JP2019055997A - Composite particles comprising metal-doped inorganic uv filter, and compositions containing them - Google Patents

Abstract

To provide composite particles comprising a metal-doped inorganic UV filter, and compositions containing them.SOLUTION: The present invention concerns composite particles comprising: i) a matrix containing at least one inorganic and/or at least one organic material; and ii) at least one inorganic UV filter doped with at least one transition metal. The present invention also concerns a composition containing, in a physiologically acceptable medium, at least the composite particles as defined above. The invention also concerns a cosmetic method for caring and/or making up a keratinous substance, which comprises applying, to the surface of the keratinous substance, at least one composition as defined above, and more particularly a cosmetic method for: a) limiting the darkening of the skin and improving the color and uniformity of the complexion, and b) treating aging of keratinous substances.SELECTED DRAWING: None

Description

The subject of the present invention is
i) a matrix containing at least one inorganic material and / or at least one organic material;
ii) to a composite particle comprising at least one inorganic UV filter doped with at least one transition metal.

  The subject of the invention is also a composition containing at least the above-defined composite particles in a physiologically acceptable medium.

  This composition is intended for topical use and more specifically aims to photoprotect the skin and / or hair from ultraviolet (UV) radiation.

  Light irradiation with a wavelength of 280 nm to 400 nm tans the human epidermis, and more specifically 280 nm to 320 nm, known as UV-B rays, can cause skin burns and erythema that can harm the progression of natural tanning. It is known to cause.

  For these reasons and for aesthetic reasons, there is a certain need for a method of controlling this natural sunburn and thereby controlling the color of the skin. Therefore, UV-B radiation should be shielded.

  It is also known that UV-A light with a wavelength of 320-400 nm, which causes skin tanning, tends to cause harmful changes in it, especially in sensitive skin or skin that has been continuously exposed to solar radiation. Yes. UV-A rays cause the generation of wrinkles that lead to premature skin aging, particularly losing skin elasticity.

  Therefore, for aesthetic and cosmetic reasons, it is increasingly desirable to control the effects of UV-A rays on the skin, for example, to protect the natural elasticity of the skin. Therefore, it is desirable to shield UV-A radiation.

There are many cosmetics containing one or more inorganic and / or organic UV screening agents. Inorganic particulates based on metal oxides such as titanium dioxide (TiO ₂ ) are usually used for children's skin or sensitive skin to protect the skin from ultraviolet radiation.

  The metal oxide fine particles generally have an average basic particle size of 0.1 μm or less, preferably 0.005 to 0.1 μm, more preferably 0.01 to 0.1 μm, and preferentially 0.015 to 0.05 μm. However, the UVA and UVB filter effectiveness of this particle is also limited.

  There are also cosmetics containing one or more spherical and / or non-spherical shielding composite particles having a particle size of more than 0.1 μm, and they have the following patent applications: WO2012105723, WO2012105060, WO2012105059, WO2011016140, WO2011016143, FR2971152, WO2012104160 and WO2012104161 It is described in. However, the UVA and UVB filter effectiveness of these composites is also limited. Furthermore, its cosmetic properties during application are completely satisfactory especially considering that the smooth feel during application of the composition on the skin can be changed to a greasy and / or sticky feel. is not.

  There are also metal oxide particles doped with transition metals having an average basic particle size of 0.001 to 0.5 μm, which are described in the following patent applications: WO9960994, WO0140114 and WO2005 / 002538. Its cosmetic properties during application are also not completely satisfactory, especially considering that the smooth feel after applying the composition on the skin can be changed to a greasy and / or sticky feel.

WO2012105723 WO2012105060 WO2012105059 WO2011016140 WO2011016143 FR2971152 WO2012104160 WO2012104161 WO9960994 WO0140114 WO2005 / 002538 WO-A-92 / 06778 EP1069142 FR2315991 FR 2416008 WO2007 / 068371 WO2008 / 155059 US5624663 US5237071 US5166355 GB2303549 DE19726184 EP893119 EP0832642 EP1027883 EP1300137 DE10162844 WO93 / 04665 DE19855649 EP0967200 DE19746654 DE19755649 EP-A-1008586 EP1133980 EP133981 WO04 / 006878 WO05 / 058269 WO06 / 032741 EP-A-0823418 EP-A-1341752 EP0841341 US6225467 WO2004 / 085412 WO06 / 035000 WO06 / 034982 WO06 / 034991 WO06 / 035007 WO2006 / 034992 WO2006 / 034985 EP-A-0518773 US4077441 US4850517

Mat. Sci. (1997) 36, 6001 ~ 6008 Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965) J. Soc. Cosm. Chem. 1954 (5), 249-256 McCutcheon's Emulsifiers & Detergents, 1998 International Edition, MC Publishing Company "Symmetrical Triazine Derivatives" IP.COM Journal, IP.COM INC West Henrietta, NY, US (September 20, 2004) Cosmetics & Toiletries, February 1990, 105, 53-64 B.L.Diffey, J. Soc. Cosmet. Chem. 40, 127-133, (1989)

  Thus, there is still a need to find new UV shielding materials containing inorganic UV filters that provide more effective photoprotection in both UVA and UVB and do not have the above disadvantages.

Surprisingly, advantageously, we have:
i) a matrix containing at least one inorganic material and / or at least one organic material;
ii) It has been shown that this need can be met by novel composite particles comprising at least one inorganic UV filter doped with at least one transition metal.

The subject of the present invention is
i) a matrix containing at least one inorganic material and / or at least one organic material;
ii) to a composite particle comprising at least one inorganic UV filter doped with at least one transition metal.

  The subject of the invention is also a composition containing at least the composite particles defined above in a physiologically acceptable medium.

The present invention also relates to a cosmetic method for caring for and / or making up keratin materials, comprising the step of applying at least one composition as defined above to the surface of said keratin materials, more particularly
a) limit skin darkening, improve facial skin color and uniformity, and
b) It also relates to a cosmetic method for treating aging of keratin substances.

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

Definitions The following definitions are used herein.

  The composition according to the present invention is a photoprotective composition intended to shield UV radiation, which composition is also known as sunscreen composition or sun protection composition.

  The phrase `` physiologically acceptable '' has any unacceptable discomfort (stimulation, stiffness or redness) that has a favorable color, smell and feel and is likely to discourage consumers from using this composition. Without compatibility, it is meant to be compatible with human keratin materials, especially the skin and / or its appendages or mucous membranes.

  The phrase “average particle size” of the particles is considered to mean the parameter D [4,3] measured using a “Mastersizer 2000” particle size analyzer (Malvern). The light intensity scattered by the particles according to the angle of illumination is converted into a particle size distribution according to Mie theory. The parameter D [4,3] is measured, which is the average diameter of a sphere with the same volume as the particle. For spherical particles, one will often refer to “average diameter”.

  The phrase “average basic particle size” means the particle size of particles that are not agglomerated.

  The phrase “human keratinous substance” means skin (body, face, area around eyes), hair, eyelashes, eyebrows, body hair, nails, lips or mucous membranes.

  The phrase “inorganic UV filter” means any compound that does not contain any carbon atoms in its chemical structure and can block UV radiation from 280 to 400 nm.

"One inorganic UV filters doped with at least one transition metal (i.e., TiO _2, metal oxides such as ZnO)" phrase at least for providing luminescence trap sites and / or killer sites By any inorganic UV filter compound comprising a host lattice incorporating one transition metal is meant. Luminescent trap sites and / or killer sites will be understood as foreign ions designed to trap electrons and positively charged holes, and thus inhibit migration. Doped metal oxides and methods for their preparation are described in WO9960994 and WO0140114.

Composite Particles The composite particles according to the present invention can be selected from spherical, non-spherical, or mixtures thereof.

  The term “spherical” is taken to mean that the sphericity index of the particle, ie the ratio of its maximum diameter to its minimum diameter, is less than 1.2.

  The term “non-spherical” refers to particles in three-dimensional space (length, width and thickness or height) where the ratio of the longest dimension to the shortest dimension is greater than 1.2. The particle size of the present invention is determined by scanning an electron microscope and analyzing the image. This includes particles of parallelepiped shape (rectangular or square surface), disc shape (circular surface) or elliptical (oval surface), characterized by three dimensions: length, width and height. When the shape is circular, the length and width are the same and correspond to the diameter of the disc, whereas the height corresponds to the thickness of the disc. When the surface is oval, the length and width correspond to the major and minor axes of the ellipse, respectively, and the height corresponds to the thickness of the elliptical disk formed by the platelets. In the case of a parallelepiped, the length and width may be the same or different. If they are the same size, the shape of the parallelepiped face is a square, otherwise the shape is a rectangle. The height corresponds to the thickness of the parallelepiped.

  The composite particles according to the present invention may be a single layer or a multilayer.

  The composite particles according to the invention preferably have an average particle size of 0.1-30 μm, preferably 0.1-20 μm, and even more preferentially 0.1-10 μm.

  According to a first variant, the composite particles contain a matrix comprising organic and / or inorganic materials in which matrix particles of inorganic UV screening agents are included. According to this embodiment, the matrix has inclusions and the inorganic UV screening agent particles are in the matrix inclusions.

  According to a second variant, the composite particles contain a matrix made of organic and / or inorganic materials, the matrix being at least one layer that may be bonded to the matrix using a binder. It is at least partially coated with an inorganic UV screening agent.

  According to a third variant, the composite particles contain an inorganic UV screening agent at least partly coated with at least one layer of organic and / or inorganic material.

  The matrix may also be formed from one or more organic or inorganic materials. In this case, this is the absence of a continuous phase of a material such as an alloy, i.e. a continuous phase in which the material can no longer dissociate, or a material composed of an organic or inorganic material, for example coated with another different organic or inorganic material layer. It may be a continuous phase.

  According to one variant, the composite particles are in particular biodegradable or biocompatible materials, fatty substances, such as surfactants or emulsifiers, especially when the composite particles comprise a matrix coated with a layer of UV screening agent. It may be further coated with an additional coating selected from polymers and oxides.

  Preferably, the content of the composite particles in the composition according to the present invention is 1% to 70% by weight, preferably 1.5% to 50% by weight, more preferably 2% by weight to the total weight of the composition. It is in the range of 40% by mass.

Non-spherical composite particles The organic material that can be used to form the matrix of non-spherical shielding particles is selected from the group consisting of polyamides, silicones, polysaccharides, polyvinyl derivatives, waxes and polyesters, and mixtures thereof.

Of the organic materials that can be used, the following are preferred:
-Triethoxycaprylylsilane, and
-Ethylene / vinyl acetate copolymer.

Inorganic materials that can be used in the matrix of non-spherical composite particles are selected from the group consisting of mica, synthetic mica, talc, silica, aluminum oxide, boron nitride, kaolin, hydrotalcite, mineral clay and synthetic clay, and mixtures thereof Is done. Preferably, these inorganic materials are selected from:
-Silica,
-Talc, and
-Alumina.

The non-spherical composite particles of the present invention are characterized by three dimensions:
The minimum is preferably greater than 0.1 μm, more preferably greater than 0.3 μm, even better is greater than 0.5 μm, and
The maximum is preferably less than 30 μm, more preferably 20 μm, even better 10 μm.

  The ratio of the largest dimension to the smallest dimension is generally above 1.2.

  The dimensions of the particles of the present invention are determined by scanning electron microscopy and image analysis.

  Non-spherical shielding composite particles that can be used in accordance with the present invention will preferably be platelet-shaped.

  The term “platelet shape” means a parallelepiped shape.

  This can be smooth, rough, or porous.

  The composite particles in the form of platelets preferably have an average thickness of 0.1 to 10 μm, an average length of generally 0.5 to 30 μm, and an average width of 0.5 to 30 μm.

  The thickness is the smallest dimension, the width is the middle dimension, and the length is the longest dimension.

  According to a first variant, the composite particles contain a matrix comprising organic and / or inorganic materials in which matrix particles of inorganic UV screening agents are included.

  According to a second variant, the composite particles are a matrix made of an organic and / or inorganic material at least partially coated with at least one layer of inorganic UV screening agent bonded to the matrix using a binder Containing.

  According to this second variant, the average thickness of the layer of inorganic UV screening agent is generally about 10 nanometers.

  The average thickness of the layer of inorganic UV screening agent is advantageously from 0.001 to 0.2 μm, preferably from 0.01 to 0.15 μm.

  According to a third variant, the non-spherical composite particles contain an inorganic UV screening agent coated with at least one layer of organic and / or inorganic material.

Preferably, the matrix of composite particles contains a material or mixture of materials selected from:
SiO ₂ ,
alumina,
A mixture of alumina / triethoxycaprylylsilane,
Talc and nylon.

More preferably, the matrix of composite particles is formed from a material or mixture of materials selected from:
alumina,
A mixture of alumina / triethoxycaprylylsilane,
Talc and silica.

Spherical composite particles According to a first variant, the spherical composite particles contain a core comprising at least one organic material and / or one inorganic material, which contains matrix particles of an inorganic UV screening agent. .

  According to a second variant, the spherical composite particles contain a core comprising at least one organic and / or inorganic material, which core may be bound to the matrix using a binder. The layer is at least partially coated with an inorganic UV screening agent.

  According to this second variant, the average thickness of the layer of inorganic UV screening agent is generally from 0.001 to 0.2 μm, preferably from 0.01 to 0.15 μm.

  According to a third variant, the spherical composite particles contain an inorganic UV screening agent core at least partially coated with at least one layer of organic and / or inorganic material.

  The inorganic material that can be used in the matrix of spherical composite particles according to the present invention can be selected from the group consisting of glass, silica and aluminum oxide, and mixtures thereof.

  Organic materials that can be used to form the matrix are cellulose, poly (meth) acrylate, polyamide, silicone, polyurethane, polyethylene, polypropylene, polystyrene, polycaprolactam, polysaccharides, polypeptides, polyvinyl derivatives, waxes, polyesters, and polyethers As well as a mixture thereof.

  Spherical composite particles are characterized by an average diameter of 0.1 μm to 30 μm, preferably 0.2 μm to 20 μm, more preferably 0.3 μm to 10 μm, advantageously 0.5 μm to 10 μm.

The inorganic material or organic material may be hollow or porous. The porosity of the material, by the BET ^{method, 0.05m 2 / g~1500m 2 / g} , more preferentially 0.1m ² / g~1000m ² / g, even more preferentially 0.2 m ^2/500 m is It may be characterized by a specific surface area of ² / g.

Preferably, the matrix of spherical composite particles contains a material or mixture of materials selected from:
-SiO ₂ ,
-Cellulose,
-Polymethyl methacrylate,
-Copolymers of styrene and (meth) acrylic acid C ₁ / C ₅ alkyl derivatives,
-Polyamide such as nylon.

Preferably, the matrix of spherical composite particles contains porous or non-porous spherical particles of crosslinked polymethyl methacrylate polymer as the organic material as follows:
-Product SSX-102 (registered trademark) sold by Sekisui Plastics Co., Ltd.
-Products sold under the trade name TECHPOLYMER MBP-8 (registered trademark) by Sekisui Plastics Co., Ltd., products sold under the trade name GANZ PEARL GMP-0800 (registered trademark), and Porous spherical particles of cross-linked polymethyl methacrylate polymer (average particle size 2-15 μm and specific surface area 75-95 m ² / g) such as products sold by SENSIENT under the trade name COVABEAD LH 85®.

  According to a preferred embodiment of the present invention, the composite particles used according to the present invention are spherical composite particles containing a core comprising at least one organic material and / or at least one inorganic material, said core being Partially coated with at least one layer of inorganic UV filter doped with at least one transition metal.

Preparation Process The composite particles according to the present invention can be prepared by a mechanochemical fusion method.

  The mechanochemical fusion method means a method of causing fusion between subjects by applying mechanical force such as impact force, friction force, or shear force to a large number of subjects.

  The mechanochemical fusion method can be performed by an apparatus including a rotating chamber and a fixed internal part having a scraper, such as a mechanofusion system commercially available from Hosokawa Micron Corporation of Japan.

  The hybridizer method is preferably used as the mechanochemical fusion method.

  The hybridizer method was developed in the 1980s. The hybridizer method is a part of a mechanochemical fusion method in which a mechanical force is applied to a large number of particles to cause a mechanochemical reaction to produce composite particles.

  According to the hybridizer method, the mechanical force is applied by a high-speed rotor that can have a diameter of 10 cm to 1 m and can rotate at a speed of 1,000 rpm to 100,000 rpm. Therefore, the hybridizer method can be defined as a mechanochemical fusion method using such a high-speed rotor. The hybridizer method is carried out in air or under dry conditions. Therefore, since the rotor rotates at a high speed, a high-speed air flow can be generated near the rotor. However, some liquid materials can be subjected to the hybridizer method with solid materials. The term “hybridizer method” is used as a technical term.

  The hybridizer method can be performed using, for example, a hybridization system marketed by Nara Machinery Co., Ltd. in Japan. In this system, at least two kinds of particles, usually core particles and fine particles, are dried under dry conditions. In a chamber with a high-speed rotor having a plurality of blades to disperse the particles in the chamber and to give the particles mechanical and thermal energy (e.g., compression, friction, and shear stress) 1-10. Minutes, preferably 1 to 5 minutes. As a result, one type of particles (eg, fine particles) is embedded or fixed on the other type of particles (eg, core particles) to form composite particles. The particles are preferably subjected to electrostatic treatment such as shaking to produce an “ordered mixture” in which one type of particles spreads and covers the other type of particles. The hybridizer method can also be carried out using a theta composer marketed by the Deoksugaku workshop in Japan.

  The hybridizer method can also be carried out using Composi Hybrid (registered trademark) or Mechano Hybrid (registered trademark) marketed by Nippon Coke Industries, Ltd.

Doped inorganic UV filter The inorganic UV filter used according to the present invention is preferably composed of metal oxide particles, preferably zinc oxide particles (ZnO), titanium dioxide particles (TiO ₂ ), iron oxide particles (FeO), And mixtures thereof.

Preferably, TiO ₂ particles (amorphous or rutile and / or anatase crystalline) are used. The rutile type is more preferable because it has better photostability than the anatase type.

  These metal oxides doped with at least one transition metal preferably have a basic average particle size of 0.001 to 0.2 μm, advantageously the metal oxide particles used have an average of 0.01 to 0.15 μm. Has a basic particle size.

  The ratio of the metal-doped inorganic UV filter is preferably in the range of 5% by mass to 80% by mass, more preferably 5% by mass to 60% by mass, with respect to the total mass of the composite particles.

  The inorganic UV filter particles are preferably doped with at least one transition metal selected from Fe, Zn, Mn, Zr, Ce and mixtures thereof, more preferably selected from Fe and Mn. These metals can be incorporated alone or in a mixture. Further details of these doped metal oxides can be found in WO99 / 60994 and WO01 / 40114.

  The optimum amount of transition metal in the metal oxide is determined by routine experimentation, but is preferably sufficiently low so that the particles are not colored. An amount as small as 0.1 mole% or more, for example 5 mole% or 10 mole%, can generally be used. The general concentration is 0.5 to 2 mole% in terms of mass relative to the total mass of the doped metal oxide.

  Metal oxide doped particles can be obtained by any one of the standard processes for preparing doped oxides. This involves combining the metal oxide particles in a solution or suspension, usually an aqueous solution, with a transition metal in the form of a salt, such as an oxygen-containing anion such as chloride or perchlorate or nitrate, and then usually at least It can be obtained by backing technology by backing it at a temperature of 300 ° C. Another route that can be used to prepare the doping material is a precipitation process of the type described in Mat. Sci. (1997) 36, 6001-6008, where a dopant salt and a host metal (ie Ti / Zn) are used. ) With the alkoxide, and then the mixed solution is heated to convert the alkoxide to the oxide. Continue heating until a dope sediment is obtained. Further details can be found in WO99 / 60994 and WO01 / 40114.

According to a preferred embodiment, the doped metal oxide particles are selected from Fe-doped TiO ₂ particles and Mn-doped TiO ₂ particles.

  Examples of metal oxide particles doped with at least one transition metal are composed of commercially available products TTO F6 (registered trademark) and Mn-doped titanium dioxide particles from Ishihara Sangyo Co., Ltd. composed of Fe-doped titanium dioxide particles. The commercial product OPTISOL OTP1-PW-WD (registered trademark) from Croda.

According to a particularly preferred embodiment, the composite particles are spherical composite particles containing a core comprising at least a porous or non-porous cross-linked polymethyl methacrylate polymer, said core comprising at least one layer of Fe-doped TiO _2. It is at least partially coated with particles.

According to another particularly preferred embodiment, the composite particle is a spherical composite particle containing a core comprising at least a porous or non-porous cross-linked polymethyl methacrylate polymer, said core comprising at least one layer of Mn-doped It is at least partially coated with TiO ₂ particles.

General Form The composition according to the invention can be prepared according to techniques well known to those skilled in the art.

  This may be in the form of an aqueous lotion or an aqueous gel, or it contains at least one fatty phase in addition to the aqueous phase and is a simple or complex emulsion such as an emulsion (O / W, W / O, O / W / O or W / O / W), cream, or cream gel. This may optionally be packaged as an aerosol and may be in the form of a spray.

  Preferably, the composition according to the invention is in the form of an oil-in-water or water-in-oil emulsion, more preferentially a water-in-oil.

  The emulsification processes that can be used are of the paddle or impeller, rotor stator and high pressure homogenizer (HPH) type.

  To obtain stable emulsions with low emulsifying compounds (oil / emulsifier ratio> 25), it is possible to make a dispersion in the concentrated phase and then dilute the dispersion with the remaining aqueous phase It is.

  It is also possible to obtain a stable dispersion which can reduce the droplet diameter to 100 nm via HPH (between 50 and 800 bar).

  Emulsions generally contain at least one emulsifier selected from amphoteric, anionic, cationic or nonionic emulsifiers used alone or as a mixture. The emulsifier is appropriately selected depending on the emulsion (W / O or O / W) to be obtained. Emulsions can also contain other types of stabilizers, such as fillers, or gelling or thickening polymers.

  For O / W emulsions, examples of emulsifiers that may be mentioned are nonionic emulsifiers such as oxyalkylenated (more specifically polyoxyethylenated) esters of fatty acids and glycerol, oxyalkylenated fatty acids and sorbitan. Esters, for example, oxyalkylenated (oxyethylenated and / or oxypropylenated) esters of fatty acids, such as PEG-100 stearate / glyceryl stearate mixture sold by ICI under the name Arlacel 165, oxy of fatty alcohols Alkyleneated (oxyethylenated and / or oxypropylenated) ethers, esters of sugars such as sucrose stearate, or fatty alcohols and ethers of sugars, in particular sold under the names Plantaren 2000 and Plantaren 1200, respectively, for example by the company Henkel Decyl glucoside and lauryl gluco Alkyl polyglucosides (APG) such as Sid, for example, sold by SEPPIC under the name Montanov68, from Goldschmidt under the name Tegocare CG90 and from Henkel under the name Emulgade KE3302, optionally with cetostearyl alcohol It includes cetostearyl glucoside as a mixture, and also arachidyl glucoside in the form of a mixture of arachidyl alcohol, behenyl alcohol and arachidyl glucoside, for example sold by the company SEPPIC under the name Montanov202. According to one particular embodiment of the invention, the mixture of alkylpolyglucoside as defined above and the corresponding fatty alcohol is a self-emulsifying composition as described, for example, in the document WO-A-92 / 06778. Form may be sufficient.

  Among other emulsion stabilizers, isophthalic acid or sulfoisophthalic acid polymers, especially phthalate / sulfoisophthalate / glycol copolymers, such as those sold by Eastman Chemical under the name Eastman AQ Polymer (AQ35S, AQ38S, AQ55S and AQ48 Ultra) Diethylene glycol / phthalate / isophthalate / 1,4-cyclohexanedimethanol copolymer (INCI name: polyester-5) can also be used.

  Among other emulsion stabilizers, mention may also be made of hydrophobically modified 2-acrylamido-2-methylpropanesulfonic acid polymers such as those described in patent application EP1069142.

  In the case of an emulsion, the latter aqueous phase is a nonionic vesicle dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965), FR2315991 and FR 2416008). Can include vesicular dispersion.

  Examples of the emulsifying surfactant that can be used in the preparation of the W / O emulsion include an emulsifying surfactant having an HLB of 5 or less at 25 ° C.

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

  The surfactant HLB used according to the present invention is HLB by Griffin as defined in the publication J. Soc. Cosm. Chem. 1954 (Vol. 5), pages 249-256.

  Non-limiting examples of surfactants with an HLB of 5 or less are described in particular in the section titled HLB Index in the title McCutcheon's Emulsifiers & Detergents, 1998 International Edition, MC Publishing Company publication.

  Examples of W / O emulsifying surfactants are sorbitan, glycerol, polyols or sugar alkyl esters or ethers, silicone surfactants such as dimethicone copolyols, for example sold under the name DC5225C by the company Dow Corning. Mixtures of cyclomethicone and dimethicone copolyol, and alkyl dimethicone copolyols, such as lauryl methicone copolyol and cetyl dimethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by the company Dow Corning For example, a product sold under the name Abil EM90R by Goldschmidt and a mixture of cetyl dimethicone copolyol, polyglyceryl isostearate (4 mol) and hexyl laurate sold under the name Abil WE O9 by Goldschmidt Can be mentioned. One or more co-emulsifiers may also be added to them, and the co-emulsifier may advantageously be selected from the group consisting of polyol alkyl esters.

  Non-silicone emulsifiers, particularly sorbitan, glycerol, polyols or sugar alkyl esters or ethers are preferred.

  Specific examples of polyol alkyl esters that may be mentioned include polyethylene glycol esters such as 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, for example the product sold under the name Isolan GI 34 from Goldschmidt, sorbitan isostearate, for example sold under the name Arlacel 987 from ICI. Products, sorbitan glyceryl isostearate, for example the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof.

  According to one particularly preferred form of the invention, the composition is in the form of a water-in-oil emulsion.

Aqueous Phase When the composition of the present invention contains an aqueous phase, the phase contains water and optionally other water-soluble or water-miscible organic solvents.

  A water phase suitable for the present invention may comprise water selected from natural spring waters such as, for example, La Roche-Posay water, Vittel water or Vichy water, or floral water.

Suitable water-soluble or water-miscible solvent in the present invention, short-chain monoalcohols, for example, C ₁ -C ₄ monoalcohols, such as ethanol or isopropanol, diols or polyols, such as ethylene glycol, 1,2-propylene glycol, 1, Includes 3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycerol, and sorbitol, and mixtures thereof.

  According to a preferred embodiment, ethanol, propylene glycol, glycerol, and mixtures thereof can be used more particularly.

  Water or aqueous phase (i.e. in the emulsion) in the composition of the present invention is 5% to 90% by weight, in particular 5% to 75% by weight, more in detail, relative to the total weight of said composition. May be present in a content ranging from 10% to 70% by weight.

  The water-soluble organic solvent may be present in the composition of the present invention in a content ranging from 1% by mass to 30% by mass, particularly from 2% by mass to 20% by mass, with respect to the total mass of the composition. it can.

Oil Phase The composition of the present invention may also comprise at least one oil phase comprising at least one oil.

  For the purposes of the present invention, the term “oil phase” refers to a phase comprising at least one oil and all fat-soluble and lipophilic components and fatty substances used in the preparation of the composition of the invention. It is thought to mean.

  The term “oil” is considered to mean any fatty substance that is in liquid form at room temperature (20-25 ° C.) and atmospheric pressure (760 mmHg).

  Oils suitable for the present invention may be volatile or non-volatile.

  Oils suitable for the present invention can be selected from hydrocarbon-based oils, silicone oils, fluorinated oils and mixtures thereof.

  Hydrocarbon based oils suitable for the present invention may be animal hydrocarbon based oils, vegetable hydrocarbon based oils, mineral hydrocarbon based oils, or synthetic hydrocarbon based oils.

  Oils suitable for the present invention can advantageously be selected from mineral hydrocarbon based oils, vegetable hydrocarbon based oils, synthetic hydrocarbon based oils, silicone oils, and mixtures thereof.

  For the purposes of the present invention, the term “silicone oil” is taken to mean an oil comprising at least one silicon atom, in particular at least one Si—O group.

  The term “hydrocarbon-based oil” is considered to mean an oil mainly containing hydrogen and carbon atoms.

  For the purposes of the present invention, the term “silicone oil” is taken to mean an oil comprising at least one silicon atom, in particular at least one Si—O group.

  The term “fluorinated oil” is considered to mean an oil containing at least one fluorine atom.

  The hydrocarbon-based oils suitable for the present invention further contain oxygen, nitrogen, sulfur and / or phosphorus atoms, for example in the form of hydroxyl groups, amine groups, amide groups, ester groups, ether groups or acidic groups, In particular, it can optionally be included in the form of hydroxyl groups, ester groups, ether groups or acidic groups.

  The oil phase typically includes at least one volatile or non-volatile hydrocarbon-based oil and / or one volatile or non-volatile silicone oil in addition to the lipophilic UV-screening agent (s). Included.

For the purposes of the present invention, the term “volatile oil” is understood to mean an oil that can evaporate in less than one hour at room temperature and atmospheric pressure when left in contact with the skin or keratin fibers. . The volatile oil of the present invention is liquid at room temperature, and at room temperature and atmospheric pressure, particularly 0.13 Pa to 40000 Pa (10 ^{−3 to} 300 mmHg), in particular 1.3 Pa to 13000 Pa (0.01 to 100 mmHg), more specifically It is a volatile cosmetic oil having a non-zero vapor pressure in the range of 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

The term “non-volatile oil” means an oil that remains at room temperature and atmospheric pressure for at least several hours on the skin or on keratin fibers, and in particular has a vapor pressure of less than 10 ⁻³ mmHg (0.13 Pa).

Hydrocarbon-based oils Non-volatile hydrocarbon-based oils that can be used according to the present invention can include in particular:
(i) hydrocarbon-based oils of plant origin, for example, generally triglyceride esters (these fatty acids are fatty acid triesters of glycerol can have various chain lengths to C ₂₄ C _4, these chains Probably linear or branched, saturated or unsaturated, these oils are, among others, wheat germ oil, sunflower oil, grape seed oil, sesame seed oil, 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 seed oil, pumpkin oil, mallow oil, blackcurrant oil, evening Primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, kukui oil, passion flower And musk rose oil, or caprylic / capric acid triglycerides such as those sold by Stearineries Dubois Inc. or those sold under the names Miglyol 810, 812 and 818 from the company Dynamit Nobel)
(ii) synthetic ethers containing 10 to 40 carbon atoms,
(iii) linear or branched hydrocarbons of inorganic or synthetic origin, such as petroleum jelly, polydecene, hydrogenated polyisobutenes such as pearl reames and squalane, and mixtures thereof;
(iv) Synthetic esters, for example oils of the formula RCOOR ′, wherein R represents a residue of a linear or branched fatty acid containing 1 to 40 carbon atoms and R ′ represents 1 to 40 Represents a hydrocarbon-based chain containing 1 carbon atom, in particular a branched hydrocarbon-based chain, where R + R ′ ≧ 10], for example, pure serine oil (cetearyl octoate), isopropyl myristate , Isopropyl palmitate, C ₁₂ -C ₁₅ alkyl benzoate, for example, products sold under the trade name Finsolv TN or Witconol TN from Witco, or products sold under the trade name Tegosoft TN from Evonik Goldschmidt, 2-ethylphenyl benzoate, such as the commercial product sold by ISP under the name X-Tend 226, isopropyl lanolinate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethyl palmitate Hexyl, isostearyl isostearate, diisopropyl sebacate, eg products sold under the name “Dub Dis” by the company Steininerie Dubois, octoate, decanoate or ricinoleate of alcohols or polyhydric alcohols, eg dioctanoate propylene glycol, hydroxylated esters, for instance isostearyl lactate or diisostearyl malate, and pentaerythritol esters, citric acid esters or tartaric acid esters, for example, straight-chain di (C ₁₂ -C ₁₃ alkyl) tartrates, for example Enichem Augusta Those sold under the name Cosmacol ETI by Industriale, or linear di (C ₁₄ -C ₁₅ alkyl) tartaric acid esters, such as those sold under the name Cosmacol ETL by the company, or acetate esters,
(v) fatty alcohols which are branched and / or unsaturated carbon chains having 12 to 26 carbon atoms and which are liquid at room temperature, such as octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyl Octanol or 2-undecylpentadecanol,
(vi) higher fatty acids such as oleic acid, linoleic acid or linolenic acid,
(vii) carbonate esters, such as dicaprylyl carbonate, such as the product sold under the name Cetiol CC by the company Cognis,
(viii) fatty amides such as isopropyl N-lauroyl sarcosinate, such as the product sold under the trade name Eldew SL205 from Ajinomoto Co., Inc.
As well as mixtures thereof.

Particularly mentioned as volatile hydrocarbon-based oils that can be used according to the invention are hydrocarbon-based oils having 8 to 16 carbon atoms, in particular branched C _{8 to} C ₁₆ alkanes, such as patents from petroleum C ₈ -C ₁₆ isoalkanes of origin (also known as isoparaffins), for instance isododecane (2,2,4,4,6 also known as pentamethylheptane), isodecane or isohexadecane, or the company Cognis Alkanes (mixtures of different alkanes differentiated by at least one carbon) as described in the application WO2007 / 068371 or WO2008 / 155059. These alkanes, fatty alcohols obtained from coconut oil or palm oil, the oils sold under the trade name Isopar or Permethyl, isohexyl neopentanoate is branched C ₈ -C ₁₆ esters, and mixtures thereof can get.

  Other volatile hydrocarbon based oils may also be used, such as petroleum distillates, especially those sold under the name Shell Solt by Shell. According to one embodiment, the volatile solvent is selected from volatile hydrocarbon-based oils having from 8 to 16 carbon atoms, and mixtures thereof.

Silicone oils Non-volatile silicone oils are in particular non-volatile polydimethylsiloxanes (PDMS), pendant and / or alkyl groups or alkoxy groups at the end of the silicone chain (these groups are each 2 to 24 carbon atoms). Polydimethylsiloxane containing) or phenylated silicones such as phenyltrimethicone, phenyldimethicone, phenyl (trimethylsiloxy) diphenylsiloxane, diphenyldimethicone, diphenyl (methyldiphenyl) trisiloxane or trimethylsiloxysilicate 2 -Can be selected from phenylethyl.

As volatile silicone oils, for example, volatile linear or cyclic silicone oils, in particular having a viscosity ≦ 8 centistokes (8 × 10 ⁻⁶ m ² / s), in particular 2 to Those having 7 silicon atoms, these silicones optionally contain alkyl or alkoxy groups having 1 to 10 carbon atoms. Among the volatile silicone oils that can be used in the present invention, mention may be made in particular of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexa Methyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof.

  Mention may also be made of linear volatile alkyltrisiloxane oils of the general formula (I):

(Wherein R represents an alkyl group containing 2 to 4 carbon atoms, one or more hydrogen atoms of which can be replaced by fluorine or chlorine atoms).

Among the oils of the general formula (I) that can be mentioned are:
3-butyl-1,1,1,3,5,5,5-heptamethyltrisiloxane,
3-propyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, and
3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane,
These correspond to oils of the formula (I) in which R is a butyl group, a propyl group or an ethyl group, respectively.

Fluorinated oils Volatile fluorinated oils such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures thereof may be used.

  The oil phase (excluding the lipophilic organic UV shielding material) is preferably in the range of 3% to 60% by weight, preferably 5% to 30% by weight, based on the total weight of the composition.

  The oil phase according to the invention can further comprise other fatty substances mixed with or dissolved in the oil.

Other fatty substances that can be present in the oil phase are for example:
-Fatty acids containing 8 to 30 carbon atoms, for example fatty acids selected from stearic acid, lauric acid, palmitic acid and oleic acid,
-Waxes selected from lanolin, beeswax, carnauba or candelilla wax, paraffin wax, lignite wax, microcrystalline wax, waxes such as ceresin or ozokerite, or synthetic waxes such as polyethylene wax or Fischer-Tropsch wax,
-Gums selected from silicone gum (dimethiconol),
-Pasty compounds such as polymeric or non-polymeric silicone compounds, esters of glycerol oligomers, arachidyl propionate, fatty acid triglycerides, and derivatives thereof,
-As well as mixtures thereof.

Additives Compositions according to the present invention are particularly suitable for organic solvents, ionic or non-ionic, hydrophilic or lipophilic thickeners, demulcents, moisturizers, opacifiers, stabilizers, emollients, silicones, Foaming agent, fragrance, preservative, anionic, cationic, nonionic, zwitterionic or amphoteric surfactant, filler, polymer, propellant, basifying agent or acidifying agent or cosmetic and / or Standard cosmetic adjuvants selected from any other ingredients commonly used in the dermatological field can also be included.

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

Hydrophilic thickeners that may be mentioned include carboxyvinyl polymers such Carbopol products (carbomers) and Pemulen products (acrylate / acrylic acid C ₁₀ -C ₃₀ alkyl copolymer), polyacrylamides, for example, from the company SEPPIC Sepigel 305 (CTFA name: polyacrylamide / C ₁₃ -C ₁₄ isoparaffin / laureth 7) or Simulgel 600 (CTFA name: acrylamide / acryloyl sodium taurate copolymer / isohexadecane / polysorbate 80) crosslinked copolymers sold under the name, any Selectively cross-linked and / or neutralized 2-acrylamido-2-methylpropane sulfonic acid polymers and copolymers, such as poly (s) sold by Clariant under the trade name Hostacerin AMPS (CTFA name: polyacryloyldimethyltaurate ammonium). 2-acrylamido-2-methylpropanesulfo Acid) or Simulgel 800 (CTFA name: polyacryloyldimethyltaurine sodium / polysorbate 80 / sorbitan oleate), a copolymer of 2-acrylamido-2-methylpropanesulfonic acid and hydroxyethyl acrylate, such as SEPPIC sold by SEPPIC Simulgel NS and Sepinov EMT 10, sold by the company, cellulose derivatives such as hydroxyethylcellulose, polysaccharides, especially gums such as xanthan gum, and mixtures thereof.

Lipophilic thickeners that may be mentioned include synthetic polymers, such as poly sold under the name Intelimer IPA13-1 and Intelimer IPA13-6 from Landec Corporation (acrylic acid C ₁₀ -C ₃₀ alkyl), or modified Included are clays such as hectorite and derivatives thereof, such as products sold under the name Bentone.

  The composition according to the invention can also further comprise additional cosmetic and dermatological active agents.

Among the active agents include the following:
-Single or mixed vitamins (A, C, E, K, PP, etc.) and their derivatives or precursors,
- Antioxidant,
-Free radical scavengers,
-An antiglycation agent,
-Sedatives,
-NO synthase inhibitors,
-Agents that stimulate the synthesis of dermal or epidermal macromolecules and / or prevent their degradation,
-Drugs that stimulate fibroblast proliferation,
-Drugs that stimulate keratinocyte proliferation,
-Muscle relaxants,
-Tension agents,
-Matting agent,
-Keratolytic agents,
-Desquamating agent,
-Humectants such as polyols such as glycerol, butylene glycol or propylene glycol,
-Anti-inflammatory agents,
-Drugs that affect the energy metabolism of cells,
-Insect repellent,
-Substance P or substance CGRP antagonist,
-Anti-hair remover and / or hair restorer,
-Antidepressants,
-Additional inorganic and organic UV screening agents, such as those mentioned above.

  According to the present invention, the composition comprises one or more complementary hydrophilic, lipophilic or insoluble organic screening agents and / or one or more inorganic screening agents that are active against UVA and / or UVB irradiation. The agent may further be contained in free form.

  More preferably, the complementary organic shielding agent is a dibenzoylmethane compound, anthranilate, cinnabar compound, salicyl compound, camphor compound, benzophenone compound, β, β-diphenylacrylate compound, triazine derivative, benzalmalonate compound In particular, those described in patent US5624663, benzimidazole compounds, imidazolines, p-aminobenzoic acid (PABA) compounds, benzotriazole compounds, described in the following patent applications: US5237071, US5166355, GB2303549, DE19726184 and EP893119 Methylene bis (hydroxyphenylbenzotriazole) compounds, the following patent applications: benzoxazole compounds, shielding polymers and silicones described in EP0832642, EP1027883, EP1300137 and DE10162844, for example those described in patent application WO93 / 04665, among others , Α -Alkyl styrene-based dimers such as those described in patent application DE19855649, 4,4-diarylbutadienes such as described in the following patent applications: EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981 Merocyanine derivatives, such as those described in the following patent applications: WO04 / 006878, WO05 / 058269 and WO06 / 032741, indanilidene shielding agents described in patents EP-A-0823418 and EP-A-1341752 And mixtures thereof.

  Examples of complementary organic UV screening agents include those indicated herein below by their INCI names:

Dibenzoylmethane derivatives:
Butylmethoxydibenzoylmethane (sold under the trade name Parsol 1789® by DSM Nutritional Products).

Para-aminobenzoic acid derivatives:
PABA,
Ethyl PABA,
Ethyldihydroxypropyl PABA,
Ethylhexyldimethyl PABA (especially sold under the name Escalol 507 by ISP),
Glyceryl PABA,
PEG-25 PABA (sold by BASF under the name Uvinul P25),

Salicylic acid derivatives:
Homosalate (sold by Merck under the name Eusolex HMS®),
Ethyl hexyl salicylate (sold under the name Neo Heliopan OS® by Symrise),
Dipropylene glycol salicylate (sold under the name Dipsal® from Lubrizol),
Salicylic acid TEA (sold under the name Neo Heliopan TS® by Symrise).

Cinnamic acid derivatives:
Ethyl hexyl methoxycinnamate (especially sold under the trade name Parsol MCX® by DSM Nutritional Products),
Isopropyl methoxycinnamate,
Isoamyl methoxycinnamate (sold under the trade name Neo Heliopan E 1000® from Symrise),
Synoxate,
Methoxycinnamic acid DEA,
Diisopropyl methylcinnamate,
Dimethoxycinnamate ethylhexanoate glyceryl.

β, β-diphenyl acrylate derivatives:
Octocrylene (especially sold under the trademark Uvinul N539® by BASF),
Etocrylene (especially sold under the trade name Uvinul N35® by BASF).

Benzophenone derivatives:
Benzophenone-1 (sold under the trade name Uvinul 400® by BASF),
Benzophenone-2 (sold under the trade name Uvinul D50® by BASF),
Benzophenone-3 or oxybenzone (sold under the trade name Uvinul M40 by BASF),
Benzophenone-4 (sold under the trade name Uvinul MS40® by BASF),
Benzophenone-5,
Benzophenone-6 (sold under the trade name Helisorb 11® from Norquay),
Benzophenone-8 (sold by Cytec under the trade name Cyasorb UV-24®),
Benzophenone-9 (sold under the trade name Uvinul DS-49 (registered trademark) by BASF),
Benzophenone-12,
N-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate (sold under the trade name Uvinul A PLUS® by BASF) or its mixed form with octyl methoxycinnamate ( (Sold by BASF under the trademark Uvinul A PLUS B)
1,1 ′-(1,4-piperazinediyl) bis [1- [2- [4- (diethylamino) -2-hydroxybenzoyl] phenyl] methanone (CAS 919803-06-8).

Benzylidene camphor derivatives:
3-benzylidene camphor (manufactured by Chimex under the name Mexoryl SD),
4-methylbenzylidene camphor (sold by Merck under the name Eusolex 6300®),
Benzylidene camphorsulfonic acid (manufactured under the name Mexoryl SL® from Chimex),
Camphorbenzalkonium methosulfate (manufactured by Chimex under the name Mexoryl SO®),
Terephthalylidene dicamphor sulfonic acid (manufactured by Chimex under the name Mexoryl SX®),
Polyacrylamide methylbenzylidene camphor (manufactured by Chimex under the name Mexoryl SW®).

Phenylbenzimidazole derivatives:
Phenylbenzimidazolesulfonic acid (especially sold by Merck under the trade name Eusolex 232®),
Phenyldibenzimidazole tetrasulfonate disodium (sold by Symrise under the trade name Neo Heliopan AP®).

Benzotriazole derivatives:
Drometrizole trisiloxane (sold by Rhodia Chimie under the name Silatrizole),
Methylenebis (benzotriazolyl) tetramethylbutylphenol (in solid form under the trade name MIXXIM BB / 100® from Fairmount Chemical, or aqueous dispersion under the trade name Tinosorb M® from BASF) Sold in micronized form),

Triazine derivatives:
Bis (ethylhexyloxyphenol) methoxyphenyltriazine (sold under the trade name Tinosorb S® from BASF),
Ethylhexyl triazone (especially sold under the trade name Uvinul T150® by BASF),
Diethylhexylbutamide triazone (sold by Sigma 3V under the trademark Uvasorb HEB®),
Silicone triazines substituted with two aminobenzoate groups, such as those disclosed in patent EP0841341, in particular the compound 2,4-bis (n-butyl 4′-aminobenzalmalonate) -6-[( 3- {1,3,3,3-tetramethyl-1-[(trimethylsilyloxy] disiloxanyl} propyl) amino] -s-triazine,
2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine,
2,4,6-tris (dineopentyl 4'-aminobenzalmalonate) -s-triazine,
2,4-bis (dineopentyl 4′-aminobenzalmalonate) -6- (n-butyl 4′-aminobenzoate) -s-triazine,
Patent US6225467, patent application WO2004 / 085412 (see compounds 6 and 9) or document `` Symmetrical Triazine Derivatives '' IP.COM Journal, IP.COM INC West Henrietta, NY, US (September 20, 2004) Symmetric triazine screening agents, especially 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 (in Beiersdorf patent applications WO06 / 035000, WO06 / 034982, WO06 / 034991, WO06 / 035007, WO2006 / 034992 and WO2006 / 034985) Is also mentioned).

Anthranyl derivatives:
Menthyl anthranilate (sold by Symrise under the trade name Neo Heliopan MA®).

Imidazoline derivatives:
Ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate,

Benzalmalonate derivatives:
Dineopentyl 4'-methoxybenzalmalonate,
Polyorganosiloxanes containing benzalmalonate functional groups, such as Polysilicone-15 (sold under the trade name Parsol SLX® from DSM Nutritional Products).

4,4-Diarylbutadiene derivatives:
1,1-dicarboxy (2,2′-dimethylpropyl) -4,4-diphenylbutadiene.

Benzoxazole derivatives:
2,4-bis [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine,
As well as mixtures thereof.

  Complementary organic UV screening agents are preferably in the composition according to the invention in the range of 0.01% to 20% by weight, preferably 0.1% by weight relative to the total weight of the composition. It is present at a rate ranging from% to 15% by mass.

  The free form of the complementary inorganic screening agent is selected from coated or uncoated metal oxide pigments having an average primary particle size preferentially of 5 nm to 100 nm (preferably 10 nm to 50 nm), e.g. titanium oxide (non-coated). Crystalline or rutile and / or anatase crystalline forms), iron oxide, zinc oxide, zirconium oxide or cerium oxide pigments, all of which are UV photoprotectors well known per se.

  The pigment may or may not be coated.

  Coated pigments include, for example, compounds described in Cosmetics & Toiletries, February 1990, 105, 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, fatty acids. 1 by sodium, potassium, zinc, iron or aluminum salt, metal alkoxide (titanium or aluminum alkoxide), polyethylene, silicone, protein (collagen, elastin), alkanolamine, silicon oxide, metal oxide, sodium hexametaphosphate, etc. A pigment that has undergone a surface treatment of one or more chemical, electrical, mechanochemical and / or mechanical properties.

  As is known, silicones are organosilicon polymers or oligomers of various molecular weights, linear or cyclic, branched or crosslinked structures, obtained by polymerization and / or polycondensation of suitably functionalized silanes. Essentially from repeating main units in which the silicon atoms are linked to one another via oxygen atoms (siloxane bonds), and optionally substituted hydrocarbon-based groups are directly bonded to the silicon atoms via carbon atoms. Become.

  The term “silicone” also includes the silanes required for their preparation, especially alkyl silanes.

  Silicones suitable for the present invention for use in pigment coating are preferably selected from the group consisting of alkylsilanes, polydialkylsiloxanes, and polyalkylhydrosiloxanes. Even more preferably, the silicone is selected from the group comprising octyltrimethylsilane, polydimethylsiloxane and polymethylhydrosiloxane.

  Of course, the metal oxide pigment may be treated with other surface agents, in particular cerium oxide, alumina, silica, aluminum compounds or silicon compounds or mixtures thereof, prior to the silicone treatment.

  Such coated or uncoated metal oxide pigments are disclosed in particular in patent application EP-A-0518773. Commercially available pigments include products sold by Sachtleben, Tayca, Merck and Evonik.

  Complementary inorganic UV filters generally account for 0.5 to 40% by weight, preferably 1 to 30% by weight, based on the total weight of the composition.

  It goes without saying that those skilled in the art will be able to make the above-mentioned options so that the advantageous properties inherently associated with the composition of the invention are not adversely affected or substantially unaffected by the envisaged addition. The additional compounds and / or their amounts will be carefully selected.

  One skilled in the art will select the active agent depending on the desired effect on the skin, hair, eyelashes, eyebrows or nails.

  The cosmetic composition according to the invention is applied in many treatments, in particular in the cosmetic treatment of skin, lips and hair, including the scalp.

  Another subject of the invention is the invention as defined above in the manufacture of products for cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyebrows and / or scalp, in particular care products, sunscreen products and makeup products. Is the use of the composition.

  The cosmetic composition according to the present invention can be used, for example, as a makeup product.

  The cosmetic composition according to the invention is a liquid to semi-liquid viscous facial and / or body care product and / or sunscreen product such as, for example, emulsions, somewhat rich creams, cream gels and pastes. Can be used as These may optionally be packaged in an aerosol form and may be in the form of a mousse or spray.

  The composition according to the invention in the form of an evaporating fluid lotion according to the invention is applied to the skin or hair in the form of fine particles by means of a pressure device. The apparatus according to the present invention is well known to those skilled in the art and includes a non-aerosol type pump or “atomizer”, an aerosol container containing a propellant, and an aerosol pump using compressed air as a propellant. These devices are described in patents US4077441 and US4850517.

  Compositions packaged as aerosols in accordance with the present invention generally contain conventional propellants such as hydrogen fluoride treated compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane or trichlorofluoromethane. Etc. They are preferably present in an amount ranging from 15% to 50% by weight relative to the total weight of the composition.

  The examples that follow serve to illustrate the invention.

(Examples 1 to 4)
Preparation of composite particles by mechanofusion hybridization process Use a hybridizer equipped with a high-speed rotor with multiple blades in a dry room sold by Nara Machinery Co., Ltd. in Japan. Then, the components shown in Table 1 were subjected to hybridization. In each example, the components shown in Table 1 were mixed at the mass ratio shown in the same table and shaken in a plastic bag for several minutes. Next, the mixture was put into a hybridizer, and the rotor was rotated at 8000 rpm (linear speed 100 m / s) for 3 minutes.

(Examples 5 to 9)
Sun / water emulsion for sun protection The following compositions 5-9 were prepared. Each component is expressed as a weight percent of active material relative to the total weight of the composition.

Emulsion preparation method:
The aqueous phases A1, A2, A3 and the oil phases B1 and B2 are prepared by mixing the raw materials at 80 ° C. with mechanical stirring, and the resulting solution is visually uniform. An emulsion is prepared by slowly introducing the oil phase into the aqueous phase while stirring for 15 minutes at a stirring speed of 4,000 rpm using a Moritz homogenizer. Cool the resulting emulsion to 40 ° C. with stirring, then add phase B3 into it with gentle stirring, followed by phases C, D, E and F. The resulting emulsion is cooled to room temperature with gentle stirring and then Phase G is added. This is characterized by droplets with a droplet size of 1-10 μm.

These compositions were evaluated according to the following properties.
-Shielding effect, and
-Sensation when applied to the skin.

Examples 5-9 were compared with an equivalent amount of active material TiO ₂ at 0.5% by weight.

In vitro SPF
The sun protection factor (SPF) is determined according to the in vitro method described by J. Soc. Cosmet. Chem. 40, 127-133, (1989) by BL Diffey. The measurement was performed using a UV-1000S spectrophotometer manufactured by Labsphere. Each composition is applied to the PMMA rough plate in the form of a uniform and uniform deposit at a rate of 1 mg / cm ² .

in vitro PPD index
To measure the UV-A protection index, the PPD (persistent deposition blackening) method is particularly recommended and used, which measures the color of the skin observed 2 to 4 hours after exposure of the skin to UV-A. It has been. This method has been adopted by the Japan Cosmetic Industry Association (JCIA) since 1996 as an official test procedure for UV-A labeling of products, and is often used in European and American test laboratories (1995). (Measurement standards for UVA protection effectiveness according to the Japan Cosmetic Industry Association's technical announcement issued on November 21 and became effective on January 1, 1996).

The UVA _PPD Sun Protection Index (UVA _PPD PF) is the UV-A dose (MPPDp) required to reach the pigmentation threshold when using a UV screening agent, and the pigmentation threshold when there is no UV screening agent. Mathematically represented by the ratio to the UV-A dose (MPPDnp) required to reach

The measurement was performed according to an in vitro test using a UV-2000S spectrophotometer manufactured by Labsphere. Each composition is applied to the PMMA blank in the form of a uniform and uniform deposit at a rate of 1 mg / cm ² .

Protocol for assessing sensory effects after application to the skin Sensory effects after applying the formulation to the skin are applied to the forearm at a ratio of ² mg / cm ² and waited for a drying time of 2 minutes. It is then evaluated by determining the frictional force felt between the finger and the forearm surface. The oily skin sensation was then evaluated after application.

result

These results are
- Composition 5 and 8 according to the present invention containing the composite particles having a doped TiO _2, compared with compositions 7 and 9 of the comparative example containing composite particles having a non-doped TiO _2, the UVA and UVB radiation More effective against it,
- Composition 5 and 8 according to the present invention containing the composite particles having a doped TiO ₂ is, contain composite particles having a composition 6 and undoped TiO ₂ of the comparative example containing doped TiO ₂ particles in the free form It shows that it has a sensory effect superior to compositions 7 and 9 of comparative examples.

Claims (16)

i) a matrix containing at least one inorganic material and / or at least one organic material;
ii) Composite particles comprising at least one inorganic UV filter doped with at least one transition metal.   2. Composite particles according to claim 1, having an average particle size of 0.1 to 30 [mu] m, preferably 0.1 to 20 [mu] m, more preferentially 0.1 to 10 [mu] m.   Spherical particles containing a core comprising at least one organic material and / or at least one inorganic material, wherein the core is partly composed of at least one layer of an inorganic UV filter doped with at least one transition metal 3. The composite particle according to claim 1, wherein the composite particle is coated on the surface. The inorganic material is selected from the group consisting of glass, silica, and aluminum oxide, and mixtures thereof;
-The organic material consists of cellulose, poly (meth) acrylate, polyamide, silicone, polyurethane, polyethylene, polypropylene, polystyrene, polycaprolactam, polysaccharides, polypeptides, polyvinyl derivatives, waxes, polyesters and polyethers, and mixtures thereof 4. Composite particle according to claim 3, characterized in that it is selected from the group.   5. The composite particle according to claim 3, wherein the core contains porous or non-porous spherical particles of a crosslinked polymethyl methacrylate polymer. The inorganic UV filter particles are composed of metal oxide particles, preferably selected from zinc oxide particles (ZnO), titanium dioxide particles (TiO ₂ ), iron oxide particles (FeO), and mixtures thereof, more preferably. 6. The composite particle according to claim 1, wherein is a particle of TiO ₂ .   7. Composite particles according to any one of claims 1 to 6, wherein the particles of the inorganic UV filter have a basic average particle size of 0.001 to 0.2 [mu] m, preferably 0.01 to 0.15 [mu] m.   The ratio of the metal-doped inorganic UV filter is 5% by mass to 80% by mass, more preferably 5% by mass to 60% by mass, based on the total mass of the composite particles, according to any one of claims 1 to 7. The composite particle as described.   The inorganic UV filter particles are doped with at least one transition metal selected from Fe, Zn, Mn, Zr, Ce and mixtures thereof, more particularly the transition metal is selected from Fe and Mn The composite particle according to any one of claims 1 to 8. The composite particle according to any one of claims 1 to 9, wherein the metal-doped inorganic UV filter is selected from Fe-doped TiO ₂ particles and Mn-doped TiO ₂ particles. The core of claim 1 comprising at least a porous or non-porous cross-linked polymethyl methacrylate polymer, wherein the core is at least partially coated with at least one layer of Fe-doped TiO ₂ particles. The composite particle according to any one of the above. It contains a core comprising at least a porous or non-porous cross-linked polymethyl methacrylate polymers, wherein the core is at least partially coated with Mn-doped TiO ₂ particles of at least one layer, of claims 1 to 11 The composite particle according to any one of the above.   A composition comprising at least the composite particles according to any one of claims 1 to 12 in a physiologically acceptable medium.   14. A cosmetic method for caring for and / or making up keratin materials, comprising applying at least one composition according to claim 13 to the surface of the keratin materials.   14. A cosmetic method for limiting skin darkening and improving facial skin color and uniformity, the method comprising applying at least one composition according to claim 13 to the surface of a keratin material.   14. A cosmetic method for treating aging of keratin materials, comprising applying at least one composition according to claim 13 to the surface of the keratin materials.