles have a size of less than 25 ⁇ , preferably less than 20 ⁇ .
  • they preferably have a particle size distribution such that 90% by weight of the particles have a size of less than 55 ⁇ and preferably of less than 40 ⁇ .
  • starches that may be used in the present invention are, for example, corn starch, potato starch, tapioca starch, rice starch, wheat starch and cassava starch.
  • the starches may be modified or unmodified.
  • a modified starch is a starch that has been modified via processes known to those skilled in the art, for instance esterification, etherification, oxidation, acid hydrolysis, crosslinking or enzymatic conversion.
  • Non-limiting examples of modified starches include aluminium starch octenylsuccinate, sodium starch octenylsuccinate, calcium starch octenylsuccinate, distarch phosphate, hydroxyethyl starch phosphate, hydroxypropyl starch phosphate, sodium carboxymethyl starch and sodium starch glycolate.
  • the starch is a starch octenylsuccinate, in particular of aluminium, the starch being from corn, wheat or rice. Mention may be made especially of the product sold by Akzo Nobel under the name Dry Flo Plus.
  • the starches are especially chosen from powders of unmodified starch such as corn starch.
  • Boron nitride particles may be mentioned, such as PUHP1030L by Saint Gobain Ceramics, UHP-1010 by Carborundum, Ronaflair Extender by Merck, Covalumine Atlas White AS by Sensient, Boroneige 601 by ESK, PUHP3008 by Saint Gobain Ceramics.
  • Clays are products that are already well known per se, which are described, for example, in the publication "Mineralogie des argiles" [Mineralogy of Clays], S. Caillere, S. Henin, M. Rautureau, 2nd Edition 1982, Masson, the teaching of which is included herein by way of reference.
  • Clays are silicates containing a cation that may be chosen from calcium, magnesium, aluminium, sodium, potassium and lithium cations, and mixtures thereof.
  • Examples of such products that may be mentioned include clays of the smectite family such as montmorillonites, hectorites, bentonites, beidellites and saponites, and also of the family of vermiculites, stevensite and chlorites.
  • the clays can be of natural or synthetic origin.
  • clays that are cosmetically compatible and acceptable with keratin fibres such as the hair are used.
  • the clay can be chosen from montmorillonite, bentonite, hectorite, attapulgite, sepiolite and mixtures thereof.
  • the clay is a bentonite or a hectorite.
  • the clays may be chosen from organophilic clays.
  • Organophilic clays are clays modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkyl aryl sulfonates and amine oxides, and mixtures thereof.
  • the organophilic clays according to the invention are clays modified with a chemical compound chosen from quaternary amines.
  • Organophilic clays that may be mentioned include quaternium-18 bentonites such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Elementis, Tixogel VP by United Catalyst, and Claytone 34, Claytone 40 and Claytone XL by Southern Clay; stearalkonium bentonites such as those sold under the names Bentone 27V by Elementis, Tixogel LG by United Catalyst, and Claytone AF and Claytone APA by Southern Clay; and quaternium-18/benzalkonium bentonites such as those sold under the names Claytone HT and Claytone PS by Southern Clay.
  • the organophilic clay is particularly chosen from modified hectorites such as the hectorite modified by C10-C12 fatty acid ammonium chloride, especially distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride.
  • the clays are especially chosen from montmorillonites and kaolin.
  • Particularly preferred particles that absorb sebum are silica powders, especially precipitated silica powders and more specifically precipitated silicas coated with wax, perlite, boron nitride, starches and acrylic polymer powders.
  • the particles have a number-average size of between 50 nm and 350 microns, better still between 100 nm and 100 microns and even more preferentially between 0.5 and 100 microns.
  • the sebum-absorbing particles may be present in the composition according to the invention in a content ranging from 0.01 % to 30% by weight, preferably ranging from 0.1 % to 20% by weight and most preferentially ranging from 0.5% to 10% by weight, relative to the total weight of the composition.
  • the sebum uptake of a powder is measured according to the method for determining the oil uptake of a powder as described in standard NF T 30-022. It corresponds to the amount of sebum adsorbed onto the available surface of the powder, by measuring the wet point.
  • the artificial sebum is incorporated into the powder using a spatula, and the addition of the artificial sebum is continued until conglomerates of artificial sebum and of powder form. At this point, the artificial sebum is added one drop at a time and the mixture is then triturated with the spatula. The addition of artificial sebum is stopped when a firm, smooth paste is obtained. This paste must be able to be spread over the glass plate without cracks or the formation of lumps.
  • the volume Vs (expressed in ml) of artificial sebum used is then noted.
  • the sebum uptake corresponds to the ratio Vs/m.
  • composition according to the invention may be cosmetic and/or dermatological, preferably cosmetic.
  • composition according to the invention is generally suitable for topical application to the skin and thus generally comprises a physiologically acceptable medium, i.e. a medium that is compatible with the skin and/or its integuments. It is preferably a cosmetically acceptable medium, i.e. which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using this composition.
  • a physiologically acceptable medium i.e. a medium that is compatible with the skin and/or its integuments.
  • a cosmetically acceptable medium i.e. which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using this composition.
  • composition according to the invention may be in any galenical form conventionally used for a topical application and especially in the form of dispersions of the gel or lotion type, emulsions of liquid or semi-liquid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase (O/W) or vice versa (W/O), or suspensions or emulsions of soft, semi- solid or solid consistency of the cream or gel type, or alternatively multiple emulsions (W/O/W or O/W/O), microemulsions, vesicular dispersions of ionic and/or nonionic type, or wax/aqueous phase dispersions.
  • the composition according to the invention may as a variant be presented in anhydrous form such as sticks or compact or free powders. These compositions are prepared according to the usual methods.
  • compositions used according to the invention can be more or less fluid and can have the appearance of a white or coloured cream, of an ointment, of a milk, of a lotion, of a serum, of a paste or of a foam. They may optionally be applied to the skin in the form of an aerosol. They can also be in solid form, for example in the form of a stick.
  • compositions are liquid.
  • composition used according to the invention comprises an oily phase
  • it preferably contains at least one oil. It may also contain other fatty substances. Mention may be made, as oils which can be used in the composition of the invention, for example, of:
  • oils of plant origin such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil;
  • esters and ethers especially of fatty acids, for instance the oils of formulae R1COOR2 and R1OR2 in which Ri represents a fatty acid residue containing from 8 to 29 carbon atoms and R2 represents a branched or unbranched hydrocarbon-based chain containing from 3 to 30 carbon atoms, for instance Purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate or isostearyl isostearate; hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate or triisocetyl citrate; fatty alcohol heptanoates, octanoates or decanoates;
  • hydrocarbons of mineral or synthetic origin such as volatile or non-volatile liquid paraffins, and derivatives thereof, petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam oil;
  • - fatty alcohols having from 8 to 26 carbon atoms such as cetyl alcohol, stearyl alcohol and a mixture thereof (cetylstearyl alcohol), octyldodecanol, 2- butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol;
  • silicone oils for instance volatile or non-volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, which are liquid or pasty at room temperature, especially cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes or 2-phenylethyl trimethylsiloxy silicates, and polymethylphenylsiloxanes;
  • PDMS volatile or non-volatile polymethylsiloxanes
  • hydrocarbon-based oil is understood to mean any oil predominantly comprising carbon and hydrogen atoms, and optionally ester, ether, fluoro, carboxylic acid and/or alcohol groups.
  • the other fatty substances that may be present in the oily phase are, for example, fatty acids containing from 8 to 30 carbon atoms, for instance stearic acid, lauric acid, palmitic acid and oleic acid; waxes, for instance lanolin wax, beeswax, carnauba wax or candelilla wax, paraffin wax, lignite wax or microcrystalline waxes, ceresin or ozokerite, and synthetic waxes, for instance polyethylene waxes and Fischer-Tropsch waxes; silicone resins such as trifluoromethyl-Ci -4 -alkyl dimethicone and trifluoropropyl dimethicone; and silicone elastomers, for instance the products sold under the name KSG by the company
  • fatty substances can be chosen in a varied manner by those skilled in the art so as to prepare a composition having the desired properties, for example of consistency or texture.
  • the composition according to the invention is a water-in-oil (W/O) or oil-in-water (O/W) emulsion, preferably an O/W emulsion.
  • W/O water-in-oil
  • O/W oil-in-water
  • the O/W emulsion also comprises emulsified gels.
  • emulsified gels means dispersions of oils in an aqueous gel. The addition of surfactant is optional for this galenical form.
  • the proportion of the oily phase of the emulsion may range from 2% to 80% by weight and preferably from 5% to 50% by weight relative to the total weight of the composition.
  • the emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic and nonionic emulsifiers, used alone or as a mixture, and optionally a co-emulsifier.
  • the emulsifiers are appropriately chosen according to the emulsion to be obtained (W/O or O/W).
  • the emulsifier and the co-emulsifier are generally present in the composition in a proportion ranging from 0.3% to 30% by weight and preferably from 0.5% to 20% by weight relative to the total weight of the composition.
  • W/O emulsions for example, as emulsifiers, of dimethicone copolyols, such as the mixture of cyclomethicone and dimethicone copolyol sold under the name DC 5225 C by Dow Corning, and alkyl dimethicone copolyols, such as the lauryl dimethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by Dow Corning and the cetyl dimethicone copolyol sold under the name Abil EM 90® by Goldschmidt.
  • dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol sold under the name DC 5225 C by Dow Corning
  • alkyl dimethicone copolyols such as the lauryl dimethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by Dow Corning and the cetyl dimethicone copoly
  • a crosslinked elastomeric solid organopolysiloxane comprising at least one oxyalkylene group such as those obtained according to the procedure of Examples 3, 4 and 8 of patent US-A-5 412 004 and of the examples of patent US-A-5 81 1 487, especially the product of Example 3 (synthesis example) of patent US-A-5 412 004, such as the product sold under the reference KSG 21 by the company Shin-Etsu, may also be used as a surfactant for W/O emulsions.
  • the composition may be an aqueous gel, and may especially comprise common aqueous gelling agents.
  • the composition is a composition comprising at least one aqueous phase.
  • the composition according to the invention comprises an aqueous phase comprising water and optionally glycols, ethanol and/or hydrophilic adjuvants, which may be water-soluble at room temperature.
  • the composition generally comprises from 30% to 95% water.
  • the composition according to the invention has a pH ranging from 3 to 8.
  • the pH of the composition ranges from 4 to 6.
  • the composition according to the invention may be a composition for caring for, cleansing or making up bodily or facial skin, in particular a care composition.
  • the skincare composition may be, for example, a facial cream, gel or fluid.
  • the skin makeup composition may be, for example, a foundation, an eyeshadow, a face powder, a concealer product, a face and body powder, or a body makeup product.
  • composition according to the present invention may also contain various adjuvants commonly used in cosmetics, such as emulsifiers; fillers; preserving agents; sequestrants; dyes; fragrances; thickeners and gelling agents, in particular acrylamide homopolymers and copolymers, acrylic homopolymers and copolymers and acrylamidomethylpropanesulfonic acid (AMPS®) homopolymers and copolymers; UV-screening agents.
  • adjuvants commonly used in cosmetics, such as emulsifiers; fillers; preserving agents; sequestrants; dyes; fragrances; thickeners and gelling agents, in particular acrylamide homopolymers and copolymers, acrylic homopolymers and copolymers and acrylamidomethylpropanesulfonic acid (AMPS®) homopolymers and copolymers; UV-screening agents.
  • the composition according to the invention also comprises at least one active agent for caring for greasy skin.
  • This active agent is preferentially chosen from desquamating agents, antimicrobial agents, anti-inflammatory agents, sebum regulators and antioxidants. It may also contain cosmetic active agents other than those for caring for greasy skin, for instance moisturizers and vitamins.
  • Active agent for caring for greasy skin is understood to mean a compound which intrinsically has, i.e. not requiring the intervention of an external agent to activate it, biological activity which may be in particular: - desquamating activity (which allows the opening of comedones), and/or
  • the term "desquamating agent” means any compound capable of acting: - either directly on desquamation by promoting exfoliation, such as ⁇ -hydroxy acids, in particular salicylic acid and derivatives thereof (including 5-n- octanoylsalicylic acid); a-hydroxy acids, such as glycolic acid, citric acid, lactic acid, tartaric acid, malic acid or mandelic acid; urea; gentisic acid; oligofucoses; cinnamic acid; extract of Saphora japonica; resveratrol and certain jasmonic acid derivatives;
  • ⁇ -hydroxy acids in particular salicylic acid and derivatives thereof (including 5-n- octanoylsalicylic acid); a-hydroxy acids, such as glycolic acid, citric acid, lactic acid, tartaric acid, malic acid or mandelic acid; urea; gentisic acid; oligofucoses; cinnamic acid; extract of Saphora ja
  • aminosulfonic compounds and in particular N-(2- hydroxyethyl)piperazine-N-2-ethanesulfonic acid (HEPES); 2-oxothiazolidine-4- carboxylic acid (procysteine) derivatives; derivatives of a-amino acids of glycine type (as described in EP-0 852 949, and also sodium methyl glycine diacetate sold by BASF under the trade name Trilon M); honey; sugar derivatives such as O-octanoyl-6-D-maltose and N-acetylglucosamine.
  • HPES N-(2- hydroxyethyl)piperazine-N-2-ethanesulfonic acid
  • procysteine 2-oxothiazolidine-4- carboxylic acid
  • derivatives of a-amino acids of glycine type as described in EP-0 852 949, and also sodium methyl glycine diacetate sold by BASF under the trade
  • 5-n-Octanoylsalicylic acid is preferred for use in the present invention.
  • antimicrobial agents that may be used in the composition according to the invention may especially be chosen from 2,4,4'-trichloro-2'-hydroxydiphenyl ether (or triclosan), 3,4,4'-trichlorobanilide, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, hexamidine isethionate, metronidazole and salts thereof, miconazole and salts thereof, itraconazole, terconazole, econazole, ketoconazole, saperconazole, fluconazole, clotrimazole, butoconazole, oxiconazole, sulfaconazole, sulconazole, terbinafine, ciclopirox, ciclopiroxolamine, undecylenic acid and salts thereof, benzoyl peroxide, 3- hydroxybenzoic acid, 4-hydroxybenzoic acid, phytic acid, N-acetyl-L-cystein
  • the preferred antimicrobial agents are octoxyglycerine, copper pidolate, zinc salicylate, salicylic acid and iodopropynyl butylcarbamate.
  • anti-inflammatory agents As anti-inflammatory or calmative agents that may be used in the composition according to the invention, mention may be made of pentacyclic triterpenes and plant extracts (e.g.: Glycyrrhiza glabra) containing the same, for instance ⁇ - glycyrrhetinic acid and salts and/or derivatives thereof (glycyrrhetinic acid monoglucuronide, stearyl glycyrrhetinate, 3-stearoyloxyglycyrrhetic acid), ursolic acid and salts thereof, oleanolic acid and salts thereof, betulinic acid and salts thereof, bisabolol, an extract of Paeonia suffruticosa and/or lactiflora, salicylic acid salts and in particular zinc salicylate, phycosaccharides from the company Codif, an extract of Laminaria saccharina, canola oil, bisabolol and extracts of cam
  • the preferred anti-inflammatory agents for use in the present invention are extracts of Centella asiatica, ⁇ -glycyrrhetinic acid and salts thereof, a-bisabolol and niacinamide. 4. Sebum regulators
  • composition according to the invention comprises a sebum regulator such as a 5cc-reductase inhibitor
  • this agent may be chosen especially from: - retinoids, and in particular retinol;
  • - zinc salts such as zinc lactate, gluconate, pidolate, carboxylate, salicylate and/or cysteate;
  • Zinc salts are preferred for use in the present invention. 5. Antioxidants
  • the antioxidants that are preferred for use in the present invention may be chosen from tocopherol and esters thereof, such as tocopheryl acetate; BHT and BHA.
  • the active agent(s) used in the composition according to the invention may represent from 0.01 % to 50%, preferably from 0.1 % to 25% and better still from 0.5% to 10% of the total weight of the composition.
  • the invention is also directed towards a cosmetic process for caring for and/or making up the skin, comprising the topical application to the skin of the composition according to the invention.
  • matting means making the skin more matt and reducing its sheen, and thus its unaesthetic highlights.
  • the invention also relates to the cosmetic use of the composition according to the invention for caring for combination skin and/or greasy skin.
  • a facial-care cream in the form of an oil/water emulsion having the composition below was prepared:
  • This composition may be applied in the morning and/or evening to the face to make combination skin and greasy skin matt.
  • Example 2 Measuring the mattness/sheen Base formulation
  • the total filler content remains constant (between 0.5% and 3%).
  • composition A according to the invention was measured using a contrast card (Pruf badge type 24/5 - 250 cm 2 ) sold by the company Erichsen.
  • the composition was spread at a rate of 2 mg/cm 2 using a mechanical film spreader.
  • a mixture 80/20 water/sebum was sprayed 10 times, then there was a 6- minute wait at room temperature, then reflection was measured using a gonioreflectonneter.
  • the result obtained is the ratio R between the specular reflection and the diffuse reflection.
  • the value of R is proportionately smaller the greater the matting effect.
  • composition according to the invention produces skin sheen inferior to that obtained with a composition containing each of the particles taken in isolation at the same total concentration.

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Abstract

The present invention relates to a cosmetic and/or dermatological composition comprising, in a physiologically acceptable medium: a) at least some hydrophobic aerogel particles; b) at least expanded copolymer particles, at least one sebum-absorbing particle. The invention also relates to a process for making the skin matt and/or for reducing its sheen.

Description

Matt-effect composition comprising hydrophobic aerogel particles and expanded polymer particles
The present invention relates to the field of caring for and/or making up keratin materials, and in particular the skin.
The invention relates to a cosmetic and/or dermatological composition comprising, in a physiologically acceptable medium, at least hydrophobic aerogel particles, at least expanded copolymer particles and at least one sebum-absorbing particle.
The invention also relates to a process for caring for and/or making up the skin, comprising the topical application of the composition to the skin. The invention also relates to a cosmetic process for making the skin matt and/or for reducing its sheen, comprising the topical application to the said skin of the abovementioned composition.
The shininess of the skin, generally associated with a substantial secretion of sebum, is a problem essentially affecting adolescents, but which may also appear in adulthood as a result especially of an overproduction of androgens, or as a result of external factors such as pollution. The shininess of the skin may also be associated with sweat resulting from physical activity or weather conditions. The sheen of the skin may be due to the combination of the two phenomena (sebum and sweat).
Obtaining a matt effect on the skin is highly desired by users who have combination skin or greasy skin, and also for cosmetic compositions that are intended to be used in hot and humid climates. The highlights caused by an excess of sebum and/or sweat on the surface of the skin are, in effect, generally considered unaesthetic.
Shiny skin also generally gives rise to poorer staying power of the makeup, which thus has a tendency to become degraded in the course of the day.
Besides the use of "sebum regulators", i.e. agents that are capable of aiding in regulating the activity of the sebaceous glands by means of an action that may be termed biological, an efficient means for rapidly reducing unsightly sheen areas consists in using "soft-focus" fillers. The use of fillers that absorb sebum and perspiration is also a means for prolonging the mattness over time. It is known practice to use perlite (FR 2 881 643), fumed fillers (EP 1 637 186) or fibres as matting agents. However, these fillers may afford adverse results, especially pilling on the skin and/or a sensation of unclean skin. It is thus sought to limit the filler content.
The need remains for matting cosmetic compositions which have good cosmetic properties, and which in particular afford an efficient (strong), immediate and/or long-lasting matting effect. The Applicant has discovered that this need can be satisfied by combining several particular fillers and especially a) at least hydrophobic aerogel particles, b) at least expanded copolymer particles, and c) at least matting particles different from the particles a) and b). The composition thus obtained makes it possible to improve the mattness of the skin in a remanent manner. The skin is thus durably rendered matt. What is more, the performance of the combination of the three types of particles is greater than that of each of the particles taken in isolation. The compositions according to the invention can also make it possible to reduce the perception of skin defects at the surface of the skin and in particular to mask wrinkles and pores and/or to hide coloured defects of the skin, namely red blotches or blemishes.
A subject of the present invention is thus a cosmetic and/or dermatological composition comprising, in a physiologically acceptable medium:
a) at least hydrophobic aerogel particles,
b) at least expanded copolymer particles, and
c) at least matting particles different from the particles a) and b), the said composition comprising at least one aqueous phase, the hydrophobic aerogel particles having a specific surface area per unit of mass ranging from 200 to 1500 m2/g and preferably a size, expressed as volume-mean diameter (D[0.5]), of less than 1500 μιτι.
The constituents of the composition according to the invention will now be described in greater detail.
HYDROPHOBIC AEROGELS: Aerogels are ultra-light porous materials. The first aerogels were made by Kristler in 1932. They are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, the one most commonly used being supercritical CO2. This type of drying makes it possible to avoid shrinkage of the pores and of the material. Other types of drying also make it possible to obtain porous materials starting from gel, namely cryodesiccation, which consists in solidifying the gel at low temperature and in then subliming the solvent, and drying by evaporation. The materials thus obtained are referred to respectively as cryogels and xerogels. The sol-gel process and the various drying operations are described in detail in Brinker C.J. and Scherer G.W., Sol-Gel Science, New York, Academic Press, 1990.
The aerogel particles in accordance with the present invention are hydrophobic aerogel particles.
The term "hydrophobic aerogel particle" means any particle of the aerogel type having a water absorption capacity at the wet point of less than 0.1 ml/g, i.e. less than 10 g of water per 100 g of particle. The wet point corresponds to the amount of water that needs to be added to 1 g of particle in order to obtain a homogeneous paste. This method is derived directly from the method for determining the oil uptake of a powder as described in standard NF T 30-022. The measurements are taken in the same manner by means of the wet point and the flow point, which have, respectively, the following definitions: wet point: weight expressed in grams per 100 g of product corresponding to the production of a homogeneous paste during the addition of a solvent to a powder.
The wet point is measured according to the following protocol:
Equipment used:
Glass plate (25 x 25 mm)
Spatula (wooden shaft and metal part, 15 x 2.7 mm)
Silk-bristled brush
Balance
The glass plate is placed on the balance and 1 g of aerogel is weighed out. The beaker containing the solvent and the liquid sampling pipette is placed on the balance. The solvent is gradually added to the powder, the whole being regularly blended (every 3 to 4 drops) with the spatula. The mass of solvent required to reach the wet point is noted. The average of three tests will be determined. The hydrophobic aerogels used according to the present invention may be organic, mineral or hybrid organic-mineral.
The organic aerogels may be based on resins from among the following: polyurethanes, resorcinol-formaldehyde, polyfurfuranol, cresol-formaldehyde, phenol-furfuranol, polybutadiene, melamine-formaldehyde, phenol-furfural, polyimides, polyacrylates, polymethacrylates, polyolefins, polystyrenes, polyacrylonitriles, phenol-formaldehyde, polyvinyl alcohol, dialdehydes, polycyanurates, epoxys, celluloses, cellulose derivatives, chitosan, agar, agarose, alginate, starches, and mixtures thereof.
Aerogels based on organic-mineral hybrids, for example silica-PMMA, silica- chitosan and silica-polyether, are also envisaged. Patent applications US 2005/0 192 366 and WO 2007/126 410 describe such organic-mineral hybrid materials.
The hydrophobic aerogel particles used in the present invention have a specific surface area per unit of mass (SM) ranging from 200 to 1500 m2/g, preferably from 600 to 1200 m2/g and better still from 600 to 800 m2/g, and a size, expressed as volume-mean diameter (D[0.5]), of less than 1500 μιτι and preferably ranging from 1 to 30 μιτι, more preferably from 5 to 25 μιτι, better still from 5 to 20 μιτι and even better still from 5 to 15 μιτι.
The specific surface area per unit of mass can be determined by the nitrogen absorption method, known as the BET (Brunauer-Emmett-Teller) method, described in the Journal of the American Chemical Society, Vol. 60, page 309, February 1938, and corresponding to international standard ISO 5794/1 (appendix D). The BET specific surface area corresponds to the total specific surface area of the particles under consideration. The sizes of the aerogel particles according to the invention can be measured by static light scattering using a commercial particle size analyzer such as the MasterSizer 2000 machine from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter. This theory is described in particular in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957.
According to an advantageous embodiment, the hydrophobic aerogel particles used in the present invention have a specific surface area per unit of mass (SM) ranging from 600 to 800 m2/g and a size, expressed as volume-mean diameter (D[0.5]), ranging from 5 to 20 μιτι and better still from 5 to 15 μιτι.
The hydrophobic aerogel particles used in the present invention can advantageously exhibit a tapped density ranging from 0.02 g/cm3 to 0.10 g/cm3 and preferably from 0.02 g/cm3 to 0.08 g/cm3.
In the context of the present invention, this density can be assessed according to the following protocol, known as the tapped density protocol:
40 g of powder are poured into a graduated measuring cylinder; the measuring cylinder is then placed on the Stav 2003 device from Stampf Volumeter; the measuring cylinder is subsequently subjected to a series of 2500 packing actions (this operation is repeated until the difference in volume between two consecutive tests is less than 2%); the final volume Vf of packed powder is then measured directly on the measuring cylinder. The tapped density is determined by the ratio m/Vf, in this instance 40/Vf (Vf being expressed in cm3 and m in g).
According to one embodiment, the hydrophobic aerogel particles used in the present invention have a specific surface area per unit of volume Sv ranging from 5 to 60 m2/cm3, preferably from 10 to 50 m2/cm3 and better still from 15 to 40 m2/cm3.
The specific surface area per unit of volume is given by the relationship: Sv = SM- p where p is the tapped density expressed in g/cm3 and SM is the specific surface area per unit of mass expressed in m2/g, as defined above.
Preferably, the hydrophobic 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 absorption capacity measured at the wet point, denoted Wp, corresponds to the amount of oil that needs to be added to 100 g of particles in order to obtain a homogeneous paste. It is measured according to the "wet point" method or method of determination of oil uptake of a powder described in standard NF T 30-022. It corresponds to the amount of oil adsorbed onto the available surface of the powder and/or absorbed by the powder by measurement of the wet point, described below:
An amount m = 2 g of powder is placed on a glass plate and the oil (isononyl isononanoate) is then added dropwise. After addition of 4 to 5 drops of oil to the powder, mixing is performed using a spatula, and addition of oil is continued until conglomerates of oil and powder have formed. From this point, the oil is added one drop at a time and the mixture is then triturated with the spatula. The addition of oil is stopped when a firm, smooth paste is obtained. This paste must be able to be spread over the glass plate without cracks or the formation of lumps. The volume Vs (expressed in ml) of oil used is then noted. The oil uptake corresponds to the ratio Vs/m.
According to a particular embodiment, the aerogel particles used are mineral and are more particularly hydrophobic silica aerogel particles having the properties stated previously.
Silica aerogels are porous materials obtained by replacing (especially by drying) the liquid component of a silica gel with air.
They are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, the one most commonly used being supercritical CO2. This type of drying makes it possible to avoid shrinkage of the pores and of the material. The sol-gel process and the various drying operations are described in detail in Brinker C.J. and Scherer G.W., Sol-Gel Science, New York, Academic Press, 1990.
The hydrophobic silica aerogels used according to the present invention are preferably silylated silica aerogels (INCI name: silica silylate).
The term "hydrophobic silica" means any silica whose surface is treated with silylating agents, for example halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups Si-Rn, for example trimethylsilyl groups. As regards the preparation of hydrophobic silica aerogel particles that have been surface-modified by silylation, reference may be made to document US 7 470 725. Use will be made in particular of hydrophobic silica aerogel particles surface- modified with trimethylsilyl groups (trimethylsilyl silica).
As hydrophobic silica aerogels that may be used in the invention, examples that may be mentioned include the aerogel sold under the name VM-2260 (INCI name: Silica silylate), by the company Dow 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 m2/g.
Mention may also be made of the aerogels sold by Cabot under the references Aerogel TLD 201 , Aerogel OGD 201 and Aerogel TLD 203, Enova® Aerogel MT 1 100 and Enova Aerogel MT 1200.
Use will more particularly be made of the aerogel sold under the name VM-2270 (INCI name: Silica silylate) by the company Dow Corning, the particles of which have a mean size ranging from 5 to 15 microns and a specific surface area per unit of mass ranging from 600 to 800 m2/g.
Use will also be made of the aerogel sold under the name Enova® Aerogel MT 1 100 (INCI name: Silica silylate) by the company Cabot, the particles of which have a mean size ranging from 2 to 25 microns and a specific surface area per unit of mass ranging from 600 to 800 m2/g.
The hydrophobic aerogel particles represent from 0.1 % to 30% by weight, preferably from 0.5% to 20% by weight, better still from 1 % to 10% by weight and more preferably from 1 .5% to 5% by weight, relative to the total weight of the composition.
Expanded polymer particles
Expanded polymer particles are different from aerogel particles a) and c).
It is preferable to use particles with a mean particle size of from 1 to 300 microns (μιτι), for example from 5 to 200 μιτι, preferably from 10 to 100 μιτι and better still from 15 to 40 μιτι.
Preferably, the expanded copolymer particles have a density of less than 0.1 , especially less than 0.09, better still less than 0.06 and even better still less than 0.04. To obtain this low density, hollow particles optionally filled with a gas are advantageously used. This gas may especially be air, nitrogen, isobutane or isopentane.
According to another advantageous characteristic of the invention, the particles are in the form of beads. It is, however, possible to use particles in the form of fibres or needles.
These particles may be made of various inert materials that do not react chemically with the medium; in particular, these particles do not react with the oils, the surfactants, the water or the various other constituents of the composition, such as the active agents.
The particles are advantageously chosen from particles of thermoplastic materials chosen from polymers or copolymers of acrylonitrile, vinylidene chloride, vinyl chloride and/or acrylic or styrene monomer, which are optionally expanded, and microporous microspheres.
The acrylic monomer is, for example, a methyl or ethyl acrylate or methacrylate. The styrene monomer is, for example, a-methylstyrene or styrene.
Preferably, the particles are deformable hollow particles of an expanded copolymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and (meth)acrylate or styrene monomer. It is possible, for example, to use a polymer containing 0-60% of units derived from vinylidene chloride, 20-90% of units derived from acrylonitrile and 0-50% of units derived from an acrylic or styrene monomer, the sum of the percentages (by weight) being equal to 100%. The acrylic monomer may be methyl or ethyl (meth)acrylate. The styrene monomer may be styrene or a-methylstyrene.
More preferentially, the particles used in the present invention are hollow particles of an expanded copolymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and methyl methacrylate. These particles may be dry or hydrated.
Preferentially, the mass per unit volume of these particles is chosen in the range from 15 to 200 kg/m3, better still from 40 to 120 kg/m3 and even better still from 60 to 80 kg/m3.
The particles that may be used in the invention are, for example, microspheres of expanded terpolymer of vinylidene chloride, acrylonitrile and methyl methacrylate, sold under the brand name Expancel by the company Nobel Casco and in particular under the references 551 DE 12 (particle size D(0.5) of about 12 μιτι and mass per unit volume of about 40 kg/m3), 551 DE 20 (particle size D(0.5) of about 15 to 25 μηη and mass per unit volume of about 60 kg/m3), 551 DE 50 (particle size D(0.5) of about 40 μηη), 461 DE 50 and 642 WE 50 of about 50 μηη of particle size D(0.5), 551 DE 80 (particle size D(0.5) of about 50 to 80 μηη). It is also possible to use particles of this same expanded terpolymer with a particle size D(0.5) of about 18 μιτι and a mass per unit volume of about 60 to 80 kg/m3 (Expancel EL23) or with a particle size D(0.5) of about 34 μιτι and a mass per unit volume of about 20 kg/m3. Mention may also be made of the Expancel particles 551 DE 40 d42 (particle size D(0.5) of approximately 30 to 50 μιτι and density of approximately 42 kg/m3), 551 DE 80 d42 (particle size D(0.5) of approximately 50 to 80 μιτι and density of approximately 42 kg/m3), 461 DE 20 d70 (particle size D(0.5) of approximately 15 to 25 μιτι and density of approximately 70 kg/m3), 461 DE 40 d25 (particle size D(0.5) of approximately 35 to 55 μιτι and density of approximately 25 kg/m3), 461 DE 40 d60 (particle size D(0.5) of approximately 20 to 40 μιτι and density of approximately 60 kg/m3), 461 DET 40 d25 (particle size D(0.5) of approximately 35 to 55 μιτι and density of approximately 25 kg/m3), 051 DE 40 d60 (particle size D(0.5) of approximately 20 to 40 μιτι and density of approximately 60 kg/m3), 091 DE 40 d30 (particle size D(0.5) of approximately 35 to 55 μιτι and density of approximately 30 kg/m3) or 091 DE 80 d30 (particle size D(0.5) of approximately 60 to 90 μιτι and density of approximately 30 kg/m3). It is also possible to use particles of a polymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and methyl methacrylate in unexpanded form, for instance those sold under the brand name Expancel with the reference 551 DU 10 (particle size D(0.5) of about 10 μηη) or 461 DU 15 (particle size D(0.5) of about 15 μηη).
The expanded copolymer particles are present in the compositions according to the invention in concentrations ranging from 0.01 % to 5% by weight and preferably from 0.05% to 2% by weight relative to the total weight of the composition.
Sebum-absorbing particles
Sebum-absorbing particles are different from the particles a) and b).
The composition according to the invention comprises a particle that absorbs sebum, in particular having a different sebum uptake from the two types of particle a) and b). Advantageously, the sebum-absorbing particles have a sebum uptake of greater than or equal to 10 ml/100 g, especially greater than or equal to 20 ml/100 g and in particular greater than or equal to 30 ml/100 g. The term "sebum-absorbing particle" means a powder that is capable of absorbing and/or adsorbing sebum. Generally, this type of particle is in the form of a powder of particles having sebum uptake.
The sebum uptake corresponds to the amount of sebum absorbed and/or adsorbed by the particle. It is measured according to the wet point method described below.
Advantageously, the sebum-absorbing particle may have a BET specific surface area of greater than or equal to 200 m2/g, preferably greater than 350 m2/g and preferentially greater than 500 m2/g, and especially less than 2000 m2/g.
The BET specific surface area is determined according to the BET (Brunauer- Emmett-Teller) method described in the Journal of the American Chemical Society, Vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (appendix D). The BET specific surface area corresponds to the total specific surface area (thus including micropores) of the particle and especially of the powder.
The sebum-absorbing particles may be a mineral powder or an organic powder. The particle or particles of one or more mineral compounds used in the cosmetic composition may have different shapes, for example sphere-shaped, full or hollow, glitter, needles or platelets and preferably they are approximately spherical.
More precisely, the sebum-absorbing particles may be chosen from:
- silica powders,
- polyamide (Nylon®) powders,
- powders of acrylic polymers, especially of polymethyl methacrylate, poly(methyl methacrylate/ethylene glycol dimethacrylate), poly(allyl methacrylate/ethylene glycol dimethacrylate), ethylene glycol dimethacrylate/lauryl methacrylate copolymer;
- powders of silicone elastomer, obtained especially by polymerization of organopolysiloxane containing at least two hydrogen atoms each bonded to a silicon atom and of an organopolysiloxane comprising at least two ethylenically unsaturated groups (especially two vinyl groups) in the presence of a platinum catalyst;
- starches, The sebum-absorbing particle may be a powder coated with a hydrophobic treatment agent. The hydrophobic treatment agent may be chosen from fatty acids, for instance stearic acid; metal soaps, for instance aluminium dimyristate, the aluminium salt of hydrogenated tallow glutamate; amino acids; N-acylamino acids or salts thereof; lecithin, isopropyl triisostearyl titanate, waxes, and mixtures thereof. The N-acylamino acids may comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group. The salts of these compounds may be the aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts. The amino acid may be, for example, lysine, glutamic acid or alanine. The term "alkyl" mentioned in the compounds cited above especially denotes an alkyl group containing from 1 to 30 carbon atoms and preferably containing from 5 to 16 carbon atoms.
As non-limiting illustrations of sebum-absorbing particles according to the invention, mention may be made most particularly of the particles below.
The silicas that can be used may be natural and untreated. Mention may thus be made of the silicas sold under the names Sillitin N85, Sillitin N87, Sillitin N82, Sillitin N85 and Sillitin V88 by the company Hoffmann Mineral.
They may be fumed silicas.
The fumed silicas can be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process makes it possible especially to obtain hydrophilic silicas which contain a large number of silanol groups at their surface. It is possible to chemically modify the surface of said silica via a chemical reaction which brings about a reduction in the number of silanol groups. It is possible in particular to substitute silanol groups with hydrophobic groups; a hydrophobic silica is then obtained.
The hydrophobic groups can be:
(a) trimethylsiloxyl groups, which are obtained in particular by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "Silica silylate" according to the CTFA (6th Edition, 1995) ; (b) dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as "Silica dimethyl silylate" according to the CTFA (6th Edition, 1995).
Silica powders that may more particularly be mentioned include:
- the porous silica microspheres sold under the name Silica Beads SB-700 by Miyoshi; Sunsphere® H51 , Sunsphere® H33 by Asahi Glass;
- the polydimethylsiloxane-coated amorphous silica microspheres sold under the name SA Sunsphere® H33 and SA Sunsphere® H53 by the company
Asahi Glass;
- precipitated silica microspheres, for example coated with mineral wax such as polyethylene, and sold especially under the name Acematt OK 412 by the company Evonik Degussa.
Mention may be made, as nylon powder, of the nylon powder sold under the name Orgasol® 4000 by Atochem.
Acrylic polymer powders that may be mentioned include:
- polymethyl methacrylate powders sold under the name Covabead® LH85 by the company Wackherr;
- the poly(methyl methacrylate/ethylene glycol dimethacrylate) powders sold under the name Dow Corning 5640 Microsponge® Skin Oil Adsorber by Dow Corning or Ganzpearl® GMP-0820 by Ganz Chemical;
- the poly(allyl methacrylate/ethylene glycol dimethacrylate) powders sold under the name Poly-Pore® L200 or Poly-Pore® E200 by Amcol Health and Beauty Solutions Inc.;
- the ethylene glycol dimethacrylate/lauryl methacrylate copolymer powders sold under the name Polytrap® 6603 from Dow Corning.
The silicone elastomers are especially elastomeric partially or completely crosslinked organopolysiloxanes, having three-dimensional structure, such as those sold under the names KSG6®, KSG16® and KSG18® by Shin-Etsu, Trefil E-505C® and Trefil E-506C® by Dow Corning, Gransil SR-CYC®, SR DMF10®, SR-DC556®, SR 5CYC gel®, SR DMF 10 gel® and SR DC 556 gel® by Grant Industries, SF 1204® and JK 1 13® by General Electric.
Silicone elastomer powders that may be mentioned include the powders sold under the names Trefil® Powder E-505C and Trefil® Powder E-506C by Dow Corning.
As silicone powder, gum beads of crosslinked polydimethylsiloxane coated with silsesquioxane resin may be mentioned, especially sold under the name KSP100 by Shin-Etsu, silicone resin powders in the form of rugby balls such as especially the product sold under the name NLK-602 by Takemoto.
Perlite is a natural glass of volcanic origin, shiny light-grey or black in colour, which results from the rapid cooling of lava and which is provided in the form of small particles resembling pearls when it is heated beyond 800°C.
The perlite particles used according to the invention are especially commercially available from World Minerals Europe under the trade name Perlite P1430, Perlite P2550 or Perlite P2040. These particles are sold as mattifying agents for paints. They are presented in the form of a white powder having a crystalline silica content below 0.1 % by weight.
Preferably, the perlite particles according to the invention have a particle size distribution such that at least 50% of the particles have a size of less than 25 μιτι, preferably less than 20 μιτι. In addition, they preferably have a particle size distribution such that 90% by weight of the particles have a size of less than 55 μιτι and preferably of less than 40 μιτι. Furthermore, it is preferable for 90% by weight of the particles to have a size of greater than 5 μιτι.
The starches that may be used in the present invention are, for example, corn starch, potato starch, tapioca starch, rice starch, wheat starch and cassava starch.
The starches may be modified or unmodified.
A modified starch is a starch that has been modified via processes known to those skilled in the art, for instance esterification, etherification, oxidation, acid hydrolysis, crosslinking or enzymatic conversion.
Non-limiting examples of modified starches include aluminium starch octenylsuccinate, sodium starch octenylsuccinate, calcium starch octenylsuccinate, distarch phosphate, hydroxyethyl starch phosphate, hydroxypropyl starch phosphate, sodium carboxymethyl starch and sodium starch glycolate.
In one particular embodiment, the starch is a starch octenylsuccinate, in particular of aluminium, the starch being from corn, wheat or rice. Mention may be made especially of the product sold by Akzo Nobel under the name Dry Flo Plus.
The starches are especially chosen from powders of unmodified starch such as corn starch. Boron nitride particles may be mentioned, such as PUHP1030L by Saint Gobain Ceramics, UHP-1010 by Carborundum, Ronaflair Extender by Merck, Covalumine Atlas White AS by Sensient, Boroneige 601 by ESK, PUHP3008 by Saint Gobain Ceramics.
Clays are products that are already well known per se, which are described, for example, in the publication "Mineralogie des argiles" [Mineralogy of Clays], S. Caillere, S. Henin, M. Rautureau, 2nd Edition 1982, Masson, the teaching of which is included herein by way of reference.
Clays are silicates containing a cation that may be chosen from calcium, magnesium, aluminium, sodium, potassium and lithium cations, and mixtures thereof.
Examples of such products that may be mentioned include clays of the smectite family such as montmorillonites, hectorites, bentonites, beidellites and saponites, and also of the family of vermiculites, stevensite and chlorites.
The clays can be of natural or synthetic origin. Preferably, clays that are cosmetically compatible and acceptable with keratin fibres such as the hair are used.
The clay can be chosen from montmorillonite, bentonite, hectorite, attapulgite, sepiolite and mixtures thereof. Preferably, the clay is a bentonite or a hectorite.
The clays may be chosen from organophilic clays.
Organophilic clays are clays modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkyl aryl sulfonates and amine oxides, and mixtures thereof.
Preferably, the organophilic clays according to the invention are clays modified with a chemical compound chosen from quaternary amines.
Organophilic clays that may be mentioned include quaternium-18 bentonites such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Elementis, Tixogel VP by United Catalyst, and Claytone 34, Claytone 40 and Claytone XL by Southern Clay; stearalkonium bentonites such as those sold under the names Bentone 27V by Elementis, Tixogel LG by United Catalyst, and Claytone AF and Claytone APA by Southern Clay; and quaternium-18/benzalkonium bentonites such as those sold under the names Claytone HT and Claytone PS by Southern Clay.
The organophilic clay is particularly chosen from modified hectorites such as the hectorite modified by C10-C12 fatty acid ammonium chloride, especially distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride. The clays are especially chosen from montmorillonites and kaolin. Particularly preferred particles that absorb sebum are silica powders, especially precipitated silica powders and more specifically precipitated silicas coated with wax, perlite, boron nitride, starches and acrylic polymer powders.
Preferably, the particles have a number-average size of between 50 nm and 350 microns, better still between 100 nm and 100 microns and even more preferentially between 0.5 and 100 microns. The sebum-absorbing particles may be present in the composition according to the invention in a content ranging from 0.01 % to 30% by weight, preferably ranging from 0.1 % to 20% by weight and most preferentially ranging from 0.5% to 10% by weight, relative to the total weight of the composition. Method for measuring the sebum uptake of a powder:
The sebum uptake of a powder is measured according to the method for determining the oil uptake of a powder as described in standard NF T 30-022. It corresponds to the amount of sebum adsorbed onto the available surface of the powder, by measuring the wet point.
An amount m (in grams) of powder of between about 0.5 g and 5 g (the amount depends on the density of the powder) is placed on a glass plate and artificial sebum having the composition below is then added dropwise:
- triolein 29%
- oleic acid 28.5%
- oleyl oleate 18.5%
- squalene 14%
- cholesterol 7%
- cholesteryl palmitate 3%
After addition of 4 to 5 drops of artificial sebum, the artificial sebum is incorporated into the powder using a spatula, and the addition of the artificial sebum is continued until conglomerates of artificial sebum and of powder form. At this point, the artificial sebum is added one drop at a time and the mixture is then triturated with the spatula. The addition of artificial sebum is stopped when a firm, smooth paste is obtained. This paste must be able to be spread over the glass plate without cracks or the formation of lumps. The volume Vs (expressed in ml) of artificial sebum used is then noted. The sebum uptake corresponds to the ratio Vs/m.
The composition according to the invention may be cosmetic and/or dermatological, preferably cosmetic.
The composition according to the invention is generally suitable for topical application to the skin and thus generally comprises a physiologically acceptable medium, i.e. a medium that is compatible with the skin and/or its integuments. It is preferably a cosmetically acceptable medium, i.e. which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using this composition. The composition according to the invention may be in any galenical form conventionally used for a topical application and especially in the form of dispersions of the gel or lotion type, emulsions of liquid or semi-liquid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase (O/W) or vice versa (W/O), or suspensions or emulsions of soft, semi- solid or solid consistency of the cream or gel type, or alternatively multiple emulsions (W/O/W or O/W/O), microemulsions, vesicular dispersions of ionic and/or nonionic type, or wax/aqueous phase dispersions. The composition according to the invention may as a variant be presented in anhydrous form such as sticks or compact or free powders. These compositions are prepared according to the usual methods.
In addition, the compositions used according to the invention can be more or less fluid and can have the appearance of a white or coloured cream, of an ointment, of a milk, of a lotion, of a serum, of a paste or of a foam. They may optionally be applied to the skin in the form of an aerosol. They can also be in solid form, for example in the form of a stick.
Preferably, the compositions are liquid.
When the composition used according to the invention comprises an oily phase, it preferably contains at least one oil. It may also contain other fatty substances. Mention may be made, as oils which can be used in the composition of the invention, for example, of:
- hydrocarbon-based oils of animal origin, such as perhydrosqualene;
- hydrocarbon-based oils of plant origin, such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil;
- synthetic esters and ethers, especially of fatty acids, for instance the oils of formulae R1COOR2 and R1OR2 in which Ri represents a fatty acid residue containing from 8 to 29 carbon atoms and R2 represents a branched or unbranched hydrocarbon-based chain containing from 3 to 30 carbon atoms, for instance Purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate or isostearyl isostearate; hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate or triisocetyl citrate; fatty alcohol heptanoates, octanoates or decanoates; polyol esters, for instance propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters, for instance pentaerythrityl tetraisostearate;
- linear or branched hydrocarbons of mineral or synthetic origin, such as volatile or non-volatile liquid paraffins, and derivatives thereof, petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam oil;
- fatty alcohols having from 8 to 26 carbon atoms, such as cetyl alcohol, stearyl alcohol and a mixture thereof (cetylstearyl alcohol), octyldodecanol, 2- butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol;
- partially hydrocarbon-based and/or silicone-based fluoro oils, for instance those described in document JP-A-2-295 912;
- silicone oils, for instance volatile or non-volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, which are liquid or pasty at room temperature, especially cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes or 2-phenylethyl trimethylsiloxy silicates, and polymethylphenylsiloxanes;
- mixtures thereof.
In the list of the abovementioned oils, the term "hydrocarbon-based oil" is understood to mean any oil predominantly comprising carbon and hydrogen atoms, and optionally ester, ether, fluoro, carboxylic acid and/or alcohol groups. The other fatty substances that may be present in the oily phase are, for example, fatty acids containing from 8 to 30 carbon atoms, for instance stearic acid, lauric acid, palmitic acid and oleic acid; waxes, for instance lanolin wax, beeswax, carnauba wax or candelilla wax, paraffin wax, lignite wax or microcrystalline waxes, ceresin or ozokerite, and synthetic waxes, for instance polyethylene waxes and Fischer-Tropsch waxes; silicone resins such as trifluoromethyl-Ci-4-alkyl dimethicone and trifluoropropyl dimethicone; and silicone elastomers, for instance the products sold under the name KSG by the company Shin-Etsu, under the name Trefil, BY29 or EPSX by the company Dow Corning, or under the name Gransil by the company Grant Industries.
These fatty substances can be chosen in a varied manner by those skilled in the art so as to prepare a composition having the desired properties, for example of consistency or texture.
According to one particular embodiment of the invention, the composition according to the invention is a water-in-oil (W/O) or oil-in-water (O/W) emulsion, preferably an O/W emulsion. The O/W emulsion also comprises emulsified gels. The term "emulsified gels" means dispersions of oils in an aqueous gel. The addition of surfactant is optional for this galenical form.
The proportion of the oily phase of the emulsion may range from 2% to 80% by weight and preferably from 5% to 50% by weight relative to the total weight of the composition.
The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic and nonionic emulsifiers, used alone or as a mixture, and optionally a co-emulsifier. The emulsifiers are appropriately chosen according to the emulsion to be obtained (W/O or O/W). The emulsifier and the co-emulsifier are generally present in the composition in a proportion ranging from 0.3% to 30% by weight and preferably from 0.5% to 20% by weight relative to the total weight of the composition.
Mention may be made, for the W/O emulsions, for example, as emulsifiers, of dimethicone copolyols, such as the mixture of cyclomethicone and dimethicone copolyol sold under the name DC 5225 C by Dow Corning, and alkyl dimethicone copolyols, such as the lauryl dimethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by Dow Corning and the cetyl dimethicone copolyol sold under the name Abil EM 90® by Goldschmidt. A crosslinked elastomeric solid organopolysiloxane comprising at least one oxyalkylene group, such as those obtained according to the procedure of Examples 3, 4 and 8 of patent US-A-5 412 004 and of the examples of patent US-A-5 81 1 487, especially the product of Example 3 (synthesis example) of patent US-A-5 412 004, such as the product sold under the reference KSG 21 by the company Shin-Etsu, may also be used as a surfactant for W/O emulsions.
For O/W emulsions, examples of emulsifiers that may be mentioned include nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fatty acid esters of sorbitan; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty acid esters; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alcohol ethers; sugar esters such as sucrose stearate; and mixtures thereof, such as the mixture of glyceryl stearate and PEG-40 stearate.
The composition may be an aqueous gel, and may especially comprise common aqueous gelling agents. Advantageously, the composition is a composition comprising at least one aqueous phase. The composition according to the invention comprises an aqueous phase comprising water and optionally glycols, ethanol and/or hydrophilic adjuvants, which may be water-soluble at room temperature. The composition generally comprises from 30% to 95% water.
Advantageously, the composition according to the invention has a pH ranging from 3 to 8. Preferably, the pH of the composition ranges from 4 to 6.
The composition according to the invention may be a composition for caring for, cleansing or making up bodily or facial skin, in particular a care composition. The skincare composition may be, for example, a facial cream, gel or fluid.
The skin makeup composition may be, for example, a foundation, an eyeshadow, a face powder, a concealer product, a face and body powder, or a body makeup product.
Additives:
The composition according to the present invention may also contain various adjuvants commonly used in cosmetics, such as emulsifiers; fillers; preserving agents; sequestrants; dyes; fragrances; thickeners and gelling agents, in particular acrylamide homopolymers and copolymers, acrylic homopolymers and copolymers and acrylamidomethylpropanesulfonic acid (AMPS®) homopolymers and copolymers; UV-screening agents.
Advantageously, to reinforce the matting effects of the composition according to the invention, it also comprises at least one active agent for caring for greasy skin. This active agent is preferentially chosen from desquamating agents, antimicrobial agents, anti-inflammatory agents, sebum regulators and antioxidants. It may also contain cosmetic active agents other than those for caring for greasy skin, for instance moisturizers and vitamins.
Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s), and/or the amount thereof, such that the advantageous properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisioned addition.
Active agent for caring for greasy skin In the context of the present invention, the expression "active agent for the care of greasy skin" is understood to mean a compound which intrinsically has, i.e. not requiring the intervention of an external agent to activate it, biological activity which may be in particular: - desquamating activity (which allows the opening of comedones), and/or
- antimicrobial activity (especially on P. acnes), and/or
- anti-inflammatory activity, and/or
- sebum-regulating activity, and/or
- antioxidant activity (which prevents the oxidation of squalene and the formation of comedones).
The active agent for caring for greasy skin may thus be chosen from: desquamating agents and/or antimicrobial agents and/or anti-inflammatory agents and/or sebum regulators and/or antioxidants.
1 . Desquamating agents
The term "desquamating agent" means any compound capable of acting: - either directly on desquamation by promoting exfoliation, such as β-hydroxy acids, in particular salicylic acid and derivatives thereof (including 5-n- octanoylsalicylic acid); a-hydroxy acids, such as glycolic acid, citric acid, lactic acid, tartaric acid, malic acid or mandelic acid; urea; gentisic acid; oligofucoses; cinnamic acid; extract of Saphora japonica; resveratrol and certain jasmonic acid derivatives;
- or on the enzymes involved in desquamation or decomposition of the corneodesmosomes, glycosidases, stratum corneum chymotryptic enzyme (SCCE) or indeed even other proteases (trypsin, chymotrypsin-like). Mention may be made of aminosulfonic compounds and in particular N-(2- hydroxyethyl)piperazine-N-2-ethanesulfonic acid (HEPES); 2-oxothiazolidine-4- carboxylic acid (procysteine) derivatives; derivatives of a-amino acids of glycine type (as described in EP-0 852 949, and also sodium methyl glycine diacetate sold by BASF under the trade name Trilon M); honey; sugar derivatives such as O-octanoyl-6-D-maltose and N-acetylglucosamine.
5-n-Octanoylsalicylic acid is preferred for use in the present invention.
2. Antimicrobial agents The antimicrobial agents that may be used in the composition according to the invention may especially be chosen from 2,4,4'-trichloro-2'-hydroxydiphenyl ether (or triclosan), 3,4,4'-trichlorobanilide, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, hexamidine isethionate, metronidazole and salts thereof, miconazole and salts thereof, itraconazole, terconazole, econazole, ketoconazole, saperconazole, fluconazole, clotrimazole, butoconazole, oxiconazole, sulfaconazole, sulconazole, terbinafine, ciclopirox, ciclopiroxolamine, undecylenic acid and salts thereof, benzoyl peroxide, 3- hydroxybenzoic acid, 4-hydroxybenzoic acid, phytic acid, N-acetyl-L-cysteine acid, lipoic acid, azelaic acid and salts thereof, arachidonic acid, resorcinol, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 3,4,4'-trichlorocarbanalide, octopirox, octoxyglycerine, octanoylglycine, caprylyl glycol, 10-hydroxy-2-decanoic acid, dichlorophenylimidazoledioxolane and derivatives thereof described in patent WO 93/18743, copper pidolate, salicylic acid, zinc salicylate, iodopropynyl butylcarbamate, farnesol and phytosphingosines, and mixtures thereof.
The preferred antimicrobial agents are octoxyglycerine, copper pidolate, zinc salicylate, salicylic acid and iodopropynyl butylcarbamate.
3. Anti-inflammatory agents As anti-inflammatory or calmative agents that may be used in the composition according to the invention, mention may be made of pentacyclic triterpenes and plant extracts (e.g.: Glycyrrhiza glabra) containing the same, for instance β- glycyrrhetinic acid and salts and/or derivatives thereof (glycyrrhetinic acid monoglucuronide, stearyl glycyrrhetinate, 3-stearoyloxyglycyrrhetic acid), ursolic acid and salts thereof, oleanolic acid and salts thereof, betulinic acid and salts thereof, bisabolol, an extract of Paeonia suffruticosa and/or lactiflora, salicylic acid salts and in particular zinc salicylate, phycosaccharides from the company Codif, an extract of Laminaria saccharina, canola oil, bisabolol and extracts of camomile, allantoin, Sepivital EPC (phosphoric diester of vitamins E and C) from SEPPIC, omega-3 unsaturated oils such as musk rose oil, blackcurrant oil, ecchium oil, fish oil, plankton extracts, capryloylglycine, Seppicalm VG (sodium palmitoylproline and Nymphea alba) from SEPPIC, an extract of Pygeum, an extract of Boswellia serrata, an extract of Centipeda cunninghami, an extract of Helianthus annuus, an extract of Linum usitatissimum, tocotrienols, extracts of Cola nitida, extracts of Centella asiatica, piperonal, an extract of clove, an extract of Epilobium angustifolium, Aloe vera, an extract of Bacopa monieri, phytosterols, niacinamide, cortisone, hydrocortisone, indomethacin and betamethasone.
The preferred anti-inflammatory agents for use in the present invention are extracts of Centella asiatica, β-glycyrrhetinic acid and salts thereof, a-bisabolol and niacinamide. 4. Sebum regulators
When the composition according to the invention comprises a sebum regulator such as a 5cc-reductase inhibitor, this agent may be chosen especially from: - retinoids, and in particular retinol;
- sulfur and sulfur derivatives;
- zinc salts such as zinc lactate, gluconate, pidolate, carboxylate, salicylate and/or cysteate;
- selenium chloride;
- vitamin B6 or pyridoxine;
- the mixture of capryloyl glycine, sarcosine and Cinnamomum zeylanicum extract sold especially by the company SEPPIC under the trade name Sepicontrol A5®;
- an extract of Laminaria saccharina sold especially by the company SECMA under the trade name Phlorogine®; - an extract of Spiraea ulmaria sold especially by the company Silab under the trade name Sebonormine®;
- extracts of plants of the species Arnica montana, Cinchona succirubra, Eugenia caryophyllata, Humulus lupulus, Hypericum perforatum, Mentha piperita, Rosmarinus officinalis, Salvia officinalis and Thymus vulgaris, all sold, for example, by the company Maruzen;
- an extract of Serenoa repens sold especially by the company Euromed;
- extracts of plants of the genus Silybum;
- plant extracts containing sapogenins and in particular extracts of Dioscorea plants rich in diosgenin; and
- extracts of Eugenia caryophyllata containing eugenol and eugenyl glucoside.
Zinc salts are preferred for use in the present invention. 5. Antioxidants
The antioxidants that are preferred for use in the present invention may be chosen from tocopherol and esters thereof, such as tocopheryl acetate; BHT and BHA.
The active agent(s) used in the composition according to the invention may represent from 0.01 % to 50%, preferably from 0.1 % to 25% and better still from 0.5% to 10% of the total weight of the composition. The invention is also directed towards a cosmetic process for caring for and/or making up the skin, comprising the topical application to the skin of the composition according to the invention.
More precisely, it is a process for making the skin matt and/or for reducing its sheen.
The term "matting" means making the skin more matt and reducing its sheen, and thus its unaesthetic highlights.
The invention also relates to the cosmetic use of the composition according to the invention for caring for combination skin and/or greasy skin.
The invention will now be illustrated with the aid of the non-limiting examples that follow. In these examples, the amounts are indicated as weight percentages. Depending on the case, the compounds are cited as the chemical names or as the CTFA names (International Cosmetic Ingredient Dictionary and Handbook). EXAMPLES Example 1 :
A facial-care cream in the form of an oil/water emulsion having the composition below was prepared:
Figure imgf000025_0001
This composition may be applied in the morning and/or evening to the face to make combination skin and greasy skin matt. Example 2: Measuring the mattness/sheen Base formulation
Figure imgf000026_0002
In this base the contents of 3 fillers are varied between 0 and 1 %.
The total filler content remains constant (between 0.5% and 3%).
The mattness of the formulation after application is then measured (immediately and in the long term). Examples for a total filler content of 0.5%
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000027_0003
Examples for a total filler content of 1 %
Figure imgf000027_0002
Figure imgf000028_0001
Figure imgf000028_0002
Measuring the mattness by in vitro evaluation
The mattness obtained with composition A according to the invention, and with composition B given as a comparative example, was measured using a contrast card (Prufkarte type 24/5 - 250 cm2) sold by the company Erichsen. The composition was spread at a rate of 2 mg/cm2 using a mechanical film spreader. A mixture (80/20 water/sebum) was sprayed 10 times, then there was a 6- minute wait at room temperature, then reflection was measured using a gonioreflectonneter. The result obtained is the ratio R between the specular reflection and the diffuse reflection. The value of R is proportionately smaller the greater the matting effect.
-: shiny
0: no effect +: matt
++: matt +
+++: very matt
These results show that the composition according to the invention produces skin sheen inferior to that obtained with a composition containing each of the particles taken in isolation at the same total concentration.

Claims

1 . Cosmetic and/or dermatological connposition comprising, in a physiologically acceptable medium:
a) at least hydrophobic aerogel particles,
b) at least expanded polymer particles,
c) at least sebum-absorbing particles different from the particles a) and b),
the said composition comprising at least one aqueous phase, the hydrophobic aerogel particles having a specific surface area per unit of mass ranging from 200 to 1500 m2/g and preferably a size, expressed as volume-mean diameter (D[0.5]), of less than 1500 μιτι.
2. Composition according to Claim 1 , in which the hydrophobic aerogel particles have a specific surface area per unit of mass ranging from 600 to 1200 m2/g and better still from 600 to 800 m2/g.
3. Composition according to either of Claims 1 and 2, in which the hydrophobic aerogel particles have a size, expressed as volume-mean diameter, ranging from 5 to 25 μιτι and better still from 5 to 20 μιτι.
4. Composition according to any one of Claims 1 to 3, in which the hydrophobic aerogel particles have a tapped density ranging from 0.02 g/cm3 to 0.10 g/cm3 and preferably from 0.03 g/cm3 to 0.08 g/cm3.
5. Composition according to any one of Claims 1 to 4, in which the hydrophobic aerogel particles have a specific surface area per unit of volume ranging from 5 to 60 m2/cm3, preferably from 10 to 50 m2/cm3 and better still from 15 to 40 m2/cm3.
6. Composition according to any one of Claims 1 to 5, in which the hydrophobic aerogel particles 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 of particles.
7. Composition according to any one of Claims 1 to 6, in which the hydrophobic aerogel particles are organic, mineral or organic-mineral hybrids.
8. Composition according to any one of Claims 1 to 7, in which the hydrophobic aerogel particles are hydrophobic silica aerogel particles, preferably of silica silylate and more particularly trimethylsilyl silica aerogel particles.
9. Composition according to any one of the preceding claims, characterized in that the hydrophobic aerogel particles represent from 0.1 % to 30% by weight, preferably from 0.5% to 20% by weight, better still from 1 % to 10% by weight and more preferably from 1 .5% to 5% by weight, relative to the total weight of the composition.
10. Composition according to any one of the preceding claims, characterized in that the particles are made of thermoplastic materials chosen from polymers or copolymers of acrylonitrile, vinylidene chloride, vinyl chloride and/or acrylic or styrene monomer, which are optionally expanded.
1 1 . Composition according to the preceding claim, characterized in that the particles are chosen from hollow particles of an expanded copolymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and methyl methacrylate.
12. Composition according to any one of the preceding claims, characterized in that the expanded polymer particles represent from 0.1 % to 30% by weight, preferably from 0.5% to 20% by weight, better still from 1 % to 10% by weight and more preferably from 1 .5% to 5% by weight, relative to the total weight of the composition.
13. Composition according to any one of Claims 1 to 12, characterized in that the sebum-absorbing particles are chosen from:
- silica powders,
- polyamide (Nylon®) powders,
- powders of acrylic polymers, especially of polymethyl methacrylate, poly(methyl methacrylate/ethylene glycol dimethacrylate), poly(allyl methacrylate/ethylene glycol dimethacrylate), ethylene glycol dimethacrylate/lauryl methacrylate copolymer;
- powders of silicone elastomer, obtained especially by polymerization of organopolysiloxane containing at least two hydrogen atoms each bonded to a silicon atom and of an organopolysiloxane comprising at least two ethylenically unsaturated groups (especially two vinyl groups) in the presence of a platinum catalyst;
- starches,
- talc, - boron nitride,
- clays,
- perlite,
- a mixture thereof.
14. Composition according to any one of Claims 1 to 5, characterized in that the sebum-absorbing particle chosen from silica powders.
15. Composition according to any one of the claims 1 to 5, characterized in that the sebum-absorbing particle is present in a content ranging from 0.01 % to 30% by weight, preferably ranging from 0.1 % to 20% by weight and most preferentially ranging from 0.5% to 10% by weight, relative to the total weight of the composition.
16. Composition according to any one of the preceding claims, characterized in that it also comprises at least one active agent for caring for greasy skin chosen from desquamating agents, antimicrobial agents, anti-inflammatory agents, sebum regulators and antioxidants.
17. Cosmetic process for caring for and/or making up the skin, comprising the topical application to the skin of a composition as defined in one of Claims 1 to 16.
18. Process according to Claim 17, characterized in that it is a process for making the skin matt and/or for reducing its sheen.
19. Cosmetic use of the composition according to any one of Claims 1 to 16, for caring for combination skin and/or greasy skin.
PCT/EP2013/063017 2012-06-21 2013-06-21 Matt-effect composition comprising hydrophobic aerogel particles and expanded polymer particles WO2013190100A2 (en)

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FR1255833A FR2992183B1 (en) 2012-06-21 2012-06-21 MATIFYING EFFECT COMPOSITION COMPRISING HYDROPHOBIC AEROGEL PARTICLES AND EXPANDED POLYMER PARTICLES
FR1255833 2012-06-21
US201261673542P 2012-07-19 2012-07-19
US61/673,542 2012-07-19

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CN109608674A (en) * 2018-11-05 2019-04-12 福建师范大学 A kind of preparation method of graphene oxide/polyvinyl alcohol composite coating

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