WO2012110303A2 - Aqueous cosmetic composition containing composite material particles and gamma-oryzanol - Google Patents

Aqueous cosmetic composition containing composite material particles and gamma-oryzanol Download PDF

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Publication number
WO2012110303A2
WO2012110303A2 PCT/EP2012/051424 EP2012051424W WO2012110303A2 WO 2012110303 A2 WO2012110303 A2 WO 2012110303A2 EP 2012051424 W EP2012051424 W EP 2012051424W WO 2012110303 A2 WO2012110303 A2 WO 2012110303A2
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WO
WIPO (PCT)
Prior art keywords
inorganic
particles
matrix
composition according
polyglyceryl
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Application number
PCT/EP2012/051424
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French (fr)
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WO2012110303A3 (en
Inventor
Cécile GRARE
Catherine Marion
Céline PHILIPPON
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L'oreal
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Publication of WO2012110303A2 publication Critical patent/WO2012110303A2/en
Publication of WO2012110303A3 publication Critical patent/WO2012110303A3/en

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Classifications

    • 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
    • A61K8/11Encapsulated compositions
    • 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
    • A61K8/0254Platelets; Flakes
    • A61K8/0258Layered structure
    • 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
    • A61K8/0283Matrix particles
    • 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
    • A61K8/26Aluminium; Compounds thereof
    • 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
    • A61K8/29Titanium; Compounds thereof
    • 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
    • A61K8/96Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783Angiosperms [Magnoliophyta]
    • A61K8/9794Liliopsida [monocotyledons]
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/412Microsized, i.e. having sizes between 0.1 and 100 microns
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60Particulates further characterized by their structure or composition
    • A61K2800/61Surface treated
    • A61K2800/62Coated
    • A61K2800/621Coated by inorganic compounds

Definitions

  • This composition is for topical use and is more particularly intended for the photoprotection of the skin and/or hair against ultraviolet (UV) radiation.
  • UV ultraviolet
  • UV-B rays rays with wavelengths more particularly between 280 and 320 nm, known as UV-B rays, cause skin burns and erythema which can harm the development of a natural tan.
  • UV-B radiation should thus be screened out.
  • UV-A rays with wavelengths between 320 and 400 nm, which cause tanning of the skin, are liable to induce adverse changes therein, in particular in the case of sensitive skin or skin that is continually exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature ageing of the skin.
  • anti-sun compositions comprising organic screening agents that are active in the UV-A range and in the UV-B range are generally used.
  • anti-sun compositions are quite often in the form of an emulsion of oil-in- water type (i.e. a cosmetically and/or dermatologically acceptable support consisting of an aqueous dispersing continuous phase and of an oily dispersed discontinuous phase) due in particular to their pleasant feel (akin to water) and to their presentation in the form of a non-greasy cream or milk.
  • oil-in- water type i.e. a cosmetically and/or dermatologically acceptable support consisting of an aqueous dispersing continuous phase and of an oily dispersed discontinuous phase
  • water-in-oil compositions that have a good water resistance and that thus retain a very good photoprotective power even after several swims.
  • Water-in-oil emulsions generally contain emulsifiers in order to stabilize the dispersion of the discontinuous aqueous phase in the oily phase and to obtain a homogeneous composition.
  • Silicone-based emulsifiers such as silicone copolyols have the drawback of sometimes being incompatible with the aqueous phase of emulsions.
  • T1O2 titanium dioxide
  • These fine metal oxide particles generally have a mean elementary particle size of less than or equal to 0.1 nm, preferably between 5 nm and 100 nm, preferably between 0.01 and 0.1 pm, and preferentially between 0.015 and 0.050 pm.
  • inorganic screening agents lies in the fact that conventional anti-sun formulations based on metal oxide pigments result, after application to the skin, in an uneven, inhomogeneous or even coarse distribution of said pigments on this skin, which may be detrimental to the quality of the overall photoprotective effect desired.
  • This poor distribution of the screening metal oxide pigments that is observed at the surface of the skin is often linked to the fact that there is, in the initial composition itself (before application), a substantial lack of homogeneity (poor dispersion of the pigment in its support). Their screening efficiency still remains insufficient.
  • compositions comprising spherical composites based on a metal oxide and on a hydrophobic polymer.
  • EP 1 388 550 which targets the use of composite particles comprising a core formed of a metal oxide coated with a silicone or fluoro compound and the use thereof as a photoprotective cosmetic composition
  • application WO 98/22539 which describes a sunscreen containing a particle of silicon and/or of another solid compound in which the silicon is in stoichiometric excess, said particle having a mean diameter of less than 0.012 nm and being covered with a layer of oxide having a thickness ranging from 0.001 to 0.3 pm.
  • Sun formulations may contain, as screening system, spherical particles of composite material having a mean size between 2 and 7 pm, ⁇ 2 encapsulated in spherical particles of silica such as those sold under the name EOSPOLY TR by CREATION COULEUR or the name SUNSIL T50 by SUNJIN CHEMICAL.
  • compositions according to the present invention are photoprotective compositions intended to screen out UV radiation; these compositions are also known as anti-sun compositions or sun protection compositions.
  • cosmetically acceptable means compatible with the skin and/or its integuments or mucous membranes, having a pleasant colour, odour and feel and not causing any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using this composition.
  • mean size of the particles is understood to mean the parameter D[4,3] measured using a "Mastersizer 2000" particle size analyser (Malvern). The light intensity scattered by the particles as a function of the angle at which they are lit is converted to size distribution according to Mie theory. The parameter D[4,3] is measured; this is the mean diameter of the sphere having the same volume as the particle. For a spherical particle, reference will often be made to the "mean diameter".
  • Gamma-oryzanol is derived from rice bran. It is extracted with an organic solvent. It is then concentrated, recrystallized and dried. The raw material obtained is a white powder.
  • the plant extract will contain gamma-oryzanol at contents preferably ranging from 1 % to 100% by weight, more preferentially ranging from 10% to 100% by weight and more preferentially still from 50% to 100% by weight relative to the total weight of the extract.
  • Oryzanol from the company TSUNO RICE FINE CHEMICALS, Gamma Orizanol from the company IKEDA or Oryzanolgamma V from the company ICHIMARU PHARCOS. SCREENING COMPOSITE PARTICLES A
  • the spherical and non-spherical particles A used according to the present invention comprise a matrix and an inorganic UV screening agent.
  • the matrix comprises one or more organic and/or inorganic materials.
  • the inorganic UV screening agent is generally chosen from metal oxides, preferably titanium, zinc or iron oxides, or mixtures thereof and more particularly from titanium dioxide, zinc oxide and mixtures thereof. Particularly preferably, the inorganic UV screening agent is T1O2.
  • metal oxides may be in the form of particles, having a mean elementary size generally of less than 200 nm.
  • the metal oxide particles used have a mean elementary size of less than or equal to 0.1 pm.
  • the composite particles A contain a matrix comprising an organic and/or inorganic material, in which matrix particles of inorganic UV screening agent are included.
  • the matrix has inclusions and particles of inorganic UV screening agent are placed in the inclusions of the matrix.
  • the composite particles A contain a matrix made of an organic and/or inorganic material, which matrix is covered with at least one layer of inorganic UV screening agent which may be connected to the matrix with the aid of a binder.
  • the composite particles A contain an inorganic UV screening agent covered with at least one layer of an organic and/or inorganic material.
  • the matrix may also be formed from one or more organic or inorganic materials. It may then be a continuous phase of materials such as an alloy, i.e. a continuous phase in which the materials can no longer be dissociated, or a discontinuous phase of materials, for example constituted of an organic or inorganic material covered with a layer of another different organic or inorganic material.
  • the weight content of metal oxide in the particles of the invention is between 1 % and 70%, preferably between 2% and 65%, and better still between 3% and 60%.
  • the composite particles A may furthermore be covered with an additional coating, in particular chosen from biodegradable or biocompatible materials, lipid materials, for instance surfactants or emulsifiers, polymers, and oxides.
  • the screening composite particles A may be chosen from those of spherical shape, those of non-spherical shape or mixtures thereof.
  • the term "spherical” is understood to mean that the particle has a sphericity index, i.e. the ratio between its largest diameter and its smallest diameter, of less than 1 .2.
  • non-spherical is understood to mean particles having three dimensions (length, width and thickness or height) for which the ratio of the largest dimension to the smallest dimension is greater than 1 .2.
  • the dimensions of the particles of the invention are evaluated by scanning electron microscopy and image analysis. They include particles of parallelepipedal shape (rectangular or square surface area), discoid shape (circular surface area) or ellipsoid shape (oval surface area), characterized by three dimensions: a length, a width and a height. When the shape is circular, the length and the width are identical and correspond to the diameter of a disc, whereas the height corresponds to the thickness of the disc.
  • the length and the width correspond, respectively, to the large axis and the small axis of an ellipse and the height corresponds to the thickness of the elliptic disc formed by the platelet.
  • the length and the width may be of identical or different dimensions: when they are of the same dimension, the shape of the surface area of the parallelepiped is a square; in the contrary case, the shape is rectangular.
  • the height it corresponds to the thickness of the parallelepiped.
  • the content of composite particles of the composition according to the invention ranges from 1 % to 70%, preferably from 1 .5% to 45%, preferably from 2% to 20% by weight relative to the total weight of the cosmetic composition.
  • the inorganic materials that can be used in the matrix of the spherical composite particles according to the present invention may be chosen from the group formed by glass, silica, aluminium oxide and mixtures thereof.
  • the organic materials that can be used to form the matrix are chosen from the group formed by poly(meth)acrylates, polyamides, silicones, polyurethanes, polyethylenes, polypropylenes, polystyrenes, polycaprolactams, polysaccharides, polypeptides, polyvinyl derivatives, waxes, polyesters, polyethers, and mixtures thereof.
  • the matrix of the spherical composite particle A contains a material or mixture of materials chosen from:
  • the composite particles A in spherical form are characterized by a mean diameter between 0.1 pm and 30 pm, preferably between 0.2 pm and 20 pm and more preferably between 0.3 pm and 10 pm, advantageously between 0.5 pm and 10 ⁇
  • the spherical composite particles A contain a matrix comprising an organic and/or inorganic material, in which matrix particles of inorganic UV screening agent are included.
  • the particles of inorganic UV screening agent are characterized by a mean elementary size generally of less than 200 nm.
  • the metal oxide particles used have a mean elementary size of less than or equal to 0.1 pm.
  • composite particles A corresponding to this variant mention may be made of the products Sunsil TIN 50 and Sunsil TIN 40 sold by the company SUNJIN CHEMICAL. These spherical composite particles having a mean size between 2 and 7 pm are formed of T1O2 encapsulated in a silica matrix. Mention may also be made of the following particles A:
  • the spherical composite particles A contain a matrix made of an organic and/or inorganic material, which matrix is covered with at least one layer of inorganic UV screening agent connected to the matrix with the aid of a binder.
  • the mean thickness of the layer of inorganic UV screening agent is generally between 0.001 and 0.2 m, preferably between 0.01 and 0.1 ⁇
  • the spherical composite particles A used according to the invention have a size of between 0.1 and 30 m, preferably between 0.3 and 20 pm and more preferably still between 0.5 and 10 pm.
  • the spherical composite particles A contain an inorganic UV screening agent covered with at least one layer of an organic and/or inorganic material.
  • the particles of inorganic UV screening agent are characterized by a mean elementary size generally of between 0.001 and 0.2 pm.
  • the metal oxide particles used have a mean elementary size between 0.01 and 0.1 pm.
  • the spherical composite particles A used according to the invention have a size of between 0.1 and 30 pm, preferably between 0.3 and 20 pm and more preferably still between 0.5 and 10 pm.
  • the organic materials that can be used to form the matrix of non-spherical screening particles A are chosen from the group formed by polyamides, silicones, polysaccharides, polyvinyl derivatives, waxes, polyesters, and mixtures thereof.
  • the organic materials that can be used are:
  • the inorganic materials that can be used in the matrix of non-spherical composite particles A are chosen from the group formed by mica, synthetic mica, talc, silica, aluminium oxide, boron nitride, kaolin, hydrotalcite, mineral clays, synthetic clays and mixtures thereof.
  • these inorganic materials are chosen from:
  • non-spherical composite particles of the invention are characterized by three dimensions, of which:
  • the smallest is greater than 0.1 pm, preferably greater than 0.3 pm and better still greater than 0.5 pm;
  • the largest is less than 30 micrometres, preferably 20 micrometres and better still 10 micrometres.
  • the ratio of the largest dimension to the smallest dimension is greater than 1 .2.
  • the dimensions of the particles A of the invention are evaluated by scanning electron microscopy and image analysis.
  • the non-spherical screening composite particles A that can be used according to the invention will preferably be platelet-shaped.
  • platelet-shaped is understood to mean a parallelepipedal shape.
  • the platelet-shaped composite particles A preferably have a mean thickness between 0.1 and 10 pm, the mean length is generally between 0.5 and 30 microns and the mean width between 0.5 and 30 microns.
  • the thickness is the smallest of the dimensions, the width the middle dimension, and the length is the largest of the dimensions.
  • the composite particles A contain a matrix comprising an organic and/or inorganic material, in which matrix particles of inorganic UV screening agent are included.
  • the particles of inorganic UV screening agent are characterized by a mean elementary size generally of less than 0.2 pm.
  • the metal oxide particles used have a mean elementary size of less than or equal to 0.1 pm.
  • the composite particles A contain a matrix made of an organic and/or inorganic material, which matrix is covered with at least one layer of inorganic UV screening agent connected to the matrix with the aid of a binder.
  • the mean thickness of the layer of inorganic UV screening agent is generally about ten nanometres.
  • the mean thickness of the layer of inorganic UV screening agent is advantageously between 0.001 and 0.2 ⁇ , preferably between 0.01 and 0.2 pm.
  • the non-spherical composite particles A contain an inorganic UV screening agent covered with at least one layer of an organic and/or inorganic material.
  • the particles of inorganic UV screening agent are characterized by a mean elementary size generally of between 0.001 and 0.2 ⁇
  • the metal oxide particles used have a mean elementary size between 0.01 and 0.1 pm.
  • the non-spherical composite particles A used according to the invention have a size between 0.1 and 30 m, preferably between 0.5 and 10 pm.
  • the inorganic UV screening agent used in the composite particle A is chosen from metal oxides, in particular from titanium, zinc or iron oxides and more particularly titanium dioxide (T1O2).
  • the matrix of the composite particle A contains a material or mixture of materials chosen from:
  • the matrix of the composite particle A is constituted of a material or mixture of materials chosen from:
  • composite particles A that can be used according to the invention, mention may also be made of the following particles:
  • talc platelets having the trade name SILSEEM MISTYPEARL YELLOW sold by the company NIHON KOKEN KOGYO (NKK).
  • SILSEEM MISTYPEARL YELLOW sold by the company NIHON KOKEN KOGYO (NKK).
  • platelet-shaped composite particles A will be used.
  • the applicant observed that the screening efficacy obtained with the combination of screening particles A with gamma-oryzanol as described previously could be improved by using, in addition, at least particles B of inorganic UV screening agent that are hydrophobically treated with at least one oil or one wax of natural origin.
  • the inorganic UV screening agent constituting these particles B is generally chosen from metal oxides, preferably titanium, zinc or iron oxides, or mixtures thereof and more particularly from titanium dioxide, zinc oxide and mixtures thereof. Particularly preferably, the inorganic UV screening agent is T1O2.
  • metal oxides may be in the form of particles, having a mean elementary size generally of less than 200 nm.
  • the metal oxide particles used have a mean elementary size of less than or equal to 100 nm.
  • These metal oxides may also be in the form of layers, preferably multilayers having a mean thickness generally of less than 200 nm.
  • the oil of natural origin used to treat said particles B so as to render them hydrophobic is preferably chosen from jojoba esters that are, in general, a complex mixture of esters produced by transesterification/interesterification starting from jojoba oil (Simmondsia chinensis) or of esters starting from hydrogenated jojoba oil, or mixtures thereof.
  • the wax of natural origin used for treating said particles B so as to render them hydrophobic is preferably a jojoba wax which is the end product of the controlled hydrogenation of jojoba oil.
  • Use will more particularly be made of particles of titanium dioxide that are treated with alumina and jojoba esters having the INCI name TITANIUM DIOXIDE (and) ALUMINA (and) JOJOBA ESTERS, such as the products sold under the name MPT-154-NJE8 or TTO-NJE8 by the company KOBO.
  • the content of particles B in the composition according to the invention is between 0.1 % and 20%, preferably between 0.5% and 10% by weight and more preferably still between 0.5% and 10% by weight relative to the total weight of the composition.
  • the applicant observed that the screening efficacy obtained with the combination of screening particles A and B as described previously could also be improved by using, in addition, an oily dispersion of hydrophobically-modified particles C of inorganic UV screening agent having a mean size of greater than 100 nm, said particles C being different from particles B.
  • the inorganic UV screening agent constituting these particles C is generally chosen from metal oxides, preferably titanium, zinc or iron oxides, or mixtures thereof and more particularly from titanium dioxide, zinc oxide and mixtures thereof. Particularly preferably, the inorganic UV screening agent is T1O2.
  • These metal oxides preferably have an elementary mean size generally of between 100 nm and 200 nm.
  • the hydrophobically-modified particles C of inorganic screening agent may be coated by undergoing one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (titanium or aluminium alkoxides), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
  • surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64 such as amino acids, beeswax, fatty acids, fatty alcohols, anionic
  • silicones are organosilicon polymers or oligomers of linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and are essentially constituted of a repetition of main units in which the silicon atoms are linked together via oxygen atoms (siloxane bond), optionally substituted hydrocarbon-based radicals being directly attached to said silicon atoms via a carbon atom.
  • sicones also includes the silanes required for their preparation, in particular alkylsilanes.
  • metal oxide particles coated with at least one linear or branched C12-C18 fatty acid and more particularly stearic acid Preferably, use will be made of metal oxide particles coated with at least one linear or branched C12-C18 fatty acid and more particularly stearic acid.
  • the hydrophobically-modified particles C of inorganic UV screening agent may also be treated with other surface agents, in particular with cerium oxide, alumina, silica, aluminium compounds or silicon compounds, or mixtures thereof.
  • the oil present in the oily dispersion of particles C of inorganic UV screening agent is preferably chosen from C12-C15 alkyl benzoates or triglycerides such as caprylic/capric triglyceride.
  • the oily dispersions of hydrophobically-modified particles C of inorganic UV screening agent may comprise, in addition, at least one dispersant such as, for example, polyhydrostearic acid.
  • TITAN IUM DIOXIDE and) C12-C15 Alkyl Benzoate (and) POLYHYDROXYSTEARIC ACID (and) STEARIC ACID (and) ALUMINA such as the product sold under the trade name SOLVEIL XT-100 by the company CRODA; - TITANIUM DIOXIDE (and) CAPRYLIC/CAPRIC TRIGLYCERIDE (and) POLYHYDROXYSTEARIC ACID (and) STEARIC ACID (and) ALUMINA such as the product sold under the trade name SOLVEIL XT-300 by the company CRODA.
  • the content of oily dispersion of particles C in the composition according to the invention is between 0.1 % and 30%, preferably between 0.5% and 20% by weight and more preferably still between 1 % and 10% by weight relative to the total weight of the composition.
  • compositions may comprise at least one anhydrous phase comprising at least one polar oil.
  • anhydrous phase is understood to mean any phase comprising less than 3% by weight of water, or less than 1 % by weight of water, or more particularly less than 0.5% by weight of water relative to the total weight of the composition, or is free of water.
  • polar oil is understood to mean any lipophilic compound having, at 25°C, a solubility parameter 5 d characteristic of dispersive interactions of greater than 16 and a solubility parameter ⁇ ⁇ characteristic of polar interactions of strictly greater than 0.
  • the solubility parameters 5 d and ⁇ ⁇ are defined according to the Hansen classification.
  • these polar oils may be chosen from esters, triglycerides and ethers.
  • the polar oil may be a volatile or non-volatile hydrocarbon-based, silicone and/or fluoro oil.
  • oils may be of plant, mineral or synthetic origin.
  • polar hydrocarbon-based oil means an oil formed essentially from, or even constituted by, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
  • silicon oil means an oil containing at least one silicon atom, and especially containing Si-O groups.
  • fluoro oil means an oil containing at least one fluorine atom.
  • the polar oil according to the invention has a surface tension greater than 10 mN/m at 25°C and under atmospheric pressure. The surface activity is measured by static tensiometry using the Du Nouy ring.
  • the principle of the measurement is the following (measurement carried out at 25°C, at atmospheric pressure):
  • the weight of the ring is neutralized by a tare.
  • r and R respectively denote the internal and external radii of the ring.
  • the polar oil may be a non-volatile oil.
  • the non-volatile polar oil may be chosen from the list of oils below, and mixtures thereof:
  • phytostearyl esters such as phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutamate (AJINOMOTO, ELDEW PS203), triglycerides consisting of fatty acid esters of glycerol, in particular the fatty acids of which may have chain lengths ranging from C 4 to C36, and especially from C18 to C36, these oils possibly being linear or branched, and saturated or unsaturated; these oils may especially be heptanoic or octanoic triglycerides, wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil (820.6 g/mol), corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil,
  • phytostearyl esters such as phytoste
  • RCOOR' hydrocarbon-based esters of formula RCOOR' in which RCOO represents a carboxylic acid residue comprising from 2 to 40 carbon atoms, and R' represents a hydrocarbon-based chain containing from 1 to 40 carbon atoms, such as cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate or isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate, cetyl octanoate, tridecyl oc
  • fatty alcohols containing from 12 to 26 carbon atoms for instance octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol and oleyl alcohol;
  • - C12-C22 higher fatty acids such as oleic acid, linoleic acid and linolenic acid, and mixtures thereof;
  • - fluoro oils that are optionally partially hydrocarbon-based and/or silicone-based; - fatty acids containing from 12 to 26 carbon atoms, for instance oleic acid;
  • non-volatile oils of high molecular weight for example between 400 and 10 000 g/mol, in particular between 650 and 10 000 g/mol, for instance:
  • esters such as:
  • the polar oil is chosen from C12-C15 alcohol benzoate, diisopropyl sebacate, isopropyl lauroyl sarcosinate, dicaprylyl carbonate, the 2-phenylethyl ester of benzoic acid, butyloctyl salicylate, 2-octyldodecyl neopentanoate, dicaprylyl ether, isocetyl stearate, isodecyl neopentanoate, isononyl isononate, isopropyl myristate, isopropyl palmitate, isostearyl behenate, myristyl myristate, octyl palmitate and tridecyl trimellitate.
  • the polar oil is a C12-C15 alcohol benzoate.
  • the weight content of polar oil relative to the total weight of the composition is between 10% and 100%, preferably between 15% and 90%.
  • the "fatty phase" of the compositions according to the invention may also comprise a wax, an apolar oil or mixtures thereof.
  • apolar oils and the waxes conventionally used in cosmetic compositions may be used in the compositions according to the present invention.
  • compositions according to the invention may also comprise additional cosmetic and/or dermatological active agents.
  • additional cosmetic and/or dermatological active agents A person skilled in the art will select said active agent(s) as a function of the effect desired on the skin, the hair, the eyelashes, the eyebrows and the nails.
  • compositions in accordance with the present invention may also comprise standard cosmetic adjuvants chosen especially from organic solvents, ionic or nonionic, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoaming agents, fragrances, preserving agents, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, fillers, polymers, propellants, alkalinizing or acidifying agents or any other ingredient commonly used in the cosmetics and/or dermatological field.
  • standard cosmetic adjuvants chosen especially from organic solvents, ionic or nonionic, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoaming agents, fragrances, preserving agents, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, fill
  • organic solvents that may be mentioned are lower alcohols and polyols.
  • the latter may be chosen from glycols and glycol ethers, for instance ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.
  • Hydrophilic thickeners that may be mentioned include carboxyvinyl polymers, such as Carbopols (Carbomers) and the Pemulens (acrylate/C10-C30 alkyl acrylate copolymer); polyacrylamides, for instance the crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide/C13-C14 isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyl taurate copolymer/isohexadecane/polysorbate 80) by the company Seppic; 2-acrylamido- 2-methylpropanesulphonic acid polymers and copolymers, optionally crosslinked and/or neutralized, for instance poly(2-acrylamido-2-methylpropanesulphonic acid) sold by the company Clariant under the trade name Hostacerin AMPS (CTFA name: ammonium polyacryloyldimethyl taurate) or SIMULGEL 800 sold by the
  • Lipophilic thickeners that may be mentioned include synthetic polymers, such as the poly(C10-C30 alkyl acrylates) sold under the names INTELIMER IPA 13-1 and INTELIMER IPA 13-6 by the company Landec, or else modified clays, such as hectorite and its derivatives, for instance the products sold under the name Bentone.
  • synthetic polymers such as the poly(C10-C30 alkyl acrylates) sold under the names INTELIMER IPA 13-1 and INTELIMER IPA 13-6 by the company Landec, or else modified clays, such as hectorite and its derivatives, for instance the products sold under the name Bentone.
  • compositions according to the invention may, in addition, also comprise additional cosmetic and dermatological active agents.
  • moisturizers for instance polyols such as glycerol, butylene glycol or propylene glycol;
  • a person skilled in the art will select the said active agent(s) as a function of the effect desired on the skin, the hair, the eyelashes, the eyebrows and the nails.
  • aqueous compositions according to the invention may be prepared according to the techniques that are well known to those skilled in the art.
  • They may be in the form of a lotion, milk, cream, cream gel, aqueous gel, aqueous-alcoholic gel, cream or foam.
  • They may comprise, in addition, at least one fatty phase and may be in the form of a simple or complex emulsion (O/W, W/O, O/W/O or W/O/W) such as a milk, a cream or a cream gel. They may optionally be packaged as an aerosol and may be in the form of a spray.
  • a simple or complex emulsion O/W, W/O, O/W/O or W/O/W
  • a milk a cream or a cream gel
  • They may optionally be packaged as an aerosol and may be in the form of a spray.
  • compositions according to the invention are preferably in the form of an oil-in- water or water-in-oil emulsion.
  • the emulsification processes that may be used are of paddle or impeller, rotor- stator and high-pressure homogenizer (HPH) type.
  • the emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture.
  • the emulsifiers are appropriately chosen according to the emulsion to be obtained (W/O or O/W).
  • the emulsions may also contain stabilizers of other types, for instance fillers, or gelling or thickening polymers.
  • emulsifiers examples include nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) esters of fatty acids and of glycerol; oxyalkylenated esters of fatty acids and of sorbitan; oxyalkylenated (oxyethylenated and/or oxypropylenated) esters of fatty acids, such as the PEG 100 stearate/glyceryl stearate mixture sold, for example, by ICI under the name Arlacel 165; oxyalkylenated (oxyethylenated and/or oxypropylenated) ethers of fatty alcohols; esters of sugars, such as sucrose stearate; or ethers of fatty alcohol and of sugar, in particular alkyl polyglucosides (APGs), such as decyl glucoside and lauryl glucoside, sold
  • APGs alkyl polyglucosides
  • the mixture of the alkyl polyglucoside as defined above with the corresponding fatty alcohol can be in the form of a self- emulsifying composition, for example as described in document WO-A-92/06778.
  • emulsion stabilizers use may also be made of isophthalic acid or sulphoisophthalic acid polymers, and in particular phthalate/sulphoisophthalate/glycol copolymers, for example the diethylene glycol/phthalate/isophthalate/1 ,4-cyclohexanedimethanol copolymer (INCI name: Polyester-5) sold under the name Eastman AQ Polymer (AQ35S, AQ38S, AQ55S and AQ48 Ultra) by the company Eastman Chemical.
  • mention may also be made of hydrophobically modified 2-acrylamido-2-methylpropanesulphonic acid polymers such as those described in patent application EP 1 069 142.
  • the aqueous phase of this emulsion may comprise a nonionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008).
  • HLB hydrophilic lipophilic balance
  • the HLB of the surfactant(s) used according to the invention is the HLB according to GRIFFIN, defined in the publication J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256.
  • Non-limiting examples of surfactants with an HLB of less than or equal to 5 are especially given in the publication entitled McCutcheon's Emulsifiers & Detergents, 1998 International Edition, MC Publishing Company, in the chapter entitled HLB Index.
  • W/O emulsifying surfactants examples that may be mentioned include alkyl esters or ethers of sorbitan, of polyol, of glycerol or of sugars; silicone surfactants, for instance dimethicone copolyols, such as the mixture of cyclomethicone and of dimethicone copolyol, sold under the name DC 5225 C by the company Dow Corning, and alkyldimethicone copolyols such as laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by the company Dow Corning; cetyldimethicone copolyol, such as the product sold under the name Abil EM 90R by the company Goldschmidt, and the mixture of cetyldimethicone copolyol, of polyglyceryl isostearate (4 mol) and of hexyl laurate, sold under the name ABIL WE 09 by the company Goldschmidt.
  • coemulsifiers may also be added thereto, which may be chosen advantageously from the group comprising polyol alkyl esters.
  • Non-silicone emulsifiers will be preferred, especially alkyl esters or ethers of sorbitan, of glycerol, of polyol or of sugars.
  • Polyol alkyl esters that may especially be mentioned include polyethylene glycol esters, for instance PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135 by the company ICI.
  • Glycerol and/or sorbitan esters that may be mentioned include, for example, polyglyceryl isostearate, such as the product sold under the name Isolan Gl 34 by the company Goldschmidt, sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company ICI, sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof.
  • compositions are in the form of a water-in-oil emulsion.
  • water-in-oil emulsion is understood to mean a composition constituted of an oily dispersing continuous phase and an aqueous dispersed discontinuous phase.
  • W/O emulsifiers use will more particularly be made of polyglycerolated diesters and polyesters especially chosen from:
  • Polycare P 5 from the company Biogenico World Wide; Sunsoft 818H, 818SK and 818TY from the company Taiyo Kagaku Company, Ltd.), - Polyglyceryl-10 Polyricinoleate (Phytoglyn AO from the company Maruzen Pharmaceuticals Co., Ltd.),
  • compositions 1 to 2 below were prepared. The ingredients are used as weight percentages of active material relative to the total weight of the composition.
  • Ai is heated at 75/80°C - (clear solution).
  • all the compounds of Bi are weighed into another beaker and stirred using a deflocculator until solubilized.
  • B 2 is sprinkled in and stirred until solubilized/gelled.
  • B 3 and then B 4 are added.
  • B is introduced into A using an emulsifying device slowly (1 to 2 min approximately) at up to 2000 rpm and then for 6 to 7 min at 3000 rpm. It is cooled using a butterfly shaft.
  • C is added. At a temperature below 30°C, D is added over 5 min.
  • the sun protection factor is determined according to the "in vitro" method described by B. L. Diffey in J. Soc. Cosmet. Chem. 40, 127-133 (1989). The measurements were carried out using a UV-2000S spectrophotometer from the company Labsphere. Each composition is applied to a rough plate of PMMA, in the form of a homogeneous and even deposit in a proportion of 0.6 mg/cm 2
  • the index of UV-A protection is particularly recommended and used.
  • This method has been adopted since 1996 by the Japanese Cosmetic Industry Association (JCIA) as official test procedure for the UV-A labelling of products and is frequently used by test laboratories in Europe and the United States (Japan Cosmetic Industry Association Technical Bulletin. Measurement Standards for UVA protection efficacy. Issued November 21 , 1995 and effective as of January 1 , 1996).
  • JCIA Japanese Cosmetic Industry Association
  • UVAppo Sun protection factor (UVAp PD PF) is expressed mathematically by the ratio of the UV-A radiation dose necessary to reach the pigmentation threshold with the UV-screening agent (MPPDp) to the UV-A radiation dose necessary to reach the pigmentation threshold without UV-screening agent (MPPDnp).
  • UVA PPD PF UVA PPD PF
  • compositions 3 to 4 below were prepared. The ingredients are used as weight percentages of active material relative to the total weight of the composition.
  • compositions were evaluated with respect to the screening efficacy.

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Abstract

One subject of the present invention is a composition containing, in a cosmetically acceptable medium: a)at least one aqueous phase; and b)at least composite particles A having a size between 0.1 and 30 µm comprising a matrix and an inorganic UV screening agent, said inorganic screening agent being present in a content ranging from 1% to 70% by weight relative to the total weight of the composite particle; and c) gamma-oryzanol or a plant extract containing it.

Description

AQUEOUS COSMETIC COMPOSITION CONTAINING COMPOSITE MATERIAL PARTICLES AND GAMMA-ORYZANOL
One subject of the present invention is a composition containing, in a cosmetically acceptable medium:
a) at least one aqueous phase; and
b) at least composite particles A having a size between 0.1 and 30 pm comprising a matrix and an inorganic screening agent, said inorganic screening agent being present in a content ranging from 1 % to 70% by weight relative to the total weight of the composite particle; and
c) gamma-oryzanol or a plant extract containing it.
This composition is for topical use and is more particularly intended for the photoprotection of the skin and/or hair against ultraviolet (UV) radiation.
It is known that light radiation with wavelengths of between 280 nm and 400 nm permits tanning of the human epidermis and that rays with wavelengths more particularly between 280 and 320 nm, known as UV-B rays, cause skin burns and erythema which can harm the development of a natural tan.
For these reasons, and also for aesthetic reasons, there is constant demand for means for controlling this natural tanning in order thus to control the colour of the skin; this UV-B radiation should thus be screened out. It is also known that UV-A rays, with wavelengths between 320 and 400 nm, which cause tanning of the skin, are liable to induce adverse changes therein, in particular in the case of sensitive skin or skin that is continually exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature ageing of the skin.
Thus, for aesthetic and cosmetic reasons, for instance conservation of the skin's natural elasticity, people increasingly wish to control the effect of UV-A rays on their skin. It is thus desirable also to screen out UV-A radiation. For the purpose of protecting the skin and keratin materials against UV radiation, anti-sun compositions comprising organic screening agents that are active in the UV-A range and in the UV-B range are generally used.
There are many cosmetic products comprising one or more inorganic and/or organic UV screening agents.
These anti-sun compositions are quite often in the form of an emulsion of oil-in- water type (i.e. a cosmetically and/or dermatologically acceptable support consisting of an aqueous dispersing continuous phase and of an oily dispersed discontinuous phase) due in particular to their pleasant feel (akin to water) and to their presentation in the form of a non-greasy cream or milk. However, one of the drawbacks of oil-in-water emulsions is that they very readily lose their UV-protecting efficacy once they come into contact with water; indeed, the screening agents that they contain in their aqueous phase are carried away by water, when bathing in the sea or in a swimming pool for example, or else under the shower or when practising water sports, and the overall photoprotective power of these compositions is greatly reduced.
This is why, in certain cases where a particularly high and long-lasting protection is sought, for instance for children's skin or else for sensitive skin, it is preferred to use water-in-oil compositions that have a good water resistance and that thus retain a very good photoprotective power even after several swims.
Water-in-oil emulsions generally contain emulsifiers in order to stabilize the dispersion of the discontinuous aqueous phase in the oily phase and to obtain a homogeneous composition. Silicone-based emulsifiers such as silicone copolyols have the drawback of sometimes being incompatible with the aqueous phase of emulsions.
For children's skin or else sensitive skin, use is usually made of fine particles of metal oxide such as titanium dioxide (T1O2) in order to protect the skin from UV rays.
These fine metal oxide particles generally have a mean elementary particle size of less than or equal to 0.1 nm, preferably between 5 nm and 100 nm, preferably between 0.01 and 0.1 pm, and preferentially between 0.015 and 0.050 pm.
One of the major drawbacks of inorganic screening agents lies in the fact that conventional anti-sun formulations based on metal oxide pigments result, after application to the skin, in an uneven, inhomogeneous or even coarse distribution of said pigments on this skin, which may be detrimental to the quality of the overall photoprotective effect desired. This poor distribution of the screening metal oxide pigments that is observed at the surface of the skin is often linked to the fact that there is, in the initial composition itself (before application), a substantial lack of homogeneity (poor dispersion of the pigment in its support). Their screening efficiency still remains insufficient.
Applications FR 2882371 , WO 2006/083326 and WO 98/37964 describe various processes for manufacturing composite particles constituted of a material comprising nanoparticles of metal oxides, such as titanium dioxide.
Application WO 2006/061835 describes compositions comprising spherical composites based on a metal oxide and on a hydrophobic polymer.
From application JP04198124, makeup powders such as foundations made of organic or mineral material are known, the surface of which is covered by and bonded to an organic or mineral UV screening agent. These anhydrous screening materials have the drawback of being difficult to apply to the body as a sun protection product. Known in the cosmetic field are application EP 1 388 550, which targets the use of composite particles comprising a core formed of a metal oxide coated with a silicone or fluoro compound and the use thereof as a photoprotective cosmetic composition, and application WO 98/22539, which describes a sunscreen containing a particle of silicon and/or of another solid compound in which the silicon is in stoichiometric excess, said particle having a mean diameter of less than 0.012 nm and being covered with a layer of oxide having a thickness ranging from 0.001 to 0.3 pm.
Sun formulations are known that may contain, as screening system, spherical particles of composite material having a mean size between 2 and 7 pm, ΤΊΟ2 encapsulated in spherical particles of silica such as those sold under the name EOSPOLY TR by CREATION COULEUR or the name SUNSIL T50 by SUNJIN CHEMICAL.
These screening materials have the drawback of leading to formulations having an efficacy that remains insufficient in aqueous sun formulations. Therefore, there remains a need to have UV sun protection compositions based on inorganic UV screening agents that are more effective in photoprotection and that do not have the drawbacks presented above.
Unexpectedly and advantageously, the inventors have shown that this need could be met by means of the compositions according to the present invention.
One subject of the present invention is a composition containing, in a cosmetically acceptable medium:
a) at least one aqueous phase; and
b) at least composite particles A having a size between 0.1 and 30 pm comprising a matrix and an inorganic UV screening agent, said inorganic UV screening agent being present in a content ranging from 1 % to 70% by weight relative to the total weight of the composite particle; and
c) gamma-oryzanol or a plant extract containing it.
The following description and examples present other advantages, aspects and properties of the present invention.
Definitions
The following definitions are used in the present text.
The compositions according to the present invention are photoprotective compositions intended to screen out UV radiation; these compositions are also known as anti-sun compositions or sun protection compositions.
The expression "cosmetically acceptable" means compatible with the skin and/or its integuments or mucous membranes, having a pleasant colour, odour and feel and not causing any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using this composition.
The expression "mean size" of the particles is understood to mean the parameter D[4,3] measured using a "Mastersizer 2000" particle size analyser (Malvern). The light intensity scattered by the particles as a function of the angle at which they are lit is converted to size distribution according to Mie theory. The parameter D[4,3] is measured; this is the mean diameter of the sphere having the same volume as the particle. For a spherical particle, reference will often be made to the "mean diameter".
The expression "mean elementary size" is understood to mean the size of non- aggregated particles. Gamma-oryzanol
The structure of gamma-oryzanol is:
Figure imgf000005_0001
and it has the CAS number: 1 1042-64-1 . It is an ester of ferulic acid and of terpene alcohol of formula:
Figure imgf000005_0002
Gamma-oryzanol is derived from rice bran. It is extracted with an organic solvent. It is then concentrated, recrystallized and dried. The raw material obtained is a white powder.
Preferably, the plant extract will contain gamma-oryzanol at contents preferably ranging from 1 % to 100% by weight, more preferentially ranging from 10% to 100% by weight and more preferentially still from 50% to 100% by weight relative to the total weight of the extract.
It is commercially available under the name Oryzanol from the company TSUNO RICE FINE CHEMICALS, Gamma Orizanol from the company IKEDA or Oryzanolgamma V from the company ICHIMARU PHARCOS. SCREENING COMPOSITE PARTICLES A
The spherical and non-spherical particles A used according to the present invention comprise a matrix and an inorganic UV screening agent. The matrix comprises one or more organic and/or inorganic materials.
The inorganic UV screening agent is generally chosen from metal oxides, preferably titanium, zinc or iron oxides, or mixtures thereof and more particularly from titanium dioxide, zinc oxide and mixtures thereof. Particularly preferably, the inorganic UV screening agent is T1O2.
These metal oxides may be in the form of particles, having a mean elementary size generally of less than 200 nm. Advantageously, the metal oxide particles used have a mean elementary size of less than or equal to 0.1 pm.
These metal oxides may also be in the form of layers, preferably multilayers having a mean thickness generally of less than 0.2 pm. According to a first variant, the composite particles A contain a matrix comprising an organic and/or inorganic material, in which matrix particles of inorganic UV screening agent are included. According to this embodiment, the matrix has inclusions and particles of inorganic UV screening agent are placed in the inclusions of the matrix.
According to a second variant, the composite particles A contain a matrix made of an organic and/or inorganic material, which matrix is covered with at least one layer of inorganic UV screening agent which may be connected to the matrix with the aid of a binder.
According to a third variant, the composite particles A contain an inorganic UV screening agent covered with at least one layer of an organic and/or inorganic material. The matrix may also be formed from one or more organic or inorganic materials. It may then be a continuous phase of materials such as an alloy, i.e. a continuous phase in which the materials can no longer be dissociated, or a discontinuous phase of materials, for example constituted of an organic or inorganic material covered with a layer of another different organic or inorganic material.
The weight content of metal oxide in the particles of the invention is between 1 % and 70%, preferably between 2% and 65%, and better still between 3% and 60%.
According to one variant, in particular when the composite particles A comprise a matrix covered with a layer of UV screening agent, the composite particles may furthermore be covered with an additional coating, in particular chosen from biodegradable or biocompatible materials, lipid materials, for instance surfactants or emulsifiers, polymers, and oxides. The screening composite particles A may be chosen from those of spherical shape, those of non-spherical shape or mixtures thereof. The term "spherical" is understood to mean that the particle has a sphericity index, i.e. the ratio between its largest diameter and its smallest diameter, of less than 1 .2.
The term "non-spherical" is understood to mean particles having three dimensions (length, width and thickness or height) for which the ratio of the largest dimension to the smallest dimension is greater than 1 .2. The dimensions of the particles of the invention are evaluated by scanning electron microscopy and image analysis. They include particles of parallelepipedal shape (rectangular or square surface area), discoid shape (circular surface area) or ellipsoid shape (oval surface area), characterized by three dimensions: a length, a width and a height. When the shape is circular, the length and the width are identical and correspond to the diameter of a disc, whereas the height corresponds to the thickness of the disc. When the surface is oval, the length and the width correspond, respectively, to the large axis and the small axis of an ellipse and the height corresponds to the thickness of the elliptic disc formed by the platelet. When it is a parallelepiped, the length and the width may be of identical or different dimensions: when they are of the same dimension, the shape of the surface area of the parallelepiped is a square; in the contrary case, the shape is rectangular. As regards the height, it corresponds to the thickness of the parallelepiped.
Preferably, the content of composite particles of the composition according to the invention ranges from 1 % to 70%, preferably from 1 .5% to 45%, preferably from 2% to 20% by weight relative to the total weight of the cosmetic composition. Spherical screening composite particles A
The inorganic materials that can be used in the matrix of the spherical composite particles according to the present invention may be chosen from the group formed by glass, silica, aluminium oxide and mixtures thereof.
The organic materials that can be used to form the matrix are chosen from the group formed by poly(meth)acrylates, polyamides, silicones, polyurethanes, polyethylenes, polypropylenes, polystyrenes, polycaprolactams, polysaccharides, polypeptides, polyvinyl derivatives, waxes, polyesters, polyethers, and mixtures thereof.
Preferably, the matrix of the spherical composite particle A contains a material or mixture of materials chosen from:
- Si02,
- polymethyl methacrylate,
- copolymers of styrene and of a C1 /C5 alkyl (meth)acrylate derivative,
- polyamides, such as nylon. The composite particles A in spherical form are characterized by a mean diameter between 0.1 pm and 30 pm, preferably between 0.2 pm and 20 pm and more preferably between 0.3 pm and 10 pm, advantageously between 0.5 pm and 10 μητ
According to a first variant, the spherical composite particles A contain a matrix comprising an organic and/or inorganic material, in which matrix particles of inorganic UV screening agent are included. According to this first variant, the particles of inorganic UV screening agent are characterized by a mean elementary size generally of less than 200 nm. Advantageously, the metal oxide particles used have a mean elementary size of less than or equal to 0.1 pm. As composite particles A corresponding to this variant, mention may be made of the products Sunsil TIN 50 and Sunsil TIN 40 sold by the company SUNJIN CHEMICAL. These spherical composite particles having a mean size between 2 and 7 pm are formed of T1O2 encapsulated in a silica matrix. Mention may also be made of the following particles A:
- spherical composite particles having a mean size between 4 and 8 m, containing T1O2 and S 1O2 and having the trade name Eospoly TR sold by the company CREATIONS COULEURS,
- composite particles containing T1O2 and a styrene/alkyl acrylate copolymer matrix sold under the name Eospoly UV TR22 HB 50 by the company CREATIONS
COULEURS,
- composite particles containing T1O2 and ZnO and a PMMA matrix and having the trade name Sun PMMA-T50 sold by the company SUNJIN CHEMICAL. According to a second variant, the spherical composite particles A contain a matrix made of an organic and/or inorganic material, which matrix is covered with at least one layer of inorganic UV screening agent connected to the matrix with the aid of a binder. According to this second variant, the mean thickness of the layer of inorganic UV screening agent is generally between 0.001 and 0.2 m, preferably between 0.01 and 0.1 μητ
The spherical composite particles A used according to the invention have a size of between 0.1 and 30 m, preferably between 0.3 and 20 pm and more preferably still between 0.5 and 10 pm.
Among the composite particles A that can be used according to the invention, mention may also be made of spherical composite particles containing T1O2 and S 1O2 and having the trade name STM ACS-0050510, supplied by the company JGC Catalysts and Chemical. According to a third variant, the spherical composite particles A contain an inorganic UV screening agent covered with at least one layer of an organic and/or inorganic material. According to this third variant, the particles of inorganic UV screening agent are characterized by a mean elementary size generally of between 0.001 and 0.2 pm. Advantageously, the metal oxide particles used have a mean elementary size between 0.01 and 0.1 pm.
The spherical composite particles A used according to the invention have a size of between 0.1 and 30 pm, preferably between 0.3 and 20 pm and more preferably still between 0.5 and 10 pm.
Non-spherical screening particles A
The organic materials that can be used to form the matrix of non-spherical screening particles A are chosen from the group formed by polyamides, silicones, polysaccharides, polyvinyl derivatives, waxes, polyesters, and mixtures thereof.
Preferably, the organic materials that can be used are:
- triethoxycaprylylsilane,
- ethylene/vinyl acetate copolymers.
The inorganic materials that can be used in the matrix of non-spherical composite particles A are chosen from the group formed by mica, synthetic mica, talc, silica, aluminium oxide, boron nitride, kaolin, hydrotalcite, mineral clays, synthetic clays and mixtures thereof. Preferably, these inorganic materials are chosen from:
- silica;
- talc;
- mica;
- alumina.
The non-spherical composite particles of the invention are characterized by three dimensions, of which:
- the smallest is greater than 0.1 pm, preferably greater than 0.3 pm and better still greater than 0.5 pm;
- the largest is less than 30 micrometres, preferably 20 micrometres and better still 10 micrometres.
The ratio of the largest dimension to the smallest dimension is greater than 1 .2. The dimensions of the particles A of the invention are evaluated by scanning electron microscopy and image analysis.
The non-spherical screening composite particles A that can be used according to the invention will preferably be platelet-shaped.
The term "platelet-shaped" is understood to mean a parallelepipedal shape.
They may be smooth, rough or porous. The platelet-shaped composite particles A preferably have a mean thickness between 0.1 and 10 pm, the mean length is generally between 0.5 and 30 microns and the mean width between 0.5 and 30 microns.
The thickness is the smallest of the dimensions, the width the middle dimension, and the length is the largest of the dimensions.
According to a first variant, the composite particles A contain a matrix comprising an organic and/or inorganic material, in which matrix particles of inorganic UV screening agent are included.
According to this first variant, the particles of inorganic UV screening agent are characterized by a mean elementary size generally of less than 0.2 pm. Advantageously, the metal oxide particles used have a mean elementary size of less than or equal to 0.1 pm.
According to a second variant, the composite particles A contain a matrix made of an organic and/or inorganic material, which matrix is covered with at least one layer of inorganic UV screening agent connected to the matrix with the aid of a binder.
According to this second variant, the mean thickness of the layer of inorganic UV screening agent is generally about ten nanometres. The mean thickness of the layer of inorganic UV screening agent is advantageously between 0.001 and 0.2 μηι, preferably between 0.01 and 0.2 pm.
According to a third variant, the non-spherical composite particles A contain an inorganic UV screening agent covered with at least one layer of an organic and/or inorganic material. According to this third variant, the particles of inorganic UV screening agent are characterized by a mean elementary size generally of between 0.001 and 0.2 μητ Advantageously, the metal oxide particles used have a mean elementary size between 0.01 and 0.1 pm. The non-spherical composite particles A used according to the invention have a size between 0.1 and 30 m, preferably between 0.5 and 10 pm.
Preferably, the inorganic UV screening agent used in the composite particle A is chosen from metal oxides, in particular from titanium, zinc or iron oxides and more particularly titanium dioxide (T1O2).
Preferably, the matrix of the composite particle A contains a material or mixture of materials chosen from:
- Si02;
- alumina;
- mica;
- alumina/triethoxycaprylylsilane mixture;
- talc; Nylon.
More preferably, the matrix of the composite particle A is constituted of a material or mixture of materials chosen from:
- alumina;
- alumina/triethoxycaprylylsilane mixture;
- talc;
- silica;
- mica.
Among the composite particles A that can be used according to the invention, mention may also be made of the following particles:
- composite particles containing ΤΊΟ2 and an alumina matrix having the trade name MATLAKE OPA sold by the company SENSIENT LCW,
- composite particles containing ΤΊΟ2 and an alumina/triethoxycaprylylsilane matrix having the trade name MATLAKE OPA AS sold by the company SENSIENT LCW,
- composite particles containing ultrafine T1O2 particles deposited on the surface of talc platelets having the trade name TTC 30 sold by the company MYOSHI KASEI,
- composite particles containing ultrafine T1O2 particles deposited on the surface of talc platelets having the trade name SILSEEM MISTYPEARL YELLOW sold by the company NIHON KOKEN KOGYO (NKK). Preferably, platelet-shaped composite particles A will be used.
PARTICLES B OF INORGANIC UV SCREENING AGENT THAT ARE HYDROPHOBICALLY TREATED WITH A NATURAL OIL OR WAX According to one particularly preferred embodiment of the invention, the applicant observed that the screening efficacy obtained with the combination of screening particles A with gamma-oryzanol as described previously could be improved by using, in addition, at least particles B of inorganic UV screening agent that are hydrophobically treated with at least one oil or one wax of natural origin.
The inorganic UV screening agent constituting these particles B is generally chosen from metal oxides, preferably titanium, zinc or iron oxides, or mixtures thereof and more particularly from titanium dioxide, zinc oxide and mixtures thereof. Particularly preferably, the inorganic UV screening agent is T1O2.
These metal oxides may be in the form of particles, having a mean elementary size generally of less than 200 nm. Advantageously, the metal oxide particles used have a mean elementary size of less than or equal to 100 nm. These metal oxides may also be in the form of layers, preferably multilayers having a mean thickness generally of less than 200 nm. The oil of natural origin used to treat said particles B so as to render them hydrophobic is preferably chosen from jojoba esters that are, in general, a complex mixture of esters produced by transesterification/interesterification starting from jojoba oil (Simmondsia chinensis) or of esters starting from hydrogenated jojoba oil, or mixtures thereof.
The wax of natural origin used for treating said particles B so as to render them hydrophobic is preferably a jojoba wax which is the end product of the controlled hydrogenation of jojoba oil.
Use will more particularly be made, as a hydrophobic treatment agent, of jojoba esters such as the commercial product sold under the name FLORAESTER 70 by the company Floratee. Particles B of inorganic UV screening agent that are hydrophobically treated with an oil or wax of natural origin are described and synthesized in patent application US 2010/0136065.
Use will more particularly be made of particles of titanium dioxide that are treated with alumina and jojoba esters having the INCI name TITANIUM DIOXIDE (and) ALUMINA (and) JOJOBA ESTERS, such as the products sold under the name MPT-154-NJE8 or TTO-NJE8 by the company KOBO.
Preferably, the content of particles B in the composition according to the invention is between 0.1 % and 20%, preferably between 0.5% and 10% by weight and more preferably still between 0.5% and 10% by weight relative to the total weight of the composition.
OILY DISPERSION OF HYDROPHOBICALLY-MODIFIED PARTICLES C OF INORGANIC UV SCREENING AGENT
According to one particularly preferred embodiment of the invention, the applicant observed that the screening efficacy obtained with the combination of screening particles A and B as described previously could also be improved by using, in addition, an oily dispersion of hydrophobically-modified particles C of inorganic UV screening agent having a mean size of greater than 100 nm, said particles C being different from particles B.
The inorganic UV screening agent constituting these particles C is generally chosen from metal oxides, preferably titanium, zinc or iron oxides, or mixtures thereof and more particularly from titanium dioxide, zinc oxide and mixtures thereof. Particularly preferably, the inorganic UV screening agent is T1O2.
These metal oxides preferably have an elementary mean size generally of between 100 nm and 200 nm.
The hydrophobically-modified particles C of inorganic screening agent, in particular of metal oxide, may be coated by undergoing one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (titanium or aluminium alkoxides), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
As is known, silicones are organosilicon polymers or oligomers of linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and are essentially constituted of a repetition of main units in which the silicon atoms are linked together via oxygen atoms (siloxane bond), optionally substituted hydrocarbon-based radicals being directly attached to said silicon atoms via a carbon atom. The term "silicones" also includes the silanes required for their preparation, in particular alkylsilanes.
Preferably, use will be made of metal oxide particles coated with at least one linear or branched C12-C18 fatty acid and more particularly stearic acid.
The hydrophobically-modified particles C of inorganic UV screening agent may also be treated with other surface agents, in particular with cerium oxide, alumina, silica, aluminium compounds or silicon compounds, or mixtures thereof. The oil present in the oily dispersion of particles C of inorganic UV screening agent is preferably chosen from C12-C15 alkyl benzoates or triglycerides such as caprylic/capric triglyceride.
The oily dispersions of hydrophobically-modified particles C of inorganic UV screening agent may comprise, in addition, at least one dispersant such as, for example, polyhydrostearic acid.
Use will more particularly be made of the oily dispersions of particles C of Ti02 that are treated with a mixture of stearic acid, polyhydroxystearic acid and alumina below:
TITAN IUM DIOXIDE (and) C12-C15 Alkyl Benzoate (and) POLYHYDROXYSTEARIC ACID (and) STEARIC ACID (and) ALUMINA such as the product sold under the trade name SOLVEIL XT-100 by the company CRODA; - TITANIUM DIOXIDE (and) CAPRYLIC/CAPRIC TRIGLYCERIDE (and) POLYHYDROXYSTEARIC ACID (and) STEARIC ACID (and) ALUMINA such as the product sold under the trade name SOLVEIL XT-300 by the company CRODA.
Preferably, the content of oily dispersion of particles C in the composition according to the invention is between 0.1 % and 30%, preferably between 0.5% and 20% by weight and more preferably still between 1 % and 10% by weight relative to the total weight of the composition.
POLAR OILS According to one particularly preferred embodiment of the invention, the compositions may comprise at least one anhydrous phase comprising at least one polar oil.
The expression "anhydrous phase" is understood to mean any phase comprising less than 3% by weight of water, or less than 1 % by weight of water, or more particularly less than 0.5% by weight of water relative to the total weight of the composition, or is free of water.
The expression "polar oil" is understood to mean any lipophilic compound having, at 25°C, a solubility parameter 5d characteristic of dispersive interactions of greater than 16 and a solubility parameter δρ characteristic of polar interactions of strictly greater than 0. The solubility parameters 5d and δρ are defined according to the Hansen classification. For example, these polar oils may be chosen from esters, triglycerides and ethers.
The definition and calculation of the solubility parameters in the Hansen three- dimensional solubility space are described in the article by CM. Hansen: "The three dimensional solubility parameters", J. Paint Technol. 39, 105 (1967).
According to this Hansen space:
- 5D characterizes the LONDON dispersion forces derived from the formation of dipoles induced during molecular impacts;
- δρ characterizes the DEBYE interaction forces between permanent dipoles and also the KEESOM interaction forces between induced dipoles and permanent dipoles;
- 5h characterizes the specific interaction forces (such as hydrogen bonding, acid/base, donor/acceptor, etc.); and
- 5a is determined by the equation: 5a = (δρ 2 + 5h2)½ .
The parameters δρ, 5h, 6D and 5a are expressed in (J/cm3)½
The polar oil may be a volatile or non-volatile hydrocarbon-based, silicone and/or fluoro oil.
These oils may be of plant, mineral or synthetic origin.
The term "polar hydrocarbon-based oil" means an oil formed essentially from, or even constituted by, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
The term "silicone oil" means an oil containing at least one silicon atom, and especially containing Si-O groups.
The term "fluoro oil" means an oil containing at least one fluorine atom. Preferably, the polar oil according to the invention has a surface tension greater than 10 mN/m at 25°C and under atmospheric pressure. The surface activity is measured by static tensiometry using the Du Nouy ring.
The principle of the measurement is the following (measurement carried out at 25°C, at atmospheric pressure): The weight of the ring is neutralized by a tare. The ring is completely immersed in the liquid to be evaluated, then withdrawn very slowly until the force reaches its maximum. From this maximum force Fmax, the surface tension is calculated according to the equation: σ = Fmax / 4nR fcorr (r, R,p)
with fcorn correction factor of the ring depending on the geometry of the ring and the density p. The parameters r and R respectively denote the internal and external radii of the ring.
According to a first embodiment, the polar oil may be a non-volatile oil. In particular, the non-volatile polar oil may be chosen from the list of oils below, and mixtures thereof:
- hydrocarbon-based polar oils such as phytostearyl esters, such as phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutamate (AJINOMOTO, ELDEW PS203), triglycerides consisting of fatty acid esters of glycerol, in particular the fatty acids of which may have chain lengths ranging from C4 to C36, and especially from C18 to C36, these oils possibly being linear or branched, and saturated or unsaturated; these oils may especially be heptanoic or octanoic triglycerides, wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil (820.6 g/mol), corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil or musk rose oil; shea butter; or alternatively 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;
- synthetic ethers containing from 10 to 40 carbon atoms, such as dicaprylyl ether;
- hydrocarbon-based esters of formula RCOOR' in which RCOO represents a carboxylic acid residue comprising from 2 to 40 carbon atoms, and R' represents a hydrocarbon-based chain containing from 1 to 40 carbon atoms, such as cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate or isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate and palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol 2-diethyl hexanoate, and mixtures thereof, C12 to C15 alcohol benzoates, hexyl laurate, neopentanoic acid esters, for instance isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate and 2-octyldodecyl neopentanoate, isononanoic acid esters, for instance isononyl isononanoate, isotridecyl isononanoate and octyl isononanoate, oleyl erucate, isopropyl lauroyl sarcosinate, diisopropyl sebacate, isocetyl stearate, isodecyl neopentanoate, isostearyl behenate, and myristyl myristate;
- polyesters obtained by condensation of an unsaturated fatty acid dimer and/or trimer and of diol, such as those described in patent application FR 0 853 634, in particular such as dilinoleic acid and 1 ,4-butanediol. Mention may especially be made in this respect of the polymer sold by Biosynthis under the name Viscoplast 14436H (INCI name: dilinoleic acid/butanediol copolymer), or else copolymers of polyols and of dimer diacids, and esters thereof, such as Hailuscent ISDA;
- polyol esters and pentaerythritol esters, for instance dipentaerythrityl tetrahydroxystearate/tetraisostearate;
- fatty alcohols containing from 12 to 26 carbon atoms, for instance octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol and oleyl alcohol;
- C12-C22 higher fatty acids, such as oleic acid, linoleic acid and linolenic acid, and mixtures thereof;
- fluoro oils that are optionally partially hydrocarbon-based and/or silicone-based; - fatty acids containing from 12 to 26 carbon atoms, for instance oleic acid;
- dialkyl carbonates, the two alkyl chains possibly being identical or different, such as dicaprylyl carbonate sold under the name CETIOL CC®, by COGNIS; and
- non-volatile oils of high molecular weight, for example between 400 and 10 000 g/mol, in particular between 650 and 10 000 g/mol, for instance:
i) vinylpyrrolidone copolymers such as the vinylpyrrolidone/1 - hexadecene copolymer, ANTARON V-216 sold or manufactured by the company ISP (MW = 7300 g/mol),
ii) esters such as:
a) linear fatty acid esters with a total carbon number ranging from 35 to 70, for instance pentaerythrityl tetrapelargonate (MW = 697.05 g/mol), b) hydroxylated esters such as polyglycerol-2 triisostearate (MW = 965.58 g/mol),
c) aromatic esters such as tridecyl trimellitate (MW = 757.19 g/mol), C12-C15 alcohol benzoate, the 2-phenylethyl ester of benzoic acid, and butyloctyl salicylate,
d) esters of C24-C28 branched fatty acids or fatty alcohols such as those described in patent application EP-A-0 955 039, and especially triisoarachidyl citrate (MW = 1033.76 g/mol), pentaerythrityl tetraisononanoate (MW = 697.05 g/mol), glyceryl triisostearate (MW = 891 .51 g/mol), glyceryl tris(2- decyl)tetradecanoate (MW = 1 143.98 g/mol), pentaerythrityl tetraisostearate (MW = 1202.02 g/mol), polyglyceryl-2 tetraisostearate (MW = 1232.04 g/mol) or else pentaerythrityl tetrakis(2-decyl)tetradecanoate (MW = 1538.66 g/mol), e) esters and polyesters of dimer diol and of monocarboxylic or dicarboxylic acid, such as esters of dimer diol and of fatty acid and esters of dimer diol and of dimer dicarboxylic acid, such as Lusplan DD-DA5® and Lusplan DD- DA7® sold by the company NIPPON FINE CHEMICAL and described in patent application US 2004/175338, the content of which is incorporated into the present application by reference,
- and mixtures thereof.
Preferably the polar oil is chosen from C12-C15 alcohol benzoate, diisopropyl sebacate, isopropyl lauroyl sarcosinate, dicaprylyl carbonate, the 2-phenylethyl ester of benzoic acid, butyloctyl salicylate, 2-octyldodecyl neopentanoate, dicaprylyl ether, isocetyl stearate, isodecyl neopentanoate, isononyl isononate, isopropyl myristate, isopropyl palmitate, isostearyl behenate, myristyl myristate, octyl palmitate and tridecyl trimellitate.
Preferably, the polar oil is a C12-C15 alcohol benzoate.
The weight content of polar oil relative to the total weight of the composition is between 10% and 100%, preferably between 15% and 90%.
The "fatty phase" of the compositions according to the invention may also comprise a wax, an apolar oil or mixtures thereof.
The apolar oils and the waxes conventionally used in cosmetic compositions may be used in the compositions according to the present invention.
The compositions according to the invention may also comprise additional cosmetic and/or dermatological active agents. A person skilled in the art will select said active agent(s) as a function of the effect desired on the skin, the hair, the eyelashes, the eyebrows and the nails.
ADDITIVES The compositions in accordance with the present invention may also comprise standard cosmetic adjuvants chosen especially from organic solvents, ionic or nonionic, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoaming agents, fragrances, preserving agents, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, fillers, polymers, propellants, alkalinizing or acidifying agents or any other ingredient commonly used in the cosmetics and/or dermatological field.
Among the organic solvents that may be mentioned are lower alcohols and polyols. The latter may be chosen from glycols and glycol ethers, for instance ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol. Hydrophilic thickeners that may be mentioned include carboxyvinyl polymers, such as Carbopols (Carbomers) and the Pemulens (acrylate/C10-C30 alkyl acrylate copolymer); polyacrylamides, for instance the crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide/C13-C14 isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyl taurate copolymer/isohexadecane/polysorbate 80) by the company Seppic; 2-acrylamido- 2-methylpropanesulphonic acid polymers and copolymers, optionally crosslinked and/or neutralized, for instance poly(2-acrylamido-2-methylpropanesulphonic acid) sold by the company Clariant under the trade name Hostacerin AMPS (CTFA name: ammonium polyacryloyldimethyl taurate) or SIMULGEL 800 sold by the company SEPPIC (CTFA name: sodium polyacryloyldimethyl taurate/polysorbate 80/sorbitan oleate); copolymers of 2-acrylamido-2-methylpropanesulphonic acid and of hydroxyethyl acrylate, for instance SIMULGEL NS and SEPINOV EMT 10 sold by the company SEPPIC; cellulose derivatives such as hydroxyethyl cellulose; polysaccharides and especially gums such as xanthan gum; and mixtures thereof.
Lipophilic thickeners that may be mentioned include synthetic polymers, such as the poly(C10-C30 alkyl acrylates) sold under the names INTELIMER IPA 13-1 and INTELIMER IPA 13-6 by the company Landec, or else modified clays, such as hectorite and its derivatives, for instance the products sold under the name Bentone.
The compositions according to the invention may, in addition, also comprise additional cosmetic and dermatological active agents.
Among the active agents, mention may be made of:
- vitamins (A, C, E, K, PP, etc.) and derivatives or precursors thereof, alone or as mixtures;
- antioxidants;
- free-radical scavengers;
- antiglycation agents;
- calmatives;
- NO-synthase inhibitors;
- agents for stimulating the synthesis of dermal or epidermal macromolecules and/or for preventing their degradation;
- agents for stimulating fibroblast proliferation;
- agents for stimulating keratinocyte proliferation;
- muscle relaxants;
- tensioning agents;
- matting agents;
- keratolytic agents;
- desquamating agents;
- moisturizers, for instance polyols such as glycerol, butylene glycol or propylene glycol;
- antiinflammatory agents;
- agents that act on the energy metabolism of cells;
- insect repellents; - substance P or substance CRGP antagonists;
- hair-loss counteractants and/or hair restorers;
- anti-wrinkle agents. Of course, a person skilled in the art will take care to select the aforementioned optional additional compound(s) and/or the amounts thereof such that the advantageous properties intrinsically associated with the compositions in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
A person skilled in the art will select the said active agent(s) as a function of the effect desired on the skin, the hair, the eyelashes, the eyebrows and the nails.
Galenic forms
The aqueous compositions according to the invention may be prepared according to the techniques that are well known to those skilled in the art.
They may be in the form of a lotion, milk, cream, cream gel, aqueous gel, aqueous-alcoholic gel, cream or foam.
They may comprise, in addition, at least one fatty phase and may be in the form of a simple or complex emulsion (O/W, W/O, O/W/O or W/O/W) such as a milk, a cream or a cream gel. They may optionally be packaged as an aerosol and may be in the form of a spray.
The compositions according to the invention are preferably in the form of an oil-in- water or water-in-oil emulsion. The emulsification processes that may be used are of paddle or impeller, rotor- stator and high-pressure homogenizer (HPH) type.
To obtain stable emulsions with a low content of emulsifying compounds (oil/emulsifier ratio > 25), it is possible to make the dispersion in concentrated phase and then to dilute the dispersion with the rest of the aqueous phase.
It is also possible, via HPH (between 50 and 800 bar), to obtain stable dispersions with drop sizes that may be as small as 100 nm. The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The emulsifiers are appropriately chosen according to the emulsion to be obtained (W/O or O/W). The emulsions may also contain stabilizers of other types, for instance fillers, or gelling or thickening polymers.
For the O/W emulsions, examples of emulsifiers that may be mentioned include nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) esters of fatty acids and of glycerol; oxyalkylenated esters of fatty acids and of sorbitan; oxyalkylenated (oxyethylenated and/or oxypropylenated) esters of fatty acids, such as the PEG 100 stearate/glyceryl stearate mixture sold, for example, by ICI under the name Arlacel 165; oxyalkylenated (oxyethylenated and/or oxypropylenated) ethers of fatty alcohols; esters of sugars, such as sucrose stearate; or ethers of fatty alcohol and of sugar, in particular alkyl polyglucosides (APGs), such as decyl glucoside and lauryl glucoside, sold, for example, by the company Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearyl glucoside, optionally as a mixture with cetostearyl alcohol, sold, for example, under the name Montanov 68 by the company SEPPIC, under the name Tegocare CG90 by the company Goldschmidt and under the name Emulgade KE3302 by the company Henkel, and also arachidyl glucoside, for example in the form of a mixture of arachidyl alcohol, behenyl alcohol and arachidyl glucoside, sold under the name Montanov 202 by the company SEPPIC. According to one particular embodiment of the invention, the mixture of the alkyl polyglucoside as defined above with the corresponding fatty alcohol can be in the form of a self- emulsifying composition, for example as described in document WO-A-92/06778.
Among the other emulsion stabilizers, use may also be made of isophthalic acid or sulphoisophthalic acid polymers, and in particular phthalate/sulphoisophthalate/glycol copolymers, for example the diethylene glycol/phthalate/isophthalate/1 ,4-cyclohexanedimethanol copolymer (INCI name: Polyester-5) sold under the name Eastman AQ Polymer (AQ35S, AQ38S, AQ55S and AQ48 Ultra) by the company Eastman Chemical. Among the other emulsion stabilizers, mention may also be made of hydrophobically modified 2-acrylamido-2-methylpropanesulphonic acid polymers such as those described in patent application EP 1 069 142.
When it is an emulsion, the aqueous phase of this emulsion may comprise a nonionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008).
As emulsifying surfactants that can be used for the preparation of W/O emulsions, mention may be made, for example, of emulsifying surfactants having an HLB of less than or equal to 5 at 25°C.
The term HLB (hydrophilic lipophilic balance) is well known to those skilled in the art, and denotes the hydrophilic-lipophilic balance of a surfactant.
The HLB of the surfactant(s) used according to the invention is the HLB according to GRIFFIN, defined in the publication J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256. Non-limiting examples of surfactants with an HLB of less than or equal to 5 are especially given in the publication entitled McCutcheon's Emulsifiers & Detergents, 1998 International Edition, MC Publishing Company, in the chapter entitled HLB Index. As W/O emulsifying surfactants, examples that may be mentioned include alkyl esters or ethers of sorbitan, of polyol, of glycerol or of sugars; silicone surfactants, for instance dimethicone copolyols, such as the mixture of cyclomethicone and of dimethicone copolyol, sold under the name DC 5225 C by the company Dow Corning, and alkyldimethicone copolyols such as laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by the company Dow Corning; cetyldimethicone copolyol, such as the product sold under the name Abil EM 90R by the company Goldschmidt, and the mixture of cetyldimethicone copolyol, of polyglyceryl isostearate (4 mol) and of hexyl laurate, sold under the name ABIL WE 09 by the company Goldschmidt. One or more coemulsifiers may also be added thereto, which may be chosen advantageously from the group comprising polyol alkyl esters. Non-silicone emulsifiers will be preferred, especially alkyl esters or ethers of sorbitan, of glycerol, of polyol or of sugars.
Polyol alkyl esters that may especially be mentioned include polyethylene glycol esters, for instance PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135 by the company ICI.
Glycerol and/or sorbitan esters that may be mentioned include, for example, polyglyceryl isostearate, such as the product sold under the name Isolan Gl 34 by the company Goldschmidt, sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company ICI, sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof.
According to one particularly preferred embodiment of the invention, the compositions are in the form of a water-in-oil emulsion.
The expression "water-in-oil emulsion" is understood to mean a composition constituted of an oily dispersing continuous phase and an aqueous dispersed discontinuous phase.
As W/O emulsifiers, use will more particularly be made of polyglycerolated diesters and polyesters especially chosen from:
- Polyglyceryl-3 Polyricinoleate (Akoline PGPR sold by the company AarhusKarlshamn AB),
- Polyglyceryl-4 Polyricinoleate (Sunsoft 818DG from the company Taiyo Kagaku Company, Ltd.),
- Polyglyceryl-5 Polyricinoleate (Sunsoft AZ-18 from the company Taiyo Kagaku Company, Ltd.),
- Polyglyceryl-6 Polyricinoleate (Nikkol Hexaglyn PR-15 from the company Nikko Chemicals Co. , Ltd. ; PELEMOL 6GPR from the company Phoenix Chemical, Inc. ;
Polycare P 5 from the company Biogenico World Wide; Sunsoft 818H, 818SK and 818TY from the company Taiyo Kagaku Company, Ltd.), - Polyglyceryl-10 Polyricinoleate (Phytoglyn AO from the company Maruzen Pharmaceuticals Co., Ltd.),
- Polyglyceryl-2 Diisostearate (Prisorine 3792 from the company Croda Europe, Ltd.; Dermol DGDIS from the company Alzo/Bernel Chemical),
- Polyglyceryl-3 Diisostearate (Lameform TGI sold by the company COGNIS),
- Polyglyceryl-6 Diisostearate (Emalex DISG-6 from the company Nihon Emulsion Company, Ltd.),
- Polyglyceryl-10 Diisostearate (Emalex DISG-10 from the company Nihon Emulsion Company, Ltd.),
and mixtures thereof.
Use will even more particularly be made of a mixture of Polyglyceryl-3 Polyricinoleate and of Polyglyceryl-3 Diisostearate. The examples that follow serve to illustrate the invention.
Examples
Compositions 1 to 2 below were prepared. The ingredients are used as weight percentages of active material relative to the total weight of the composition.
Phase Ingredients Ex. 1 Ex. 2
(outside the
invention)
Ai TOCOPHEROL 0.50 0.50
SIMMONDSIA CHINENSIS
(JOJOBA) SEED OIL 8.00 8.00
POLYGLYCERYL-3
DIISOSTEARATE 2.00 2.00
BEESWAX 0.50 0.50
ORYZANOL
(TSUNO RICE FINE CHEMICALS) 3.00
DICAPRYLYL ETHER 8.00 8.00
POLYGLYCERYL-3
POLYRICINOLEATE 2.00 2.00
TITANIUM DIOXIDE (and)
POLYHYDROXYSTEARIC ACID
(and) ALUMINA (and) STEARIC
A2
ACID (and) CAPRYLIC/CAPRIC
TRIGLYCERIDE
(SOLAVEIL XT 300 CRODA) 3.80 3.80
Bi SODIUM PHYTATE 0.15 0.15
POTASSIUM SORBATE 0.30 0.30
WATER (QS) 47.01 44.01
GLYCEROL 5.00 5.00
SODIUM BENZOATE 0.50 0.50
B2 XANTHAN GUM 0.20 0.20
B3 MAGNESIUM SULPHATE 1 .50 1 .50
B4 CITRIC ACID
0.04 0.04
C TALC (and) TITANIUM DIOXIDE
(and) MAGNESIUM STEARATE
(and) ALUMINIUM HYDROXIDE
(TTC 30 MYOSHI) 9.65 9.65
ALUMINIUM OXIDE HYDRATED
(and) TITANIUM DIOXIDE (and)
JOJOBA ESTERS
(KOBO MPT-154-NJE8) 5.85 5.85
D ALCOHOL
5.00 5.00 Emulsion preparation method:
Ai is heated at 75/80°C - (clear solution). At the same time, all the compounds of Bi are weighed into another beaker and stirred using a deflocculator until solubilized. B2 is sprinkled in and stirred until solubilized/gelled. B3 and then B4 are added. B is introduced into A using an emulsifying device slowly (1 to 2 min approximately) at up to 2000 rpm and then for 6 to 7 min at 3000 rpm. It is cooled using a butterfly shaft. C is added. At a temperature below 30°C, D is added over 5 min.
In vitro protocol for evaluating the screening efficacy In vitro SPF
The sun protection factor (SPF) is determined according to the "in vitro" method described by B. L. Diffey in J. Soc. Cosmet. Chem. 40, 127-133 (1989). The measurements were carried out using a UV-2000S spectrophotometer from the company Labsphere. Each composition is applied to a rough plate of PMMA, in the form of a homogeneous and even deposit in a proportion of 0.6 mg/cm2
In vitro PPD index
The index of UV-A protection, the PPD (persistent pigment darkening) method, which measures the skin colour observed 2 to 4 hours after exposure of the skin to UV-A rays, is particularly recommended and used. This method has been adopted since 1996 by the Japanese Cosmetic Industry Association (JCIA) as official test procedure for the UV-A labelling of products and is frequently used by test laboratories in Europe and the United States (Japan Cosmetic Industry Association Technical Bulletin. Measurement Standards for UVA protection efficacy. Issued November 21 , 1995 and effective as of January 1 , 1996).
The UVAppo Sun protection factor (UVApPD PF) is expressed mathematically by the ratio of the UV-A radiation dose necessary to reach the pigmentation threshold with the UV-screening agent (MPPDp) to the UV-A radiation dose necessary to reach the pigmentation threshold without UV-screening agent (MPPDnp).
MPPDp
UVAPPD PF =
MPPDnp
The measurements were carried out according to an in vitro test using a UV- 2000S spectrophotometer from the company Labsphere. Each composition is applied to a rough plate of PMMA, in the form of a homogeneous and even deposit in a proportion of 0.6 mg/cm2. Results
TABLE I
Figure imgf000025_0001
These results show that the addition of gamma-oryzanol to the aqueous composition 2 of the invention, based on screening composite particles, makes it possible to increase the efficacy, in particular the SPF, significantly relative to Example 1 without gamma-oryzanol.
Examples 3 and 4 (outside the invention):
Compositions 3 to 4 below were prepared. The ingredients are used as weight percentages of active material relative to the total weight of the composition.
Ingredients Ex. 3 Ex. 4
(outside the (outside the
invention) invention)
TOCOPHEROL 0.50 0.50
POLYGLYCERYL-3
DIISOSTEARATE 2.00 2.00
BEESWAX 0.50 0.50
ORYZANOL
(TSUNO RICE FINE CHEMICALS) 3.00
DICAPRYLYL ETHER 10.00 10.00
POLYGLYCERYL-3
POLYRICINOLEATE 2.00 2.00
TITANIUM DIOXIDE (and)
ISOHEXADECANE (and)
TRIETHYLHEXANOIN (and)
ALUMINIUM STEARATE (and)
ALUMINA (and)
POLYHYDROXYSTEARIC ACID
(SOLAVEIL CT 200 LQ (CRODA) 25.00 25.00
POTASSIUM SORBATE 0.30 0.30
GLYCEROL 5.00 5.00
SODIUM BENZOATE 0.50 0.50
XANTHAN GUM 0.20 0.20
MAGNESIUM SULPHATE 1 .50 1 .50
Figure imgf000026_0001
These compositions were evaluated with respect to the screening efficacy.
Figure imgf000026_0002
These results show that the addition of gamma-oryzanol to the aqueous composition 4 of the invention, based on conventional titanium oxide pigments, does not make it possible to increase the efficacy significantly relative to Example 1 without gamma-oryzanol.

Claims

1. Composition containing, in a cosmetically acceptable medium:
a) at least one aqueous phase; and
b) at least composite particles A having a size between 0.1 and 30 pm comprising a matrix and an inorganic UV screening agent, said inorganic screening agent being present in a content ranging from 1 % to 70% by weight relative to the total weight of the composite particle; and
c) gamma-oryzanol or a plant extract containing it.
2. Composition according to Claim 1 , in which the matrix comprises one or more organic and/or inorganic materials.
3. Composition according to Claim 1 or 2, where the composite particles A are constituted of a matrix comprising an organic and/or inorganic material, in which matrix particles of inorganic UV screening agent are included.
4. Composition according to Claim 1 or 2, where the composite particles A contain a matrix made of an organic and/or inorganic material, which matrix is covered with a layer of inorganic UV screening agent connected to the matrix with the aid of a binder.
5. Composition according to any one of Claims 1 to 4, in which the inorganic UV screening agent is chosen from metal oxides.
6. Cosmetic composition according to Claim 5, in which the inorganic UV screening agent is chosen from metal oxides, in particular from titanium, zinc or iron oxides and more particularly titanium dioxide (T1O2).
7. Composition according to any one of Claims 1 to 6, in which the organic materials constituting the matrix are chosen from:
- acrylic polymers such as polymethyl methacrylate and acrylic copolymers comprising other types of monomers such as styrene;
- polyamides, such as nylon.
8. Composition according to any one of Claims 1 to 7, in which the inorganic materials constituting the matrix are chosen from:
- silica;
- talc;
- mica;
- alumina.
9. Composition according to any one of Claims 1 to 8, where the matrix of the composite particles A contains a material or mixture of materials chosen from:
- alumina;
- alumina/triethoxycaprylylsilane mixture;
- talc;
- silica; mica.
10. Composition according to any one of Claims 1 to 9, in which the composite particles A are platelet-shaped.
11. Composition according to any one of Claims 1 to 10, in which the oily phase comprises at least one polar oil, preferably having a surface tension greater than or equal to 10 mN/m at 25°C and under atmospheric pressure and more particularly dicaprylyl ether.
12. Composition according to any one of Claims 1 to 1 1 , comprising, in addition, particles B of inorganic UV screening agent that are hydrophobically treated with at least one oil or one wax of natural origin and optionally, in addition, an oily dispersion of hydrophobically-modified particles C of inorganic UV screening agent having a mean size of greater than 0.1 pm, said particles C being different from particles B.
13. Composition according to any one of Claims 1 to 12, characterized in that it is in the form of a water-in-oil emulsion.
14. Composition according to Claim 13, comprising at least one emulsifying surfactant preferably having an HLB of less than or equal to 5 at 25°C and more preferably chosen from alkyl esters or ethers of sorbitan, of polyol, of glycerol or of sugars.
15. Composition according to Claim 14, where the emulsifying surfactant is chosen from polyglycerolated diesters and polyesters and especially chosen from:
- Polyglyceryl-3 Polyricinoleate,
- Polyglyceryl-4 Polyricinoleate,
- Polyglyceryl-5 Polyricinoleate,
- Polyglyceryl-6 Polyricinoleate,
- Polyglyceryl-10 Polyricinoleate,
- Polyglyceryl-2 Diisostearate,
- Polyglyceryl-3 Diisostearate,
- Polyglyceryl-6 Diisostearate,
- Polyglyceryl-10 Diisostearate,
and mixtures thereof and more particularly a mixture of Polyglyceryl-3 Ricinoleate and of Polyglyceryl-3 Diisostearate.
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EP3154510A4 (en) * 2014-06-11 2017-11-01 L'oreal Composition for protecting keratin materials from sun
US10653588B2 (en) 2014-06-11 2020-05-19 L'oreal Composition for protecting the keratin materials from sun
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