FR2971148A1 - COSMETIC COMPOSITION IN EMULSION FORM WATER-IN-OIL WITHOUT EMULSIFIER SILICONE CONTAINING NON-SPHERICAL PARTICLES OF COMPOSITE MATERIAL - Google Patents

Abstract

The subject of the present invention is a composition in the form of a water-in-oil emulsion containing, in a cosmetically acceptable medium, at least non-spherical composite particles of average size of between 100 nm and 30 μm comprising a matrix and an inorganic UV filter. said inorganic filter being present in a content ranging from 1% to 70% by weight relative to the total weight of the composite particle, said composition containing no silicone emulsifier.

Description

The subject of the present invention is a cosmetic composition in the form of a water-in-oil emulsion containing, in a cosmetically acceptable medium, at least one of the water-in-oil emulsion compositions. non-spherical composite particles having a size of between 100 nm and 30 μm comprising a matrix and a filter material. This composition is for topical use and more particularly for the photo-protection of the skin and / or hair against ultraviolet (UV) radiation.

It is known that the luminous radiations of wavelength lying between 280 nm and 400 nm allow the browning of the human epidermis, and that the wavelength rays more particularly between 280 and 320 nm, known under the name UV -B, cause erythema and burns that can affect the development of natural tanning.

For these reasons, as well as for aesthetic reasons, there is a constant demand for control means of this natural tan to thereby control the color of the skin: it is therefore necessary to filter the UV-B radiation.

It is also known that the UV-A rays, of wavelength between 320 and 400 nm, which cause browning of the skin, are capable of inducing an alteration thereof, particularly in the case of a skin sensitive or skin continuously 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 cutaneous aging.

Thus, for aesthetic and cosmetic reasons, such as the preservation of the natural elasticity of the skin, for example, more and more people want to control the effect of UV-A on their skin. It is therefore desirable to also filter the UV-A radiation.

In order to ensure protection of the skin and keratin materials against UV radiation, antisolar compositions, comprising organic screening agents, active in the UV-A and active in the UV-B, are generally used.

There are many cosmetic products comprising one or more inorganic and / or organic UV filters.

These antisolar compositions are quite often in the form of an oil-in-water emulsion (ie a cosmetically and / or dermatologically acceptable support consisting of an aqueous dispersant continuous phase and a dispersed discontinuous phase. oily) because of their pleasant touch (close to water) and their presentation in the form of milk or non-fat cream.

However, one of the drawbacks of oil-in-water emulsions is that they very easily lose their effectiveness in UV protection when they come into contact with water; in fact, the filters they contain in their aqueous phase are entrained by the water, during bathing at sea or in the pool for example, or in the shower or during the practice of water sports and the overall photoprotective power of these compositions are greatly diminished.

Therefore, in some cases where a particularly high and durable protection is sought, as for the skins of children or for sensitive skin, it is preferred to use water-in-oil compositions which have good persistence to the skin. water and thus retain a very good photoprotective power even after several baths.

The water-in-oil emulsions generally contain emulsifiers to stabilize the dispersion of the discontinuous aqueous phase in the oily phase and to obtain a homogeneous composition. Silicone emulsifiers, such as silicone copolyols, have the disadvantage of being sometimes incompatible with the fatty phases containing polar oils of the emulsions.

For children's skin or sensitive skin, it is most often used fine metal oxide particles such as titanium dioxide (TiO2) 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 100 nm, preferably between 5 nm and 100 nm, preferably between 10 nm and 100 nm, and preferably between 15 and 50 nm. .

One of the major drawbacks of inorganic filters lies in the fact that the conventional antisolar formulations based on metal oxide pigments lead, after application to the skin, to an irregular, inhomogeneous or even coarse distribution of said pigments on this skin. , which can affect the quality of the desired global photoprotective effect. This poor distribution of the filtering metal oxide pigments found on the surface of the skin is often linked to the fact that there is, at the level of the initial composition itself (before application), a substantial lack of homogeneity ( poor dispersion of the pigment in its support).

The applications FR2882371, WO2006 / 083326 and WO 98/37964 describe various processes for manufacturing composite particles made of a material comprising nanoparticles of metal oxides, such as titanium dioxide.

WO 2006/061835 discloses compositions comprising spherical composites based on metal oxide and a hydrophobic polymer.

In the field of cosmetics, we know the application EP 1388550 which aims the use of composite particles comprising a core formed of a metal oxide coated with a silicone or fluorinated compound and its use as a photoprotective cosmetic composition and the application WO 98/22539 which describes a solar filter 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 120 nm and being covered with a layer of oxide with a thickness ranging from 1 to 300 nm.

Solar formulations are known which can contain, as filter system, spherical particles of composite material of average size of between 2 and 7 μm, TiO2 encapsulated in spherical silica particles such as those sold under the name EOSPOLY TR by CREATION COLOR or the denomination SUNSIL T50 by SUNJIN CHEMICAL. These filtering materials have the drawbacks of leading to formulations whose effectiveness is insufficient in the formulations in the form of water-in-oil emulsions.

There remains a need for UV sunscreen compositions in the form of water-in-oil emulsion without silicone emulsifier that are effective in photoprotection and do not have the disadvantages presented above. Unexpectedly and advantageously, the inventors have shown that this need can be met by means of the compositions according to the present invention.

A first subject of the present invention relates to a composition in the form of a water-in-oil emulsion containing in a cosmetically acceptable medium at least non-spherical composite particles of average size of between 100 nm and 30 μm comprising a matrix and a inorganic UV filter, said inorganic filter being present in a content ranging from 1% to 70% by weight relative to the total weight of the composite particle, said composition 30 not containing silicone emulsifier.

The composition according to the present invention is effective in photoprotection.

The following description and examples have other advantages, aspects and properties of the present invention.

Definitions

The following definitions are used in this text. The compositions according to the present invention are photoprotective compositions for filtering UV radiation, these compositions are also called sunscreen compositions or sunscreen compositions.

By "water-in-oil emulsion" is meant a composition consisting of an oily dispersant continuous phase and an aqueous dispersed discontinuous phase. 40 By "cosmetically acceptable" is meant compatible with the skin and / or its integuments or mucous membranes which has a pleasant color, odor and feel and which does not generate unacceptable discomfort (tingling, tightness, redness), likely to divert the consumer from using this composition.

By "silicone emulsifier" is meant any emulsifying agent comprising in its structure at least one silicon atom, for example polyoxyalkylenated silicones such as PEG-10 Dimethicone. By "not containing silicone emulsifier" is meant containing less than 10/0 by weight of silicone emulsifier, preferably less than 0.50 / 0 by weight and better still less than 0.10 / 0 by weight with respect to total weight of the composition or even free of silicone emulsifier. By "average size" of the particles is meant the parameter D [4.3] measured using a "Mastersizer 2000" granulometer (Malvern). The light intensity scattered by the particles as a function of the angle at which they are illuminated is converted into a size distribution according to Mie's theory. The parameter D [4.3] is measured; it is the average diameter of the sphere having the same volume as the particle. For a spherical particle, we often speak of "average diameter".

"Elementary average size" means the size of non-aggregated particles. "Non-spherical" means particles in three dimensions (length, width, thickness or height) for which the ratio of the largest dimension to the smallest dimension is greater than 1.2. The particle size of the invention is evaluated by scanning electron microscopy and image analysis. They comprise parallelepipedal (rectangular or square surface), discoidal (circular surface) or ellipsoidal (oval surface) particles, characterized by three dimensions: a length, a width and a height. When the shape is circular, the length and width are the same and correspond to the diameter of a disc, while the height corresponds to the thickness of the disc. When the surface is oval, the length and the width respectively correspond to the major axis and the minor axis of an ellipse and the height corresponds to the thickness of the elliptical disk formed by the wafer. When it is a parallelepiped, the length and the width may be of identical or different dimensions: when they are of the same size, the shape of the surface of the parallelepiped is square; otherwise, the shape is rectangular. As for the height, it corresponds to the thickness of the parallelepiped.

Composite Particles The non-spherical composite particles used according to the present invention, also referred to as "composite particles", comprise a matrix and an inorganic UV filter. The matrix comprises one or more organic and / or inorganic materials. The inorganic UV filter is generally chosen from metal oxides.

According to a preferred variant, the matrix consists essentially of organic and / or inorganic material.

The matrix of filtering particles of the invention may be organic or inorganic in nature.

The organic materials that can be used to form the matrix of the non-spherical filtering particles are chosen from the group formed by poly (meth) acrylates, polyamides, silicones, polyurethanes, polyethylenes, polypropylenes, polystyrenes, polyhydroxyalkanoates, polycaprolactams, poly (butylene) succinates and polysaccharides. , polypeptides, polyvinylalcohols, polyvinyl resins, fluoropolymers, waxes, polyesters, polyethers, and mixtures thereof.

Preferably, the organic materials that can be used include: - triethoxycaprylylsilane - acrylic polymers such as polymethyl methacrylate and acrylic copolymers comprising other types of monomers such as styrene, - polyamides such as nylon.

The inorganic materials that can be used in the non-spherical composite particle matrix are chosen from the group formed by mica, synthetic mica, talc, sericite, boron nitride, glass, calcium carbonate and barium sulfate. hydroxyapatite, silica, silicate, magnesium sulfate, magnesium carbonate, magnesium trisilicate, aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clays, synthetic clays and mixtures thereof.

Preferably, these inorganic materials are chosen from: - silica, - talc, - mica, - alumina.

The inorganic UV filters that can be used in the composite particle are chosen from metal oxides.

Preferably, these metal oxides are selected from titanium dioxide TiO 2, zinc oxide ZnO, and iron oxide FeO. These metal oxides are in the form of particles of average size generally less than 200 nm. These metal oxides can also be in the form of layers, preferably multilayers of average thickness generally less than 200 nm.

In a particularly preferred manner, the inorganic UV filter is TiO2.

Advantageously, the TiO2 particles used have an average size of less than or equal to 100 nm.

The mass content of metal oxide in the particles of the invention is between 10/0 and 700/0, preferably between 20/0 and 650/0, and more preferably between 3% and 60%.

The non-spherical composite particles of the invention are characterized by three dimensions of which: the smallest is greater than 100 nm, preferably 300 nm and even more preferably 500 nm, the largest is less than 20 micrometers, preferably 15 micrometers and more better 10 micrometers.

The ratio of the largest 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.

The non-spherical composite particles that can be used according to the invention will preferably be platelet-forming.

By "platelet" is meant a parallelepipedal shape.

Preferably, the content of composite particles of the composition according to the invention ranges from 1 to 700/0, preferably from 1.5 to 45%, preferably from 2 to 20% by weight relative to the total weight of the composition. cosmetic.

They can be smooth, rough, or porous.

The platelet composite particles preferably have an average thickness of between 100 nm and 10 μm, the average length is generally between 500 nm and 30 microns and the average width between 40 500 nm and 30 microns.

The thickness is the smallest of the dimensions, the width the average dimension, and the length is the largest of the dimensions.

According to a first variant, the composite particles contain a matrix comprising an organic and / or inorganic material in which particles of inorganic UV filter are included. According to a first variant, the composite particles consist of a matrix comprising an organic and / or inorganic material in which particles of inorganic UV filter are included.

According to this first variant, the inorganic UV filter particles are characterized by an average elementary size generally less than 200 nm. Advantageously, the metal oxide particles used have an average elementary size of less than or equal to 100 nm.

According to a second variant, the composite particles contain a matrix made of an organic and / or inorganic material covered with at least one inorganic UV filter layer connected to the matrix by means of a binder.

According to this second variant, the average thickness of the inorganic UV filter layer is generally about ten nanometers. The average thickness of the inorganic UV filter layer is advantageously between 1 and 200 nm, preferably between 10 and 200 nm.

The composite particles used according to the invention have a size of between 100 nm and 30 μm, preferably between 300 nm and 20 μm, and still more preferably between 500 nm and 10 μm.

According to a third variant, the nonspherical composite particles contain an inorganic UV filter coated with at least one layer of an organic and / or inorganic material. According to this third variant, the particles of inorganic UV filter are characterized by an average elementary size generally between 1 and 200 nm. Advantageously, the metal oxide particles used have an average elementary size of between 10 nm and 100 nm. Preferably, the content of composite particles of the composition according to the invention ranges from 1 to 700/0, preferably from 1.5 to 45%, preferably from 2 to 20% by weight relative to the total weight of the composition. cosmetic composition.

The mass content of metal oxide in the particles of the invention is between 10/0 and 700/0, preferably between 20/0 and 650/0, and more preferably between 3% and 60%.

According to a variant, in particular when the composite particles comprise a matrix covered with a UV filter layer, the composite particles may also be covered with an additional coating, in particular chosen from biodegradable or biocompatible materials, lipid materials such as for example, surfactants or emulsifiers, polymers, and oxides. The matrix may also be formed of one or more organic or inorganic materials. It can then be a continuous phase of materials such as an alloy, that is to say a continuous phase in which the materials are no longer dissociable, or a discontinuous phase of materials, for example consisting of an organic or inorganic material covered with a layer of another organic or inorganic material different.

Preferably, the inorganic UV filter used in the composite particle is chosen from metal oxides, in particular from titanium, zinc or iron oxides and more particularly titanium dioxide (TiO 2).

Preferably, the matrix of the composite particle contains a material or a mixture of materials chosen from: - SiO 2, - alumina, - mica, - the mixture alumina / triethoxycaprylylsilane, - talc, - PMMA (polymethyl methacrylate) , - Nylon.

More preferably, the matrix of the composite particle consists of a material or a mixture of materials chosen from: - alumina, - the mixture alumina / triethoxycaprylylsilane - talc, - silica, - mica. .

Among the composite particles that can be used according to the invention, mention may also be made of the following particles: TiO 2 -containing composite particles and a MATLAKE OPA alumina matrix marketed by the company SENSIENT LCW; composite particles containing TiO 2 and an alumina matrix / triethoxycaprylylsilane trade name MATLAKE OPA AS marketed by the company SENSIENT LCW, - Composite particles containing ultrafine TiO2 particles deposited on the surface of talc platelets of commercial name TTC 30 marketed by the company MYOSHI KASEI. Composite particles containing ultrafine TiO2 particles deposited on the surface of talc platelets of commercial name SILSEEM MISTYPEARL YELLOW marketed by the company NIHON KOKEN KOGYO (NKK).

Preferably, the oily phase of the emulsions according to the invention comprises at least one polar oil.45 POLAR OILS

The term "polar oil" is intended to mean any lipophilic compound having, at 25 ° C., a bd solubility parameter characteristic of dispersive interactions greater than 16 and a solubility parameter 8p characteristic of polar interactions greater than strictly 0. The solubility parameters bd and 8p are defined according to Hansen's 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 C. M. HANSEN: "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967).

According to this Hansen space: - Vp characterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular shocks; - 8p characterizes the DEBYE interaction forces between permanent dipoles as well as the KEESOM interaction forces between induced dipoles and permanent dipoles; bh characterizes the specific interaction forces (hydrogen bond, acid / base, donor / acceptor type, etc.); and - ba is determined by the equation: ba = (bp2 + Sh2) 'i2. The parameters 8p, 8h, 8p and ba are expressed in (J / cm3) '2. The polar oil may be a hydrocarbon, silicone and / or fluorinated, volatile or non-volatile oil. These oils can be of vegetable, mineral or synthetic origin.

By "polar hydrocarbon oil" is meant an oil formed essentially or even consisting of carbon and hydrogen atoms, and optionally oxygen, nitrogen, and not containing a silicon atom or of fluorine. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups.

By silicone oil is meant an oil containing at least one silicon atom, and in particular containing Si-O groups.

By fluorinated oil is meant 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 at atmospheric pressure.

The surface activity is measured by static tensiometry using the Du Noüy ring.

The principle of the measurement is as follows (measurement carried out at 25 ° C., at atmospheric pressure 45). The weight of the ring is neutralized by a tare. The ring is immersed entirely in the liquid to be evaluated, then removed very slowly until the force reaches its maximum. From this maximum force Finax, the surface tension is calculated according to the equation:

6 = Finax / 47tR torr (r, R, p)

with torr: correction factor of the ring according to the geometry of the ring and the density p.

The parameters r and R respectively designate the inner and outer 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 following list of oils, and their mixtures: polar hydrocarbon oils such as phytostearyl esters, such as phytostearyl oleate, isostearate of physostearyl and Iauroyl glutamate / octyldodecyl / phytostearyl (AJINOMOTO, ELDEW PS203), triglycerides consisting of esters of fatty acids and glycerol, in particular of which the fatty acids may have chain lengths ranging from C4 to C36, and in particular from C18 to C36, these oils being linear or branched, saturated or unsaturated; these oils may especially be heptanoic or octanoic triglycerides, wheat germ, sunflower, grape seed, sesame (820.6 g / mol), maize, apricot, castor oil, shea butter oils. avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, squash, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose; shea butter; or alternatively caprylic / capric acid triglycerides, such as 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 having from 10 to 40 carbon atoms, such as dicaprylyl ether, hydrocarbon esters of formula RCOOR 'in which RCOO represents a carboxylic acid residue containing from 2 to 40 carbon atoms, and R' represents a hydrocarbon chain containing from 1 to 40 carbon atoms, such as cetostearyl octanoate, esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate 40, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 4-diheptanoate and ethyl palmitate 2-45 hexyl, alkyl benzoate , polyethylene glycol diheptanoate, propylglycol diethyl 2-hexanoate and mixtures thereof, C12-C15 alcohol benzoates, hexyl Iaurate, neopentanoic acid esters such as isodecyl neopentanoate, isotridecyl neopentanoate, neopentanoate Isostearyl, octyl-2-dodecyl neopentanoate, esters of isononanoic acid such as isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, oleyl erucate ; lauroyl isopropyl sarcosinate, diisopropyl sebaccate, isoketyl stearate, isodecyl neopentanoate, isostearyl behenate, myristyl myristate; the polyesters obtained by condensation of dimer and / or trimer of unsaturated fatty acid and of diol, such as those described in patent application FR 0 853 634, such as in particular dilinoleic acid and 1,4-diol; butanediol. Mention may in particular be made of the polymer marketed by Biosynthis under the name Viscoplast 14436H (INCI name: dilinoleic acid / butanediol copolymer), or the copolymers of polyols and diacid dimers, and their esters, such as Hailuscent ISDA, polyol esters and pentaerythritol esters, such as dipentaerythritol tetrahydroxystearate / tetraisostearate; - fatty alcohols having from 12 to 26 carbon atoms, such as octyl dodecanol, 2-butyloctanol, 2-hexyl decanol, 2- undecyl pentadecanol, oleic alcohol; higher C12-C22 fatty acids, such as oleic acid, linoleic acid, linolenic acid, and mixtures thereof; fluorinated oils that may be partially hydrocarbon-based and / or silicate; fatty acids having from 12 to 26 carbon atoms, such as oleic acid; di-alkyl carbonates, the 2 alkyl chains 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 ranging from 400 to 10,000 g / mol, in particular from 650 to 10,000 g / mol, for example: i) copolymers of vinylpyrrolidone such as vinylpyrrolidone / 1-copolymer; hexadecene, ANTARON V-216 sold or manufactured by ISP (MW = 7300 g / mol), -ii) esters such as: a) linear fatty acid esters having a total carbon number ranging from 35 to 70 such as 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 alcohols benzoate, benzoic acid 2-phenyl ethyl ester, butyl octyl salicylate, d) fatty alcohol esters or d C24-C28 branched fatty acids such as those described in application EP-A-0 955 039, and in particular triisoarachidyl citrate (MW = 1033.76 g / mol ), pentaerythrityl tetraisonanoate (MW = 697.05g / mol), glyceryl triisostearate (MW = 891.51 g / mol), glyceryl tri-2-tetradecanoate (MW = 1143.98 g / mol), tetraisostearate 45 pentaerythrityl (MW = 1202.02 g / mol), polyglyceryl-2 tetraisostearate (MW = 1232.04 g / mol) or pentaerythrityl tetradecyl-2 tetradecylate (MW = 1538.66 g / mol), e) esters and polyesters of dimer diol and of mono- or dicarboxylic acid, such as esters of diol dimer and of fatty acid and esters of dimer diols and dimer of dicarboxylic acid, such as Lusplan DD-DA5® and Lusplan DD-DA7® marketed by NIPPON FINE CHEMICAL and described in application US 2004-175338, the contents of which are incorporated herein by reference - and mixtures thereof.

The polar oil is preferably chosen from C12-C15 alcohols benzoate, diisopropyl sebaccate, lauroyl isopropyl sarcosinate, dicaprylyl carbonate, benzoic acid 2-phenyl ethyl ester and butyl octyl. salicylate, octyl-2-dodecyl neopentanoate, dicaprylyl ether, isoketyl stearate, isodecyl neopentanoate, isononyl isononate, isopropyl myristate, isopropylpalmitate, isostearyl behenate, myristyl myristate, octylpalmitate, and tridecyltrimillitate. preferred way, the polar oil is dicaprylyl ether.

The "fatty phase" of the compositions according to the invention may also comprise a wax, an apolar oil or their mixtures. By wax is meant a compound that is solid or substantially solid at room temperature and whose melting point is generally greater than 35 ° C.

The apolar oils and waxes conventionally used in cosmetic compositions can 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 ingredients. The skilled person will choose said active (s) depending on the desired effect on the skin, hair, eyelashes, eyebrows, nails.

Advantageously, the composition according to the invention further comprises at least one organic UV filter.

Among the organic UV filters, there are in particular the following hydrophobic or hydrophilic UV filters.

The term "hydrophobic filter" is understood to mean any lipophilic filter, namely capable of being completely dissolved in the molecular state in a liquid fatty phase or of being solubilized in colloidal form (for example in micellar form) in a liquid phase. liquid fatty phase - any insoluble filter both in a liquid fatty phase and in a liquid aqueous phase.

The term "hydrophilic filter" is understood to mean any filter capable of being completely dissolved in the molecular state in a liquid aqueous phase or of being solubilized in colloidal form (for example in micellar form) in a liquid aqueous phase.

Hydrophobic UV-A filters

Derivatives of dibenzoylmethane: Butyl Methoxydibenzoylmethane sold in particular under the trade name "PARSOL 1789" by DSM Nutritional Products, Inc .; Isopropyl Dibenzoylmethane;

Aminobenzophenones: - n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) -benzoate sold especially under the trade name "Uvinul A +" by BASF; 1,1 '- (1,4-piperazinediyl) bis [1- [2- [4- (diethylamino) -2-hydroxybenzoyl] phenyl] -15-methanone (CAS 919803-06-8)

Anthranilic derivatives: - Menthyl anthranilate sold in particular under the trade name "Neo Heliopan MA" by SYMRISE; 4,4-Diarylbutadiene derivatives: 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene;

Merocyanine Derivatives: 25-Octyl-5-N, N-diethylamino-2-phenysulfonyl-2,4-pentadienoate;

In the context of the invention, and according to a particular embodiment, the following hydrophobic filters (A) are used: butyl methoxydibenzoylmethane; and / or n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate;

The hydrophobic organic screening agents (A) when present are present at levels ranging from 0.01% to 30% by weight and preferably from 0.1% to 20% by weight relative to the total weight of the composition.

Hydrophilic UV-A filters

- Terephthalylidene Dicamphor Acid Sulfonic Acid manufactured under the name "MEXORYL SX" by CHIMEX,

- bis-benzoazolyl derivatives as described in patents EP 669 323, and US 2,463,264 and more particularly the compound Disodium Phenyl Dibenzimidazo tetra-sulfonate sold under the trade name "NEO HELIOPAN AP" by SYMRISE;

The preferred water-soluble UVA filter is Terephthalylidene Dicamphor Acid Sulfonic Acid. 10 20 35 40 45 Hydrophobic UV-B filters

Para-aminobenzoates: - Ethyl PABA; - Ethyl Dihydroxypropyl PABA; Ethylhexyl Dimethyl PABA (ESCALOL 507 from ISP);

Salicylic derivatives: Homosalate sold in particular under the name "Eusolex HMS" by Rona / EM Industries; Ethylhexyl salicylate sold in particular under the name "NEO HELIOPAN OS" by SYMRISE; Dipropylene glycol salicylate sold in particular under the name "DIPSAL" by SCHER; TEA Salicylate and under the name "NEO HELIOPAN TS" by SYMRISE;

Cinnamates Ethylhexyl Methoxycinnamate sold in particular under the trade name "PARSOL MCX" by DSM Nutritional Products, Inc.; Isopropyl Methoxy cinnamate; Isoamyl Methoxy cinnamate sold in particular under the trade name "NEO HELIOPAN E 1000" by SYMRISE; Diisopropyl Methylcinnamate; Cinnoxate; Glyceryl Ethylhexanoate Dimethoxycinnamate; Derivatives of 13,13'-diphenylacrylate Octocrylene, sold in particular under the trade name "UVINUL N539" by BASF; Etocrylene, sold in particular under the trade name "UVINUL N35" by BASF;

Derivatives of benzylidene camphor: 3-Benzylidene camphor manufactured under the name "MEXORYL SD" by CHIMEX; Methylbenzylidene camphor sold in particular under the name "Eusolex 6300" by Merck; Polyacrylamidomethyl Benzylidene Camphor manufactured under the name "MEXORYL SW" by CHIMEX; Triazine derivatives: Ethylhexyl triazone sold in particular under the trade name Uvinul T150 by BASF; Diethylhexylbutamido triazone sold in particular under the trade name "UVASORB HEB" by SIGMA 3V; 2,4,6-tris (dineopentyl 4'-amino benzalmalonate) -s-triazine; 2,4,6-tris (diisobutyl 4'-amino benzalmalonate) -s-triazine; 2,4-bis (dineopentyl 4'-amino benzalmalonate) -6- (n-butyl 4'-aminobenzoate) -s-triazine; 2,4-bis (4'-amino-n-butyl benzoate) -6- (aminopropyltrisiloxane) -s-triazine; the symmetrical triazine filters described in US Pat. No. 6,225,467, WO 2004/085412 (see compounds 6 and 9) or the "Symetrical Triazine Derivatives" document IP.COM Journal, IP.COM INC. WEST HENRIETTA, NY, US (September 20 2004) including 2,4,6-tris- (biphenyl) -1,3,5-triazine (especially 2,4,6-tris (biphenyl-4-yl-1,3,5-triazine) and 2,4,6-tris (terphenyl) -1,3,5-triazine, these last two filters being described in the applications of BEIERSDORF WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007 , WO 2006/034992, WO 2006/034985).

Imidazoline Derivatives: Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate, Benzalmalonate Derivatives: Benzalmalonate-functional polyorganosiloxanes such as Polysilicone-15 sold in particular under the trade name "PARSOL SLX" by DSM Nutritional Products, Inc.; Di-neopentyl 4'-methoxybenzalmalonate; In the context of the invention and according to a particular embodiment, the following hydrophobic UV-B filters are used in the composition according to the invention: - ethylhexylsalicylate; Octocrylene; - Ethylhexyl triazone.

Hydrophilic UV-B Filters The following p-aminobenzoic acid (PABA) derivatives: PABA, Glyceryl PABA and PEG-25 PABA sold in particular under the trade name Uvinul P25 by BASF. Phenylbenzimidzaole Sulfonic Acid sold in particular under the trade name "Eusolex 232" by MERCK, ferulic acid, salicylic acid, DEA methoxycinnamate, benzylidene camphor Sulfonic acid manufactured under the name "MEXORYL SL" by CHIMEX, camphor Benzalkonium Methosulfate manufactured under the name "MEXORYL SO" by CHIMEX.

The preferred hydrophilic UVB filter is Phenylbenzimidazole Sulfonic Acid. Mixed hydrophobic UVA and UVB filters Derivatives of benzophenone Benzophenone-1 sold in particular under the trade name "UVINUL 400" by BASF; Benzophenone-2 sold in particular under the trade name Uvinul D50 by BASF Benzophenone-3 or Oxybenzone sold in particular under the trade name Uvinul M40 by BASF; Benzophenone-6 sold in particular under the trade name "Helisorb 11" by Norquay; Benzophenone-8 sold in particular under the trade name "Spectra-Sorb UV-24" by American Cyanamid; Benzophenone-10; Benzophenone-11; Benzophenone-12; Derivatives of benzotriazole phenyl: - Drometzole Trisiloxane sold in particular under the name Silatrizole by Rhodia Chimie or manufactured under the name Meroxyl XL by the company Chimex; Methylene bis-benzotriazolyl tetramethylbutylphenol, sold in solid form, for example under the trade name "MIXXIM BB / 100" by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion, especially under the trade name "TINOSORB M" by CIBA SPECIALTY CHEMICALS;

Derivatives bis-resorcinyl triazines Bis-Ethylhexyloxyphenol Methoxyphenyl triazine sold in particular under the trade name "Tinosorb S" by Ciba Geigy;

Benzoxazole derivatives: 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine sold in particular under the name Uvasorb K2A by Sigma 3V;

The hydrophobic organic UVA and UVB preferential filters are chosen from: - Drometzole Trisiloxane; Methylene bis-benzotriazolyl tetramethylbutylphenol; Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine.

Hydrophilic mixed UVA and UVB filters

Derivatives of benzophenone containing at least one sulphonic radical such as benzophenone-4 sold in particular under the trade name "UVINUL MS 40" by BASF, Benzophenone-5 and Benzophenone-9.

The organic screening agents, when present, are present at levels ranging from 0.01% to 30% by weight and preferably from 0.1% to 20% by weight relative to the total weight of the composition of the invention. .

Additives

The compositions in accordance with the present invention may furthermore comprise conventional cosmetic adjuvants, chosen in particular from organic solvents, ionic or nonionic, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers, stabilizers, emollients and silicones. , anti-foam agents, perfumes, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, fillers, polymers, propellants, basifying or acidifying agents or any other ingredient usually used in the field cosmetic and / or dermatological.

Among the organic solvents, mention may be made of lower alcohols and polyols. These can be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.

As hydrophilic thickeners, mention may be made of carboxyvinyl polymers such as Carbopols (Carbomers) and Pemulen (acrylate / C10-C30-alkylacrylate copolymer); polyacrylamides, for example crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide / C13-C14 isoparaffin / Laureth 7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by the company Seppic ; polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally crosslinked and / or neutralized, such as Poly (2-acrylamido-2-methylpropanesulphonic acid) marketed by the company Clariant under the trademark "Hostacerin AMPS" (name CTFA: ammonium polyacryloyldimethyl taurate) or SIMULGEL 800 sold by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate / polysorbate 80 / sorbitan oleate); copolymers of 2-acrylamido-2-methylpropanesulphonic acid and of hydroxyethyl acrylate, such as SIMULGEL NS and SEPINOV EMT 10 sold by the company SEPPIC; cellulosic derivatives such as hydroxyethylcellulose; polysaccharides and especially gums such as Xanthan gum; and their mixtures.

Mention may be made, as lipophilic thickeners, of synthetic polymers such as the poly C10-C30 alkyl acrylates sold under the name "IPA INTELIMER 13-1" and "INTELIMER IPA 13-6" by the company Landec, or modified clays such as I hectorite and its derivatives, such as the products marketed under the Bentone name.

The compositions according to the invention may also comprise, in addition, additional cosmetic and dermatological active ingredients.

Among the active ingredients, mention may be made of: vitamins (A, C, E, K, PP) and their derivatives or precursors, alone or in mixtures, antioxidant agents; 17 - anti-radical agents; anti-glycation agents; the soothing agents; the NO-synthase inhibitors; agents stimulating the synthesis of dermal or epidermal macromolecules and / or preventing their degradation; agents stimulating the proliferation of fibroblasts; agents stimulating the proliferation of keratinocytes; - muscle relaxants; tensing agents, mattifying agents, keratolytic agents, desquamating agents; - Moisturizing agents such as polyols such as glycerin, butylene glycol, propylene glycol. anti-inflammatory agents; agents acting on the energetic metabolism of cells; insect repellents; antagonists of substances P or CRGP. - anti-hair loss and / or hair regrowth agents - anti-wrinkle agents. Of course, one skilled in the art will take care to choose the optional additional compound (s) mentioned above and / or their amounts in such a way that the advantageous properties intrinsically attached to the compositions in accordance with the invention are not, or substantially, not, altered by the addition or additions envisaged.

The skilled person will choose the active agent (s) depending on the desired effect on the skin, hair, eyelashes, eyebrows, nails.

Qalenic forms

The water-in-oil emulsions according to the invention can be prepared according to the techniques well known to those skilled in the art.

The emulsification processes that can be used are of the pale type or helix, rotor-stator and HHP.

The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The emulsions may also contain other types of stabilizers, for example fillers, gelling or thickening polymers.

Preferably, emulsifying surfactants having an HLB of less than or equal to 5 at 25 will be used.

The term HLB (Hydrophilic Lipophilic Balance) is well known to those skilled in the art, and refers to the hydrophilic-lipophilic balance of a surfactant.

The HLB of the surfactant (s) used according to the invention is HLB according to GRIFFIN defined in J. Soc. Cosm. Chem. 1954 (Volume 5), pages 249-256.

Nonlimiting examples of HLB surfactants up to 5 are, for example, given in Mc Cutcheon's Emulsifiers & Detergents, 1998 International Edition, MC Publishing Company, chapter HLB Index.

As emulsifying surfactants that may be used for the preparation of W / O emulsions, mention may be made, for example, of alkyl esters or ethers of sorbitan, of polyol, of glycerol or of sugars, in particular polyglycerolated esters and polyesters. One or more coemulsifiers may also be added, which advantageously may be selected from the group consisting of alkylated polyol esters.

Examples of alkylated polyol esters that may be mentioned include polyethylene glycol esters such as PEG-30 dipolyhydroxystearate, such as the product marketed under the name Arlacel P135 by the company ICI.

Examples of glycerol esters that may be mentioned are polyglycerol isostearate, such as the product sold under the name Isolan GI 34 by the company Goldschmidt.

As sorbitan esters, mention may be made of sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company ICI; sorbitan isostearate and glycerol, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof.

Polyglycerolated diesters and polyesters, chosen in particular from: - Polyglyceryl-3-Polyricinoleate (Akoline PGPR sold by Aarhus Karlshamn AB), - Polyglyceryl-4-Polyricinoleate (Sunsoft 818DG from Taiyo Kagaku Company, Ltd), will be used more preferentially. Polyglyceryl-S-Polyricinoleate (Sunsoft AZ-18 from Taiyo Kagaku Company, Ltd.), Polyglyceryl-6-Polyricinoleate (Nikkol Hexaglyn PR-15 from Nikko Chemicals Co., Ltd.). PELEMOL 6GPR from Phoenix Chemical, Inc., Polycare P 5 from Biogenico World Wide, Sunsoft 818H, 818SK, 818TY from Taiyo Kagaku Company, Ltd.) - Polyglyceryl-10-Polyricinoleate (Phytoglyn AO). Maruzen 45 Pharmaceuticals Co., Ltd.) - Polyglyceryl-2 Diisostearate (Prisorine 3792 from Croda Europe, Ltd. Dermol DGDIS from Alzo / Bern) Chemical) - Polyglyceryl-3-Diisostearate (Lameform TGI sold by the company COGNIS), - Polyglyceryl-6 Diisostearate (Emalex DISG-6 from Nihon Emulsion Company, Ltd.) - Polyglyceryl-10 Diisostearate (Emalex DISG-10 from Nihon Emulsion Company, Ltd.) and mixtures thereof

A mixture of Polyglyceryl-3-Polyricinoleate and Polyglyceryl-3-Diisostearate will be used more particularly.

Examples

The following compositions 1 to 3 were produced. The ingredients are used in weight percentage of active ingredient relative to the total weight of the composition. Phase Ingredients EX 1 EX2 EX 3 off the invention invention A POLYGLYCERYL-3 2 2 2 DIISOSTEARATE POLYGLYCERYL-3 2 2 2 POLYRICINOLEATE BEE WAX 0.5 0.5 0.5 OIL OF JOJOBA - - 10 ALMOND OIL SOFT 11 11 - DICAPRYL ETHER 8 8 10 TOCOPHEROL 0.5 0.5 0.5 B1 GLYCERIN 5 5 WATER qs 100 qs 100 qs 100 PRESERVATIVES 0.2 0.2 0.2 B2 MAGNESIUM SULFATE 1.5 1.5 1.5 B3 XANTHAN GUM 0.2 0.2 0.2 B4 CITRIC ACID 0.037 0.037 0.037 C EOSPOLY TR 10% MA - - SUNSIL TIN 50 - 100/0 MA _ MATLAKE OPA - _ 100/0 MA ALCOHOL 5 These compositions were evaluated on the filtering efficiency of the emulsion preparation method:

A is heated to 75/80 ° C (clear solution). At the same time, all the B1 compounds are weighed in another beaker and stirred under deflocculant until solubilization. B2 is dusted and stirred until solubilization / gelation. B3 and then B4 are added. Introduce B into A under an emulsifier slowly (1 to 2 min approximately) until 2000T then 6 to 7min 3000T. It is cooled under butterfly axis. C. is added. At a temperature below 30 ° C., D is added for 5 min.

In vitro evaluation protocol for filtering efficiency

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 regular deposit at a rate of 1 mg / cm 2.

Results TABLE 1 Examples SPF in vitro Example 1 6.57 +/- 0.19 Example 2 2.5 +/- 0.06 Example 3 28.7 +/- 4 (invention) These results show that only the use of a platelet-shaped composite material in an inverse emulsion makes it possible to obtain a filtering system of high efficiency with a low level of filters, unlike emulsions 1 and 2 comprising a filtering composite material of spherical shape. 21 35

Claims (15)

REVENDICATIONS1. Composition in the form of a water-in-oil emulsion containing, in a cosmetically acceptable medium, at least non-spherical composite particles of average size of between 100 nm and 30 μm comprising a matrix and an inorganic UV filter, said inorganic filter being present in a content ranging from 1/0 to 70% by weight relative to the total weight of the composite particle, said composition containing no silicone emulsifier. 2. Composition according to claim 1 wherein the matrix comprises one or more organic and / or inorganic materials. 3. The composition of claim 1 or 2 wherein the composite particles consist of a matrix comprising an organic and / or inorganic material in which inorganic UV filter particles are included. A composition according to claim 1 or 2 wherein the composite particles contain a matrix of an organic and / or inorganic material coated with an inorganic UV filter layer connected to the matrix by means of a binder. 5. Cosmetic composition according to any one of claims 1 or 2 wherein the composite particle contains an inorganic UV filter coated with at least one layer of an organic material and / or inorganic. 25 6. Composition according to any one of claims 1 to 5, wherein the inorganic UV filter is selected from metal oxides. 7. Cosmetic composition according to claim 6 wherein the inorganic UV filter is selected from metal oxides, in particular from oxides of titanium, zinc or iron and more particularly titanium dioxide (TiO2). 8. Composition according to any one of claims 1 to 7, wherein 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. 9. Composition according to any one of claims 1 to 8, wherein the inorganic materials constituting the matrix are selected from - silica, - talc, - mica, - alumina. 45 10. Composition according to any one of claims 1 to 9, wherein the matrix of composite particles contains a material or a mixture of materials selected from: alumina, alumina / triethoxycaprylylsilane mixture talc, la silica, - mica .. 11. Composition according to any one of claims 1 to 10, wherein the composite particles are platelet. 12. Composition according to any one of claims 1 to 11, wherein 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 at atmospheric pressure and especially dicaprylyl ether. 13. Composition according to any one of claims 1 to 11, additionally containing an organic UV filter. 14. Composition according to any one of claims 1 to 13, comprising at least one emulsifying surfactant preferably having an HLB less than or equal to 5 at 25 ° C and more preferably chosen from alkyl esters or ethers of sorbitan, polyol, glycerol or sugars. 15. A composition according to claim 14, wherein the emulsifying surfactant is chosen from polyglycerolated diesters and polyesters and in particular 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 Polyglyceryl-3-diisostearate.