EP1895974A1

EP1895974A1 - Make-up compositions for keratinous materials

Info

Publication number: EP1895974A1
Application number: EP06778638A
Authority: EP
Inventors: Christophe Dumousseaux
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2005-06-22
Filing date: 2006-06-22
Publication date: 2008-03-12
Also published as: JP2008546746A; JP2008546747A; JP2008546745A; WO2006136721A1; WO2006136723A2; US20090117160A1; WO2006136725A3; WO2006136723A3; WO2006136719A1; US20090041695A1; WO2006136720A1; EP1895976A2; WO2006136722A1; US20080268002A1; EP1895975A1; WO2006136725A2; EP1898870A2; WO2006136724A2; WO2006136724A3; US20090041696A1

Abstract

The invention concerns a cosmetic composition comprising: a physiologically acceptable medium, monodispersed particles including an insoluble core from which extend, in particular by grafting, polymeric chains soluble in the medium, the monodispersed particles being capable of forming an ordered network of monodispersed particles on a support whereon the composition is applied.

Description

MAKE-UP COMPOSITIONS OF KERATINIC MATERIALS

The present invention relates to cosmetic compositions and more particularly those intended for the makeup of keratin materials, in particular the skin, the lips, the nails, the eyelashes and the hair. Background

It is known to use in the makeup compositions pigments and dyes.

The use of such pigments and dyes can however raise difficulties. Thus, the pigments and dyes may have relatively low UV resistance and become light-impaired.

In addition, when the color is provided by an absorption phenomenon, the color produced may not be as bright and bright as desired.

Finally, the choice of pigments and dyes used in cosmetics may be insufficient.

Pigments and dyes can still impose formulation constraints.

It is known to obtain a goniochromatic effect of using interferential pigments. These are nevertheless relatively complex and expensive to manufacture. A goniochromatic effect present in the formulation can still be provided by an ordered network of monodisperse particles, as taught in particular in WO 00/47167.

Despite the relative antiquity of this publication, to date, to the best of the applicant's knowledge, there is not yet on the market a cosmetic product that makes it possible to obtain a bright and luminous coloration for a period of time acceptable to the consumer by means of an ordered network of monodisperse particles after application to keratin materials.

The publication WO 02/056854 of the applicant company discloses an iridescent composition for topical application, comprising at least one water-soluble surfactant and monodisperse particles in aqueous dispersion, these particles having a number-average size ranging from 50 to 300 nm and the amount of these particles being at least 3% by weight relative to the total weight of the composition. The application WO 05/018566 discloses a topical system for application to the skin, comprising a colloidal crystalline lattice in a hydrophilic phase and at least one phase containing an oil.

SUMMARY There is a need to benefit from novel compositions for producing a color or for absorbing UV or IR by at least one ordered array of monodisperse particles, such a grating being sometimes referred to as a "photonic crystal".

The subject of the invention is a cosmetic composition comprising: a physiologically acceptable medium, monodisperse particles comprising an insoluble core in the medium, from the surface of which, especially by grafting, polymer chains that are soluble in the medium extend. The set of polymer chains is still called "bark". These so-called "hairy" particles can be stabilized in the medium not only by electrostatic interactions but also by steric interactions of excluded volume type.

The additional stabilization and the volume provided by the polymer chains makes it easy to incorporate other components, particularly particulate, in the composition without risk of destabilization and aggregation of the particles. These other components are, for example, coloring agents, in particular larger particles such as, for example, at least one effect pigment, or fillers intended, for example, to modify the appearance of the composition or the support coated therewith, or, for example, polymers intended to thicken the formulation or improve the holding of the deposit.

The polymer chains may comprise graft polymer chains, which may contain chemical functions (carboxylic acid, amine, amide, thiol, etc.) capable of interacting with the keratin materials and of improving the adhesion of the composition to the covered support. Polymeric chains can also improve the resistance of the particle network after application to keratin materials. The invention can make it possible to produce, if desired, a cosmetic composition free of dye or pigment, the color being produced by the ordered network of monodisperse particles.

The invention can also make it possible to form a colored deposit after application of an initially colorless composition.

The invention may also make it possible to produce a colored deposit sensitive to an external stimulus such as, for example, temperature, humidity or ultraviolet radiation.

Such a stimulus can influence the distance between the particles of the network and thus change the color.

The distance between the particles can be modified, for example due to a variation of the particle size under the effect of the external stimulus and / or a variation of the distance between the particles with a substantially constant size, for example due to a variation of the repulsive forces therebetween and / or a variation in the size of at least one compound present between the particles. The refractive index of the medium may possibly vary under the effect of the external stimulus, for example the temperature.

The invention may also make it possible to produce, where appropriate, a deposit whose color changes as a function of the degree of drying of the composition.

The invention can make it possible to obtain a durable and luminous coloration over a large surface.

Hairy monodisperse particles

The expression "hairy monodisperse particles" denotes, according to the invention, particles whose average size after application and drying has a coefficient of variation CV of less than or equal to 30%, better still 15%.

The coefficient of variation CV is defined by the relation CV = -, where s is the difference

type of the particle size distribution and D the average size thereof.

The average size D and the standard deviation of the particles after application to a support and drying can be measured on 250 particles by analysis of an image obtained by means of a scanning electron microscope, for example that of reference S-4,500 from HITACHI. An image analysis software can be used to facilitate this measure, for example the Winroof ^® software, marketed by Mitani Corporation.

Preferably, the coefficient of variation of the monodisperse hairy particles is less than or equal to 10%, better still less than or equal to 7%, even better still less than or equal to 5%, being for example substantially of the order of 3.5% . A small dispersion of the particle size is favorable to the quality of the compact crystalline network formed and thus to obtaining bright and brilliant colors.

The average size D of the monodisperse hairy particles may be generally between 50 and 800 nm, better still between 50 and 500 nm, for example between 150 and 450 nm, which may be chosen as a function, for example, of the color or colors to be obtained and the medium surrounding.

The size of the monodisperse particles in solution, as determined by the average hydrodynamic diameter, may range from 100 nm to 2 μm. The average hydrodynamic diameter is measured by dynamic light scattering. The sample is placed in a quartz cell and illuminated with a laser. The aurocorrelation function is then measured at a detection angle of 90 °. The average hydrodynamic diameter is then calculated from the Gaussian distribution of volume diameters. An apparatus of Nicomp 380 type marketed by the company • Particle Sizing System, without Barbara can for example be used. The mass content of monodisperse hairy particles can range from 1 to

70%, preferably 5 to 60%, more preferably 10 to 50%. The content may be greater than or equal to 15% or even 20%. Depending on the concentration of particles used in the composition, the periodic network formed after drying may be monolayer or multilayer, compact or not. The hairy particles can be obtained each by grafting a polymer on the surface of a monodisperse heart. The grafting can be done from a macromonomer previously polymerized and functionalized at the end of the chain. This macromonomer can be added after the synthesis of the monodisperse particles or during the synthesis thereof. The polymer chains can also be synthesized by initiating the polymerization from the surface of the cores. A review of the different surface polymerization techniques in the case of silica cores is given in publication by Rhadakrishnan et al., Soft Matter, 2, pp386-396 (2006), the contents of which are incorporated by reference.

The hairy particles can also be obtained from block polymers for effecting emulsion polymerization. Block polymers formed of soluble and insoluble sequences in the medium can also form hairy particles by micelle-like association in the medium.

The refractive index n _p of the monodisperse hairy particles is different from that U ₀ of the continuous medium extending around the particles after application of the composition and the difference of these refractive indices is preferably greater than or equal to 0.02, better than or equal to 0.05, more preferably greater than or equal to 0.1, being for example between 0.02 and 2, in particular between 0.05 and 1.

A difference in refractive index n _p -ri _c too low requires a large number of layers of particles of the ordered network to obtain the desired result. An excessive index difference accentuates the phenomena of diffusion of light by the layer and brings about a bleaching of the deposit after application.

The refractive index of the hairy monodisperse particles is defined as the average refractive index, being calculated linearly as a function of the volume proportion of each component.

The refractive index of the monodisperse hairy particles may be greater than or equal to that of the medium, for example being greater than or equal to 1.4, in particular between 1.4 and 1.7.

All monodisperse hairy particles corresponding to the same average size D may have substantially the same refractive index.

The core of the monodisperse particles may be colored, that is to say not white, for example to enhance the intensity of the color produced and / or to avoid a whitening phenomenon of the composition after application to the keratin materials.

An example of a colored particle used to form a colloidal crystal is given in publication WO 05/012961.

The color of the monodisperse particles may be provided by the choice of the material or materials constituting each monodisperse particle. It can have the effect of increasing the absorption of light by the particles and decrease the diffusion. The monodisperse hairy particles may in particular incorporate in the heart at least one pigment or dye, organic or inorganic, the latter may optionally have a fluorescence in the ultraviolet or infrared.

When the heart of the monodisperse hairy particles is inorganic, the core may for example comprise at least one oxide, in particular a metal oxide and chosen, for example, from oxides of silica, iron, titanium, aluminum, chromium and zinc, copper, zirconium, cerium and mixtures thereof. The core of the monodisperse particles may also comprise a metal, in particular titanium, silver, gold, aluminum, zinc, iron, copper, and their mixtures and alloys. A silica-based core is particularly suitable.

The monodisperse hairy particles may comprise an organic heart.

Among the materials that may be suitable for producing the organic core of monodisperse hairy particles, mention may be made of polymers, in particular with a carbon or silicone chain, for example polystyrene (PS), polymethylmethacrylate (PMMA), polyacrylamide (PAM), silicone polymers.

The heart of the monodisperse hairy particles may be hollow. The presence of air or another gas inside the core makes it possible to obtain a large difference in refractive index between the particles and the surrounding medium, which is favorable in terms of intensity of the diffraction peak. and therefore the development of a very intense coloring. It is then easier to add many non-volatile compounds to the composition or to the composition without losing the color and ending up with a transparent composition.

As polymers that can be used to form the polymer or "hair" chains, mention may be made of acrylic polymers, polymers based on acrylic or methacrylic acid, acrylate or methacrylate of isobornyl, of isobutyl acrylate or methacrylate, of methacrylate of methyl, styrenic polymers, styrene-based copolymers such as styrene / acrylic, styrene / maleic acid, styrene / ethylene-polypropylene copolymers, silicone or acrylic silicone polymers, polyacrylamides such as polyisopropylacrylamide. The number average molecular weight of a polymer chain can range from 1,000 to 1,000,000, preferably from 5,000 to 100,000. Examples of "hairy" particles are given for example in the publication Ishizu et al., Kagaku To Kogyo, 57 (7) (2004) in the case of a polymer core or in the publication Okubo et al., Colloid & Polymer Science, 280 (3), pp290-295 (2002) in the case of a silica core and polymers polymethyl methacrylate or poly (styrene co maleic anhydride) in bark. Another example of a hairy particle is given for example in the publication Tsuji et al., Langmuir, 21, pp2434-2437 (2005) in the case of a polystyrene core and polymeric chains of poly N isopropylacrylamide.

Medium containing the monodisperse particles According to the invention, the hairy monodisperse particles may be contained at least before application in a physiologically acceptable medium for forming on the support on which the composition is applied an ordered network of monodisperse particles.

By "physiologically acceptable medium", synonymous with the expression "cosmetically acceptable medium" means a non-toxic medium and may be applied to keratin materials of human beings, including the skin, mucous membranes or superficial body growths.

The physiologically acceptable medium is generally adapted to the nature of the support on which the composition is to be applied and to the form in which the composition is intended to be packaged.

The monodisperse hairy particles may be contained in a liquid phase, the core of the particles being insoluble in this phase and the polymer chains at least partially soluble therein.

The medium containing the monodisperse particles may be entirely liquid or may contain other particles, as appropriate.

The medium may be chosen so as to promote the dispersion of the particles in the medium before the application thereof, in order to avoid aggregation of the particles.

The medium may be chosen such that the ordered network of monodisperse particles is formed by regular stacking thereof, after application to the keratin materials, the network not existing in the composition before application and forming for example during the evaporation of a solvent contained in the composition. The refractive index of the medium advantageously has, as indicated previously, a difference with that of the monodisperse particles, this difference being in absolute value preferably greater than or equal to 0.02, better still greater than or equal to 0.05, in particular between 0 , 05 and 1, more preferably greater than or equal to 0.1. The medium may be aqueous, the monodisperse hairy particles may be contained in an aqueous phase. By "aqueous medium" is meant a liquid medium at room temperature and atmospheric pressure which contains a significant fraction of water based on the total weight of the medium. The additional fraction may contain or consist of physiologically acceptable organic solvents miscible with water, for example alcohols or alkylene glycols. The mass content of water of the aqueous medium is preferably greater than or equal to 30%, better still 40%, even more preferably 50%.

The medium may be monophasic or multiphasic and may or may not include solids other than monodisperse particles, especially smaller particles or larger particles.

The medium may comprise at least one compound having an OH bond, especially an alcohol function, in a mass content for example greater than or equal to 5%, more preferably 10%. Such a compound can slow evaporation without disturbing the formation of an ordered network. The medium may comprise an alcohol, such as ethanol or isopropanol, for example, or a derivative of glycol, especially ethylene glycol or propylene glycol.

The conductivity of the composition may be between 5 and 2,000 μS.cm ^-1 , in particular between 10 and 4,000 μS cm ^-1 , or even between 20 and 400 μS cm ^-1 .

The medium can be transparent or translucent, and colored or not. The medium containing the monodisperse particles may contain no pigment or dye. The coloration of the medium may correspond to the addition of an additional coloring agent.

The color of the medium corresponds for example to one of the colors likely to be generated by the ordered network of monodisperse particles, for example the color produced by the network when observed at normal incidence. The color of the medium can also be black in order to limit the diffusion of light. The ordered network of monodisperse particles can make it possible to easily obtain the colors green, red or blue. The color domain can be extended by the presence of an additional coloring agent, for example a dye, an absorbent pigment or an effect pigment, for example at a concentration of 0.1 to 15% by weight.

By "effect pigment" is meant, inter alia, reflective particles, nacres, goniochromatic coloring agents or diffractive pigments, as defined below.

The presence of pigments of a relatively large size, such as nacres for example, may not prevent the formation of the network next to the pigment particles, but on the contrary promote its formation by improving the confinement of the monodisperse particles, the large particles which can be introduced in certain dislocations of the network.

The medium may thus comprise larger particles having a size at least 3, better 5 times that of the monodisperse particles, more preferably 10 times higher.

These large particles may be particles of a pigment or a non-coloring filler.

The medium may thus comprise at least one effect pigment. The presence of monodisperse particles makes it possible to produce a periodic network after application to the keratin materials. This network makes it possible to obtain a color effect by diffraction of light and the Applicant has found that it is possible to associate a second optical effect with an effect pigment while maintaining the periodic grating. The two optical effects will be additional and the presence of the pigment thus makes it possible to extend the color range and the optical effects obtained by the network formed on the keratin materials.

The effect pigment may be present in the formulation at a concentration of between 0.1 and 70%, preferably 1 to 50%, preferably 5 to 20%.

Reflective particles Reflective particles can be used to create highlight points visible to the naked eye. Reflective particles can have various shapes. These particles may in particular be in the form of platelets or globular, in particular spherical. These particles may comprise a substrate covered with a reflective material. The substrate may be chosen from glasses, metal oxides, aluminas, silicas, silicates, especially aluminosilicates and borosilicates, mica, synthetic mica, synthetic polymers and mixtures thereof.

The reflective material may include a layer of metal or a metal compound. Platelet-coated silver-coated glass substrate particles are sold under the name METASHINE by Nippon Sheet Glass.

By way of example of reflective particles, mention may also be made, for example, of particles comprising a synthetic mica substrate coated with titanium dioxide, or particles of coated glass of brown iron oxide, of titanium oxide, of tin oxide or a mixture thereof such as those sold under the trade name REFLECKS® by ENGELHARD.

Also suitable for the invention are the pigments of the METASHINE 1080R range marketed by NIPPON SHEET GLASS CO. LTD. These pigments, more particularly described in the patent application JP 2001-11340, are C-GLASS glass flakes comprising 65 to 72% SiO ₂ , covered with a layer of rutile titanium oxide (TiO ₂ ) . These glass flakes have an average thickness of 1 micron and an average size of 80 microns, a ratio in average size / average thickness of 80. They have blue, green, yellow or silver-tone reflections depending on the thickness of the glass. TiO ₂ layer. It is also possible to mention particles having a size of between 80 and 100 μm, comprising a synthetic mica substrate (fluorophlogopite) coated with titanium dioxide representing 12% of the total weight of the particle, sold under the name PROMINENCE by the company NIHON KOKEN.

The reflective particles may also be chosen from particles formed from a stack of at least two layers with different refractive indices. These layers may be polymeric or metallic in nature and in particular include at least one polymeric layer. Thus, the reflective particles can be particles derived from a multilayer polymeric film. Such particles are described in particular in WO 99/36477, US Pat. No. 6,299,979 and US Pat. No. 6,387,498. Reflective particles comprising a stack of at least two polymer layers are marketed by the company 3M under the name MIRROR GLITTER. These particles comprise 2,6-PEN and polymethyl methacrylate layers in a weight ratio of 80/20. Such particles are described in US Pat. No. 5,825,643. Nacres

By "nacres", it is necessary to include colored particles of any shape, iridescent or not, in particular produced by certain shellfish in their shell or else synthesized and which exhibit a color effect by optical interference.

The nacres may be chosen from pearlescent pigments such as iron oxide coated titanium mica, bismuth oxychloride-coated mica, titanium mica coated with chromium oxide, titanium mica coated with an organic dye. especially of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. It may also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic dyestuffs.

Mention may also be made, by way of example of nacres, of natural mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride. Among the nacres available on the market, mention may be made of Flamenco nacres marketed by ENGELHARD and TIMIRON nacres marketed by MERCK.

Goniochromatic coloring agents

The goniochromatic coloring agents in the sense of the present invention have a color change, also called "color flop", depending on the angle of observation, greater than that which can be encountered with nacres.

The goniochromatic coloring agent may be chosen, for example, from interferential multilayer structures and liquid crystal coloring agents.

Examples of symmetrical interferential multilayer pigments that can be used in compositions produced in accordance with the invention are, for example:

CHROMAFLAIR by the company FLEX; SICOPEARL by BASF; pigments XIRONA by MERCK (Darmstadt) and INFINITE COLORS pigments from SHISEIDO and COLOR RELIEF pigments from CCIC.

It is also possible to use goniochromatic coloring agents having a multilayer structure comprising an alternation of polymeric layers, for example of the polyethylene naphthalate and polyethylene terephthalate type. Such agents are described in particular in WO-A-96/19347 and WO-A-99/36478.

Mention may be made, by way of example of pigments with a polymeric multilayer structure, those marketed by 3M under the name COLOR GLITTER or those marketed by Venture Chemical under the name Micro Glitter Pearl.

The liquid crystal coloring agents comprise, for example, silicones or cellulose ethers onto which mesomorphic groups are grafted.

As liquid crystal goniochromatic particles, it is possible to use, for example, those sold by the company Chenix as well as those sold under the name Helicone® HC by the company SICPA.

The composition may further comprise dispersed goniochromatic fibers. Such fibers may, for example, have a size of between 50 μm and 2 mm. Goniochromatic fibers with a polyethylene terephthalate / nylon-6 bilayer structure are marketed by TEIJIN under the name MORPHOTEX and MORPHOTONE. Diffracting pigments

By diffractive pigment is meant a pigment comprising a periodic pattern constituting a diffraction grating. Since the distance between the periodic patterns is of the same order of magnitude as the visible light, this pigment will be able to diffract the light and produce, for example, a rainbow effect.

Such pigments are commercially available under the name SPECTRAFLAIR from JDS Uniphase Corporation.

Such pigments can also be made according to the methods taught by patents US6818051, US6894086 and EP 1634619. These patents describe pigments consisting of a 3-dimensional network of silica particles similar to the structure of opals. Inverse opal structures can also be obtained and used. The medium in which the ordered network of monodisperse particles is formed can evaporate or not after application of the composition.

Preferably, the medium may comprise a volatile solvent. For the purposes of the invention, the term "volatile solvent" means any liquid capable of evaporating on contact with the skin at ambient temperature and under atmospheric pressure.

The medium can in particular be chosen so that the composition contains at least 10%, or even at least 30% of volatile solvent.

The pH of the composition may range from 1 to 11, for example from 3 to 9. The pH most suitable for the formation of the network may depend on the nature of the monodisperse particles. A basic pH is preferred when the monodisperse particles are inorganic, especially comprising silica.

The medium may comprise smaller particles having an average size D less than that of the monodisperse particles by a factor of at least 2, better still at least 3, in order to allow their insertion into the voids left between the monodisperse particles. network.

These interstitial particles can be inorganic or organic and can improve the cohesion of the network or change the absorption of light by the layers of the network. As an example of interstitial particles, mention may be made of nanoparticles of titanium dioxide, silica, iron oxide, carbon black, of average size ranging from 5 to 150 nm, for example from 10 to 100 nm.

As another example of interstitial particles, there may be mentioned particles of a polymer, which is for example in the already polymerized state in the composition before its application to keratin materials, the medium comprising, for example, a latex.

The size of the interstitial particles may, where appropriate, vary depending on an external stimulus and / or the concentration of a compound in the medium. The interstitial particles may be water-absorbing. The size of the particles may then for example vary according to the concentration of water in the medium. The variation in size of the interstitial particles may, if necessary, exert an action on the distance between the monodisperse particles and thus have an action on the color produced by the network.

The medium may comprise at least one polymer to improve the behavior of the network after its formation.

This polymer is for example in the not completely polymerized and / or crosslinked state in the composition before the application thereof and its drying.

When the medium contains a polymer which is not completely polymerized and / or crosslinked before the application of the composition to the keratin materials, the crosslinking and / or polymerization may take place after the application of the composition to the keratin materials.

The polymerization and / or crosslinking may occur for example after formation of the monodisperse particle network or alternatively before and / or concomitantly with the latter. The medium may comprise a film-forming polymer.

Film-forming polymer

In the present invention, the term "film-forming polymer" is intended to mean a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a film which is macroscopically continuous and adheres to the keratin materials, and preferably a cohesive film. and more preferably a film whose cohesion and mechanical properties are such that said film can be isolable and manipulable in isolation, for example when said film is produced by casting on a non-stick surface such as a Teflon or silicone surface.

The composition may comprise an aqueous phase and the film-forming polymer may be present in this aqueous phase. In this case it will preferably be a dispersion polymer or an amphiphilic or associative polymer.

By "dispersed polymer" is meant non insoluble polymers in water present in the form of particles of variable size. The polymer may be crosslinked or not. The average particle size is typically between 25 and 500 nm, preferably between 50 and 200 nm. The following aqueous dispersion polymers can be used: Ultrasol 2075 from Ganz Chemical, Daitosol 5000AD from Daito Kasei, Avalure UR 450 of Noveon, DYNAMX of National Starch, Syntran 5760 of Interpolymer, Acusol OP 301 of Rohm & Haas, Neocryl A 1090 of Avecia.

The acrylic dispersions sold under the names Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®, Neocryl BT-62®, Neocryl A-1079® and Neocryl A-523® by the company Avecia-Neoresins, Dow Latex 432® by DOW CHEMICAL, Daitosol 5000 AD® or Daitosol 5000 SJ® by DAITO KASEY KOGYO; Syntran 5760® by the company Interpolymer, Allianz OPT by the company Rohm & Haas, aqueous dispersions of acrylic or styrene / acrylic polymers sold under the trade name JONCRYL® by the company JOHNSON POLYMER or the aqueous polyurethane dispersions sold under the denominations Neorez R-981® and Neorez R-974® by the company AVECIA-NEORESINS, Avalure UR-405®, Avalure UR-410®, Avalure UR-425®, Avalure UR-450®, Sancure 875®, Sancure 861 ®, Sancure 878® and Sancure 2060® by the company GOODRICH, Impranil 85® by the company BAYER, Aquamere H-1511® by the company HYDROMER; the sulfopolyesters sold under the brand name Eastman AQ® by the company Eastman Chemical Products, the vinyl dispersions, such as the Mexomère PAM® from the company Chimex and their mixtures, are other examples of an aqueous dispersion of water-dispersible film-forming polymer particles.

By "amphiphilic or associative polymers" is meant polymers having one to several hydrophilic moieties which render them partially soluble in water and one or more hydrophobic moieties through which the polymers associate or interact. The following associative polymers may be used: Nuvis FX1100 from Elementis, Aculyn 22, Aculyn 44, Aculyn 46 from Rohm & Haas, Viscophobe DB 1000 from Amerchol. The diblock copolymers consisting of a hydrophilic block (polyacrylate, polyethylene glycol) and a hydrophobic block (polystyrene, polysiloxane, can also be used.

Polymers soluble in an aqueous phase containing the monodisperse hairy particles can be avoided because they can cause aggregation of the monodisperse particles. Thus, the film-forming polymer may be insoluble in such a phase. The composition may comprise an oily phase and the film-forming polymer may be present in this oily phase. The polymer may then be in dispersion or in solution. NAD (non-aqueous dispersion) type polymers or microgels (for example KSG) may be used, as well as polymers of the PS-PA type or styrene-based copolymers (Kraton, Regalite).

Examples of non-aqueous dispersions of lipid-dispersible film-forming polymer in the form of non-aqueous dispersions of polymer particles in one or more silicone and / or hydrocarbon oils and which can be stabilized at their surface by at least one stabilizing agent, in particular a block polymer, grafted or statistical, mention may be made of acrylic dispersions in isododecane, such as Mexomère PAP ® from Chimex, and dispersions of particles of a grafted ethylenic polymer, preferably acrylic, in a liquid fatty phase, the ethylenic polymer advantageously being dispersed in the absence of additional stabilizer at the surface of the particles as described in particular in WO 04/055081. Among the film-forming polymers that can be used in the composition of the present invention, mention may be made of synthetic polymers, of free-radical type or of polycondensate type, polymers of natural origin, and mixtures thereof.

By radical-forming film-forming polymer is meant a polymer obtained by polymerization of unsaturated monomers, especially ethylenic monomers, each monomer being capable of homopolymerizing (unlike polycondensates).

The radical-type film-forming polymers may in particular be polymers, or copolymers, vinylic polymers, in particular acrylic polymers.

The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers having at least one acidic group and / or esters of these acidic monomers and / or amides of these acidic monomers.

As monomer bearing an acid group, it is possible to use α, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid. It is preferable to use (meth) acrylic acid and crotonic acid, and more preferably (meth) acrylic acid. The acidic monomer esters are advantageously chosen from esters of (meth) acrylic acid (also called (meth) acrylates), in particular alkyl (meth) acrylates, in particular C 1 -C 30 alkyl, preferably C 1 -C 20, W

17

(meth) acrylates of aryl, in particular of C 6 -C 10 aryl, hydroxyalkyl (meth) acrylates, in particular hydroxy C 2 -C 6 alkyl.

Among the alkyl (meth) acrylates, mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate.

Among the hydroxyalkyl (meth) acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

Among the aryl (meth) acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

Particularly preferred (meth) acrylic acid esters are alkyl (meth) acrylates.

According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, ie some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

Amides of the acidic monomers include, for example, (meth) acrylamides, and especially N-alkyl (meth) acrylamides, in particular C 2 -C 12 alkyl. Among the N-alkyl (meth) acrylamides, mention may be made of N-ethyl acrylamide, N-t-butyl acrylamide, N-t-octyl acrylamide and N-undecylacrylamide. The vinyl film-forming polymers can also result from rhomopolymerization or the copolymerization of monomers chosen from vinyl esters and styrene monomers. In particular, these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above. Examples of vinyl esters include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate.

Styrene monomers include styrene and alpha-methyl styrene. Among the film-forming polycondensates, mention may be made of polyurethanes, polyesters, polyester amides, polyamides, and epoxy ester resins, polyureas. The polyurethanes may be chosen from anionic, cationic, nonionic or amphoteric polyurethanes, polyurethane-acrylics, poly-urethanes-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea-polyurethanes, and their polyurethanes. mixtures. The polyesters can be obtained, in known manner, by polycondensation of dicarboxylic acids with polyols, especially diols.

The dicarboxylic acid can be aliphatic, alicyclic or aromatic. Examples of such acids are: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-acid. dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-acid, cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers may be used alone or in combination with at least two dicarboxylic acid monomers. Among these monomers, phthalic acid, isophthalic acid and terephthalic acid are preferably chosen.

The diol may be chosen from aliphatic, alicyclic and aromatic diols. A diol chosen from among: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol, 4-butanediol is preferably used. As other polyols, it is possible to use glycerol, pentaerythritol, sorbitol, trimethylolpropane.

The polyester amides can be obtained in a similar manner to the polyesters by polycondensation of diacids with diamines or amino alcohols. As the diamine, there can be used ethylenediamine, hexamethylenediamine, meta- or para-phenylenediamine. As aminoalcohol, monoethanolamine can be used.

The polyester may further comprise at least one monomer bearing at least one -SO3M group, with M representing a hydrogen atom, an NH4 + ammonium ion or a metal ion, for example an Na +, Li +, K +, Mg2 + or Ca2 + ion. , Cu2 +, Fe2 +, Fe3 +. In particular, it is possible to use a bifunctional aromatic monomer comprising such a group -SO3M. The aromatic nucleus of the bifunctional aromatic monomer additionally carrying a group -SO3M as described above may be chosen for example from benzene, naphthalene, anthracene, diphenyl, oxydiphenyl, sulfonyldiphenyl and methylenediphenyl nuclei. An example of a bifunctional aromatic monomer also bearing an -SO 3 M group is sulfoisophthalic acid, sulphoterephthalic acid, sulphophthalic acid and 4-sulphonaphthalene-2,7-dicarboxylic acid.

According to an exemplary composition according to the invention, the film-forming polymer may be a polymer solubilized in a liquid fatty phase comprising organic oils or solvents (it is said that the film-forming polymer is a liposoluble polymer). Preferably, the liquid fatty phase comprises a volatile oil, optionally mixed with a non-volatile oil.

As an example of a fat-soluble polymer, mention may be made of vinyl ester copolymers (the vinyl group being directly connected to the oxygen atom of the ester group and the vinyl ester having a saturated hydrocarbon radical, linear or branched, from 1 to 19 carbon atoms, linked to the carbonyl ester group) and from at least one other monomer which may be a vinyl ester (different from the vinyl ester already present), an α-olefin (having from 8 to 28 carbon atoms), an alkyl vinyl ether (the alkyl group of which contains 2 to 18 carbon atoms), or an allyl or methallyl ester (having a linear or branched, saturated hydrocarbon radical of 1 to 19 carbon atoms, bonded to the carbonyl ester group).

These copolymers may be crosslinked using crosslinking agents which may be of the vinyl type, or of the allyl or methallyl type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and octadecanedioate. divinyl. Examples of such copolymers include copolymers: vinyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecylvinylether vinyl propionate / allyl laurate, vinyl propionate / vinyl laurate, vinyl stearate / octadecene-1, vinyl acetate / dodecene-1, vinyl stearate / ethyl vinyl ether, vinyl propionate / cetyl vinyl ether, stearate of vinyl vinyl / allyl acetate, 2,2-dimethyl-2 vinyl octanoate / vinyl laurate, 2,2-dimethyl-2-allyl pentanoate / vinyl laurate, vinyl dimethyl propionate / vinyl stearate, dimethyl allyl propionate / stearate of vinyl, vinyl propionate / vinyl stearate, cross-linked with 0.2% divinyl benzene, vinyl dimethyl propionate / vinyl laurate, cross-linked with 0.2% divinyl benzene, vinyl acetate / octadecyl vinyl ether, cross-linked with 0 , 2% tetraallyloxyethane, vinyl acetate / allyl stearate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecene-1 crosslinked with 0.2% divinyl benzene and allyl propionate / stearate allyl crosslinked with 0.2% divinyl benzene.

As examples of liposoluble film-forming polymers, mention may be made of vinyl ester copolymers and at least one other monomer which may be a vinyl ester, in particular vinyl neodecanoate, vinyl benzoate and vinyl t-butyl benzoate, an α olefin, an alkyl vinyl ether, or an allylic or methallyl ester.

Liposoluble film-forming polymers that may also be mentioned include liposoluble copolymers, and in particular those resulting from the copolymerization of vinyl esters having from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals having from 10 to 20 carbon atoms.

Such liposoluble copolymers may be chosen from copolymers of vinyl polycrystearate, vinyl polystearate crosslinked with divinylbenzene, diallyl ether or diallyl phthalate, copolymers of stearyl poly (meth) acrylate, polyvinylpolate , poly (meth) acrylate lauryl, these poly (meth) acrylates can be crosslinked using dimethacrylate ethylene glycol or tetraethylene glycol.

The liposoluble copolymers defined above are known and in particular described in application FR-A-2232303; they can have a weight average molecular weight ranging from 2,000 to 500,000 and preferably from 4,000 to 200,000. As liposoluble film-forming polymers that can be used in the invention, mention may also be made of polyalkylenes and especially copolymers of C2-C20 alkenes, such as polybutene, alkylcelluloses with a linear or branched, saturated or non-saturated C1 to C8 alkyl radical, for example ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and of C2 to C40 and better still of C3 to C20 alkene. By way of example of a copolymer of VP which may be used in the invention, mention may be made of the copolymer of VP / vinyl acetate, VP / ethyl methacrylate, polyvinylpyrrolidone (PVP) butylated, VP / ethyl methacrylate / methacrylic acid, VP / eicosene, VP / hexadecene, VP / triacontene, VP / styrene, VP / acrylic acid / lauryl methacrylate.

Mention may also be made of silicone resins, generally soluble or swellable in silicone oils, which are crosslinked polyorganosiloxane polymers. The nomenclature of the silicone resins is known under the name of "MDTQ", the resin being described according to the different siloxane monomeric units that it comprises, each of the letters "MDTQ" characterizing a type of unit.

By way of examples of commercially available polymethylsilsesquioxane resins, mention may be made of those which are marketed: by the company Wacker under the reference Resin MK such as Belsil PMS

MK:

- by the company SHIN-ETSU under the references KR-220L. As siloxysilicate resins, mention may be made of trimethylsiloxysilicate (TMS) resins such as those sold under the reference SR100O by the company General Electric or under the reference TMS 803 by the company Wacker. Mention may also be made of timethylsiloxysilicate resins sold in a solvent such as cyclomethicone, sold under the name "KF-7312J" by the company Shin-Etsu, "DC 749", "DC 593" by the company Dow Corning.

Mention may also be made of silicone resin copolymers such as those mentioned above with polydimethylsiloxanes, such as the pressure-sensitive adhesive copolymers marketed by Dow Corning under the reference BIO-PSA and described in document US 5 162 410 or the silicone copolymers resulting from the reaction of a silicone resin, such as those described above, and a diorganosiloxane as described in document WO 2004/073626. According to an exemplary embodiment of the invention, the film-forming polymer is a film-forming linear ethylenic polymer, which preferably comprises at least a first block and at least a second block having different glass transition temperatures (Tg). first and second sequences being interconnected by an intermediate sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block. Advantageously, the first and second sequences and the block polymer are incompatible with each other.

Such polymers are described for example in EP 1411069 or WO04 / 028488. The film-forming polymer may be chosen from block or static polymers and / or copolymers comprising, in particular, polyurethanes, polyacrylics, silicones, fluorinated polymers, butyl gums, copolymers of ethylene, natural gums and polyvinyl alcohols, and mixtures thereof. The monomers of the block or static copolymers comprising at least one combination of monomers whose polymer results in a glass transition temperature below room temperature (25 ° C.) may be chosen from, in particular, butadiene, ethylene, propylene and acrylic. , methacrylic, isoprene, isobutene, silicone and mixtures thereof.

The film-forming polymer may also be present in the composition in the form of particles in dispersion in an aqueous phase or in a non-aqueous solvent phase, generally known under the name of latex or pseudolatex. The techniques for preparing these dispersions are well known to those skilled in the art.

The composition according to the invention may comprise a plasticizer promoting the formation of a film with the film-forming polymer. Such a plasticizer may be chosen from all compounds known to those skilled in the art as being capable of performing the desired function.

Of course, this list of polymers is not exhaustive.

Preferably, when the medium containing the monodisperse particles contains a film-forming polymer, the latter is, for example, an aqueous dispersion of acrylic, vinylic, fluorinated or silicone polymer, or mixtures thereof. The mass content of the film-forming polymer (s) in the composition containing the monodisperse particles ranges, for example, from 0.1 to 10%.

When the composition containing the monodisperse particles contains a polymer which is not completely polymerized and / or crosslinked, the polymerization and / or crosslinking may be carried out by thermal initiation or by ultraviolet radiation. The polymerization can also be carried out by adding an initiator and optionally a crosslinking agent. When it is desired to make a network of monodisperse particles in the medium, it is possible to add a monomer and an initiator and optionally a crosslinking agent, and then perform the polymerization.

This can take place at the time of manufacture of the formulation or after application to the skin. This method allows the production of high molecular weight polymers or crosslinked polymers. This can make it possible to vary the rheology of the system formed.

The medium may also comprise a polymer allowing the formation of a gel, for example before or after the application of the composition to the support to be made up. Polymers allowing the formation of a gel

The formation of a gel may, for example, improve the cohesion of the network of monodisperse particles and / or render the latter sensitive to an external stimulus and / or to the concentration of a compound in the medium, for example the concentration of water.

The polymer allowing the formation of a gel may be chosen from cellulose derivatives, alginates and their derivatives, especially their derivatives such as propylene glycol alginate, or their salts such as sodium alginate, calcium alginate, derivatives thereof. polyacrylic or polymethacrylic acid, polyacrylamide derivatives, polyvinylpyrrolidone derivatives, ether or polyvinyl alcohol derivatives, and mixtures thereof, among others. The polymer may in particular be chosen from chemically modified cellulose derivatives, for example chosen from carboxymethylcellulose, sodium carboxymethylcellulose, carboxymethylhydroxyethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, hydroxyethylethylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose, methylcellulose, sodium methylcellulose, microcrystalline cellulose, sodium cellulose sulfate and mixtures thereof.

The polymer that makes possible the formation of a gel may also be chosen from natural polymeric derivatives, for example gelatin and glucomannan and galactomannan polysaccharides extracted from seeds, plant fibers, fruits, seaweeds, starch, plant resins, or of microbial origin.

The mass quantity of polymer intended for the formation of a gel in the composition may be between 0.5 and 40%, better still between 1 and 20%. The polymer intended for the formation of a gel can polymerize after the application of the composition to the support to be made up. Alternatively, the gel is formed before applying the composition to the keratin materials, and then applied thereto. Hydrogels can be obtained from acrylamide monomers, acrylic monomers, vinylpyrrolidone for example. An example of a hydrogel obtained by this method based on N-isopropylacrylamide polymerized under a UV lamp in a colloidal polystyrene crystal is for example described in the patent WO 98/41859. The article by FOULGER et al, Advanced Materials, 13, 1898-1901 (2001) describes a hydrogel based on polyethylene glycol methacrylate and dimethacrylate.

The realization of the gel can also take place before the manufacture of the composition. It is possible, for example, to produce an oily gel based on polydimethylsiloxane elastomer from a network of polystyrene spheres as described in the article by H. Fudouzi et al, Langmuir, 19, 9653-9660 (2003). Fatty phase

Although the composition containing the monodisperse particles may be oil-free, the composition according to the invention may nevertheless comprise, in certain embodiments, a fatty phase. The monodisperse particles may or may not be present in this fatty phase. The fatty phase can in particular be volatile.

The introduction of one or more oils can be done so as not to lose the staining effect or spectral reflectance sought.

The composition may comprise an oil such as, for example, esters and synthetic ethers, linear or branched hydrocarbons of mineral or synthetic origin, fatty alcohols having from 8 to 26 carbon atoms, partially hydrocarbon-based fluorinated oils and / or or silicone, silicone oils such as volatile or non-volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, liquid or pasty at room temperature, and mixtures thereof, other examples being given below. A composition according to the invention may comprise at least one volatile oil. Volatile oils

For the purposes of the present invention, the term "volatile oil" means an oil (or non-aqueous medium) capable of evaporating on contact with the skin in less than one hour, at ambient temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10 ^"3 to 300 mm Hg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mm Hg) The volatile hydrocarbon oils may be chosen from hydrocarbon oils of animal or vegetable origin having from 8 to 16 carbon atoms, and especially branched C ₈ -C ₁₆ alkanes (also known as isoparaffins) such as isododecane (still known as 2,2,4,4,6-pentamethyl), isodecane isohexadecane, and for example the oils sold under the trade names Isopar ^® or Permethyls® ^®.

As volatile oils, it is also possible to use volatile silicones, for example volatile linear or cyclic silicone oils, in particular those having a viscosity <8 centistokes (8 × 10 ^-6 m ² / s), and having in particular from 2 to 10 silicon atoms, and in particular 2 to 7 silicon atoms, these silicones optionally containing alkyl or alkoxy groups having from 1 to 10 carbon atoms, for example the volatile silicone oil that can be used in the invention. dimethicones of viscosity 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl disiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and their mixtures.

Fluorinated volatile oils such as nonafluoromethoxybutane or perfluoromethylcyclopentane and mixtures thereof can also be used.

It is also possible to use a mixture of the above-mentioned oils. Non-volatile oils A composition according to the invention may comprise at least one non-volatile oil.

For the purposes of the present invention, the term "non-volatile oil" means an oil having a vapor pressure of less than 0.13 Pa and especially oils of high molecular weight.

The non-volatile oils may in particular be chosen from fluorinated hydrocarbon oils which may be fluorinated and / or non-volatile silicone oils. As non-volatile hydrocarbon oil which may be suitable for the implementation of the invention, mention may be made in particular of: hydrocarbon-based oils of animal origin,

hydrocarbon-based oils of vegetable origin, such as phytostearyl esters, such as phytostearyl oleate, physostearyl isostearate and lauroyl / octyldodecylglutanate / phytostearyl glutanate, for example sold under the name ELDEW PS203 by AJINOMOTO, triglycerides consisting of esters of fatty acids and of glycerol, the fatty acids of which can have various chain lengths of C ₄ to C ₂₄ , the latter being linear or branched, saturated or unsaturated; these oils are in particular heptanoic or octanoic triglycerides, wheat germ, sunflower, grape seed, sesame, corn, apricot, castor oil, shea, 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 triglycerides of caprylic / capric acids 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,

hydrocarbon oils of mineral or synthetic origin, for example:

Synthetic ethers having from 10 to 40 carbon atoms; Linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam, squalane and their mixtures, and in particular hydrogenated polyisobutene,

Synthetic esters such as oils of formula R ₁ COOR ₂ in which R ₁ represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R ₂ represents a hydrocarbon chain, in particular branched, containing from 1 to 40 carbon atoms with the proviso that R ₁ + R ₂ is> 10. The esters may in particular be chosen from esters, in particular of fatty acids, for example:

Cetostearyl octanoate, esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, stearate or isostearate Isostearyl isostearate, octyl stearate, hydroxylated esters such as isostearyl lactact, octyl hydroxystearate, diisopropyl adipate, heptanoates, and especially heptanoate. isostearyl, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 4-diheptanoate and 2-hexyl ethyl palmitate, benzoate alkyl, polyethylene glycol diheptanoate, propylene glycol diethyl-2-hexanoate and mixtures thereof, C12-C15 alcohol benzoates, hexyl laurate, esters of neopentanoic acid such as neopentanoate; isodecyl, isotridecyl neopentanoate, neopentanoate isostearyl e, octyldocecyl neopentanoate, esters of isononanoic acid such as isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, hydroxylated esters such as isostearyl lactate, di-isostearyl malate;

Polyol esters and pentaerythritol esters, such as dipentaerythritol tetrahydroxystearate / tetraisostearate,

The esters of diol dimers and diacid dimers, such as Lusplan DD-DA5® and Lusplan DD-D A7®, marketed by the company Nippon Fine Chemical and described in the application FR 03 02809,

Branched-chain and / or unsaturated carbon-containing liquid alcohols having 12 to 26 carbon atoms, such as 2-octyldodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol or 2-butyloctanol, and 2- undecylpentadecanol,

Higher fatty acids such as oleic acid, linoleic acid, linolenic acid and mixtures thereof, and

Di-alkyl carbonates, the 2 alkyl chains which may be identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC®, by Cognis,

Non-volatile silicone oils, for example non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising pendant alkyl or alkoxy groups and / or silicone chain ends, groups each having 2 to 24 carbon atoms, phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes; and 2-phenylethyl trimethylsiloxysilicates, dimethicones or phenyltrimethicone with a viscosity less than or equal to 100 Cst, and mixtures thereof, and mixtures thereof.

The composition containing the monodisperse particles may be free of oil, in particular containing no non-volatile oil. Kits

The invention also relates to kits comprising a composition according to the invention.

These kits may comprise at least one composition intended to form a base layer, also called "base coat" and / or a layer of recouyrement, also called "top coat".

The kit can thus include:

a first composition comprising:

- monodisperse hairy particles,

a medium allowing the formation on a support on which the composition is applied of an ordered network of monodisperse particles,

a second composition comprising a film-forming polymer.

Such a composition may allow the formation of a base layer or covering. The kit may also comprise, according to a variant:

a first composition comprising:

- monodisperse hairy particles,

a physiologically acceptable medium for forming on a support on which the composition is applied an ordered network of monodisperse particles, - A second composition comprising at least one coloring agent, for example a pigment or black dye, or an effect pigment (reflective particles, nacres, goniochromatic coloring agent).

Such a second composition can improve the optical properties of the first composition.

The base layer and the cover layer may be simultaneously present, the kit may then comprise:

a first cosmetic composition comprising:

- monodisperse hairy particles, - a physiologically acceptable medium for forming on a support on which the composition is applied an ordered network of monodisperse particles,

a second cosmetic composition to be applied to the support before the application of the first composition, so as to improve its adhesion to the support and smooth the keratinous surfaces,

a third cosmetic composition. apply on the first composition so as to change the color or another visible characteristic and possibly improve the behavior of the second composition.

Base layer The base layer is compatible with its application on keratin materials, for example skin, lips, nails, eyelashes or hair, depending on the nature of the makeup sought, including one of those listed above. .

The base layer may comprise a polymer chosen in particular from film-forming polymers. The base layer can, according to different aspects of the invention, perform one or more of the following functions:

the base layer can smooth the support before the application of the composition comprising the monodisperse particles in order to facilitate the formation of the first layers of the network and to obtain a network with the widest possible monocrystalline zones,

the base layer can color the support in order to bring out or modify the color produced by the network. For this purpose, the base layer may comprise at least one coloring agent to reduce the clarity of the support. The base layer may for example comprise a pigment or a black dye, or a different color, to create a colored background for adding an additional color to a given color by the network of monodisperse particles. Among the dyes or pigments that may be present in the base layer, there may be mentioned in particular black iron oxide, carbon black, black titanium dioxide;

the base layer can improve the adhesion of the composition containing the monodisperse particles to the coated support. For this purpose, the base layer may comprise at least one polymer having adhesive or adhesive properties, that is to say capable of becoming adhesive by interaction with another compound. The polymer may especially have adhesive or adhesive properties as defined in patents FR 2834884, FR 2811546 and FR 2811547:

The base layer may further exert an action on the surface tension of the keratin materials to allow, for example, good wettability by the composition layer containing the monodisperse particles and to promote the stacking of the monodisperse particles.

The base layer may comprise the same polymer providing at least two of the aforementioned functions, for example those of smoothing and increasing adhesion, or possibly a coloring function. The base layer can be formulated according to the nature of the monodisperse particles.

In non-limiting examples of implementation of the invention, the monodisperse particles may be of polystyrene and the base layer comprise a non-aqueous dispersion NAD in isododecane or polymers DAITOSOL (Daito Kasei) or ULTRASOL (Ganz Chemical) . In other examples, the monodisperse particles being silica, the base layer may comprise Eastman AQ polymer (20%) or PVA (10%).

The base layer may comprise a volatile phase.

The polymer is preferably capable of forming a film after application and drying of the composition. The formation of the film can be done with the aid of a coalescing agent. The polymer may be in dispersion or in solution in an aqueous or anhydrous phase. This polymer is preferably dispersed in water or in an oil. Of even more preferably, the polymer contains at least one function capable of being ionized in aqueous solution, such as a carboxylic acid. The polymer will preferably be insoluble in contact with an aqueous phase after application and drying.

It is also possible to use according to this process in the base layer monomers or prepolymers which are also able to polymerize after application to the skin, either by UV action, heat or the presence of water for example. Examples that may be mentioned include cyanoacrylate monomers or low mass silicone polymers carrying reactive functions.

Examples of polymers in aqueous dispersion that may be mentioned include: Ultrasol 2075 from Ganz Chemical, Daitosol 5000AD from Daito Kasei, Avalure UR 450 from Noveon, DYNAMX from National Starch, Syntran 5760 from Interpolymer, Acusol OP 301 from Rohm & Haas, Neocryl A 1090 of Avecia.

As an example of an oily dispersion polymer, mention may be made of: NAD and the polymers as disclosed in EP-A-749,746 of the company L'Oréal, the acrylic-silicone polymer dispersion ACRJT 8HV-1023 from the company Tasei Chemical industries.

The volatile phase may be an aqueous phase or an anhydrous phase. In the case of an aqueous phase it is preferably water, alcohol and glycol. In the case of an anhydrous phase, it preferably consists of at least one volatile oil.

Coating layer

The covering layer may in particular have the function of changing a visible characteristic such as color or brightness and / or the function of improving the resistance of the network of monodisperse particles to the support, in particular to increase the resistance to friction of the network and avoid its crumbling.

The covering layer may comprise one or more polymers that may or may not penetrate into the particle network, the penetration of the polymer causing a change in the refractive index of the medium around the particles and thus a change in the color. The covering layer may have a volatile phase, which may make it possible to limit the color change over time, which may cease during the evaporation of the volatile phase.

The second composition may especially comprise a volatile oil, as defined above.

The cover layer may include a non-volatile solvent, which may increase the durability of the color change. This solvent will penetrate and remain in the medium between the particles and modify the refractive index around the particles.

The second composition intended to form the covering layer may thus comprise a non-volatile oil, as defined above.

The cover layer may have a high transparency to avoid affecting color and / or color intensity from the monodisperse particle array.

The covering layer can be colored further, for example to exert an influence on the color and / or the brightness produced by the network of monodisperse particles.

The cover layer can further slow down moisture uptake or drying of the composition layer containing the ordered network and reduce the variability of the result over time. The covering layer can, on the contrary, increase the sensitivity to the environment, in order to create, for example, a dependence of the color on the ambient temperature or humidity.

The covering layer preferably comprises a film-forming polymer.

The formulation of the covering layer can be adapted to the nature of the monodisperse hairy particles.

The covering layer may contain monodisperse hairy or non-hairy particles having an average size different from those of the monodisperse particles covered by the covering layer. This can change the color of the underlying composition. The covering layer may in this case be covered, optionally, by a layer intended to improve the holding. Galenic forms

The composition containing the monodisperse particles may be in different galenical forms used in the cosmetic field, used for topical application: direct, inverse or multiple emulsions, gel, creams, solutions, suspensions, lotions.

The composition may be in the form of an aqueous solution or an oily solution, in particular a gelled solution, of a liquid or semi-liquid consistency emulsion of the milk type, obtained by dispersion of a fatty phase in an aqueous phase (HJE) or conversely (E / H), a triple emulsion (W / O / E or H / E / H), or suspension or emulsion of soft consistency.

The composition according to the invention may constitute a skincare, make-up and / or sun protection composition. In the case of a sunscreen composition, the size of the particles may be chosen so as to reflect the wavelengths of the UVA and / or UVB, the choice of the size of the particles being effected for example from the relation Bragg mλ = 2ndsinθ, where m is the diffraction order, n the mean refractive index of the medium, θ the angle of incidence between the incident light and the distance between the diffraction planes.

The composition may be in the form of a facial makeup product, especially the skin and / or lips, eyes or nails. Makeup processes

The subject of the invention is also a method for making up keratin materials, comprising the following steps:

- apply on a support to make up a base layer,

- Apply on the base layer a cosmetic composition comprising monodisperse hairy particles and a medium for the formation of an ordered network of monodisperse particles.

Such a process makes it possible to improve the quality of application of the composition comprising the monodisperse particles, especially when they are in an aqueous medium, and also makes it possible to obtain good "crystallization" after application to the skin or the hair for example.

The base layer makes it possible, as mentioned above, to control and standardize the surface properties of keratin materials, in particular the tension of area. It also smoothes and evenens surface roughness. An electrostatic repulsion effect can also occur if the base layer is likely to create an electrostatic charge in contact with water.

Apart from the very substantial improvement in the arrangement of the particles, the base layer may optionally have the effect of fixing the layer of monodisperse hairy particles, making it more stable with respect to external aggressions.

The base layer, according to this process, preferably contains a polymer and a volatile phase.

The composition containing the monodisperse hairy particles may comprise an aqueous medium.

The base layer may comprise, as mentioned above, a polymer having adhesive properties and / or a coloring agent, in particular of black color.

The application of the composition containing the monodisperse particles may be carried out after drying of the base layer, for example for a duration greater than or equal to 30 s.

The subject of the invention is, according to another of its aspects, a method comprising the following steps:

applying a composition comprising monodisperse hairy particles and a medium enabling the formation of an ordered network of monodisperse particles to be applied to a makeup carrier, optionally covered with a base layer,

- Apply on the deposition of the composition containing the monodisperse hairy particles an overcoat layer to improve the strength of the composition layer containing the monodisperse particles. The covering layer may comprise a film-forming polymer, as mentioned above.

The application of the covering layer can be carried out after drying of the composition layer containing the monodisperse particles, for example for a duration greater than or equal to 30 s. The invention also relates to a method in which a first network of monodisperse hairy particles having a mean size is formed, and then forming above this first network a second network of monodisperse hairy particles having an average size different from those of the first network.

The subject of the invention is, according to another of its aspects, a method comprising the following steps: - applying a first composition comprising monodisperse hairy particles and a medium allowing the formation of a network of these particles, to apply on the first composing a second composition making it possible to change the color or a visible characteristic of the first composition, in particular by modifying the refractive index of the medium around the particle network and / or by modifying the distance between the particles of the network.

The applicant has in particular found that it is possible to modify the coloration obtained by a first cosmetic composition by a second non-colored composition, subsequently applied.

The crystal lattice formed by the first composition may be composed of a continuous layer or of discontinuous islands. The light is diffracted by this crystal lattice and the diffracted wavelength depends on the. distance between the particles and the refractive index.

The second composition, which forms the cover layer, may contain at least one liquid medium capable of penetrating into the first composition and modifying the distance between the particles and / or the refractive index. The liquid medium may be volatile or not. In the case where it is completely volatile, the color change is temporary and the color gradually returns to the initial state. In the case where a large proportion of the liquid medium is non-volatile, a lasting change in the color can be obtained. The crystal lattice may be compact or not, continuous or not. It can be formed prior to application or formed during application.

The second composition may contain at least one liquid phase, which may come to swell the network or change the refractive index of the medium. In the case of a simple change in refractive index, the liquid phase may have a different refractive index of the medium surrounding the monodisperse particles.

The second composition may also contain a polymer to fix the first composition. It is also possible to use monomers or prepolymers which are also able to polymerize after application to the skin, either by UV action, heat or the presence of water, for example. Examples that may be mentioned include cyanoacrylate monomers or low mass silicone polymers carrying reactive functions. A colored or non-colored base layer may optionally be applied before these two compositions to the keratin materials.

Another subject of the invention, according to another of its aspects, is a process in which an array of monodisperse particles is formed on the keratin materials and a composition is applied to this network making it possible to modify the refractive index around the particles of the keratinous material. networks, especially those of the network surface layer, which may make it possible to change the color.

Modes of application

The composition containing the monodisperse particles, and possibly the compositions intended to form the base and covering layers, can be applied using an applicator, preferably flocked, for example a tip or a flocked foam, or a brush, especially with fine and supple hair.

The application may also be carried out differently, for example by means of a foam, a felt, a spatula, a frit, a brush, a comb, a woven or not woven. The application may also be carried out with the finger or by directly depositing the composition on the support to be treated, for example by spraying or spraying using for example a piezoelectric device or by transfer of a layer of composition deposited on an intermediate support.

The composition containing the monodisperse particles may be applied in a thickness of, for example, between 1 and 10 μm, better still between 2 and 5 μm.

The application of the composition containing the monodisperse particles is carried out for example with a specific gravity of between 1 and 5 mg / cm ² .

The network of monodisperse particles that is formed comprises for example at least six layers of particles, better between six and 20 layers. The application of the composition to the keratin materials can be done in such a way as to allow the network of monodisperse particles to form after the deposition. Thus, the medium of the composition can be formulated so that the evaporation of the solvents it contains is slow enough to allow the particles time to order and also limit the risk of disorderly agglomeration of particles before application.

The covering layer is for example applied to a thickness ranging from 0.5 to 10 μm. The base layer is for example applied to a thickness ranging from 0.5 to 10 μm.

The application of the covering layer can be done by spraying, which reduces the risk of damage to the underlying lattice

Packaging The composition containing the monodisperse hairy particles may be packaged in any receptacle or on any support provided for this purpose.

The composition may be in the form of a kit comprising two compositions packaged in two separate receptacles.

The composition may be in the form of a kit comprising a first receptacle containing the composition comprising the monodisperse hairy particles and a second receptacle containing at least one of the compositions intended to form the base layer and the covering layer.

Proposed example The contents indicated are mass.

a) Synthesis of Polvstyrene-PNIPAM Hairy Particles

Polystyrene particles (size 290 nm, CV = 3.5%, known under the reference Optibind ^® and sold by the supplier Seradyn) are reacted with sodium N, N-diethyldithiocarbamate for 12 hours then purified. 1 g of these particles, 4 g of N-isopropylacrylamide and 400 g of water are then mixed. The mixture is irradiated under UV until the end of the controlled radical polymerization. The particles are then carefully washed and concentrated.

b) Composition containing the monodisperse hairy particles

Hairy monodisperse particles * * * 10

Ethanol 5 Ethylene Glycol 10

Water 75

*** Synthesized according to a).

c) A base layer can be applied first, before the composition according to b). After application and drying of the composition containing the monodisperse particles, a very bright red color is obtained.

Base coat: Ultrasol® 2075 (Ganz Chemical) * 80

Cab-O- Jet 200 Black Coloring * * 10

Water 10

* Copolymer Acrylate / ammonium methacrylate dispersed in water at a mass concentration of 50%. ** Carbon black 130nm in aqueous dispersion 20% marketed by Cabot Corp.

The expression "having one" shall be understood as being synonymous with "having at least one", unless the opposite is specified. The expression "included between" must be understood as inclusive, unless the opposite is specified.

Claims

1. Cosmetic composition comprising: a physiologically acceptable medium, monodisperse particles comprising an insoluble core from which, especially by grafting, polymer chains which are soluble in the medium extend, the monodisperse particles being capable of forming an ordered network of particles monodisperse on a support on which the composition is applied.

2. Composition according to the preceding claim, the heart of the monodisperse particles comprising an organic compound.

3. Composition according to claim 2, the core comprising a polymer chosen from polymers or copolymers based on styrene or acrylate.

4. Composition according to claim 1, the core of the monodisperse particles comprising an inorganic compound.

5. Composition according to claim 4, the core comprising silica.

6. The composition as claimed in claim 1, the polymer chains being chosen from acrylic polymers, polymers based on acrylic or methacrylic acid, isobornyl acrylate or methacrylate, isobutyl acrylate or methacrylate, methyl methacrylate, styrenic polymers, styrene-based copolymers such as styrene / acrylic, styrene / maleic acid, styrene / ethylene-polypropylene copolymers, silicone or acrylic silicone polymers, polyacrylamides such as polyisopropylacrylamide.

7. Composition according to any one of claims 1 to 6, the number-average molecular mass of a polymer chain being between 1,000 and 1,000,000.

8. Composition according to any one of the preceding claims, the polymer chains containing at least one chemical function selected from a carboxylic acid, an amine, an amide, a thiol.

9. Composition according to any one of claims 1 to 8, the average particle size after application and drying of the composition ranging from 50 nm to 800 nm, preferably from 100 to 500 nm

10. Composition according to any one of claims 1 to 9, the average hydrodynamic diameter of the monodisperse particles in solution ranging from 100 nm to 2 microns.

11. Composition according to any one of claims 1 to 10, the medium containing the monodisperse particles being aqueous, the monodisperse particles being contained in an aqueous phase.

12. Composition according to any one of the preceding claims, the heart of the monodisperse particles being hollow.

13. Composition according to any one of the preceding claims, the medium comprising particles other than monodisperse particles.

14. Composition according to claim 13, the other particles comprising particles larger than the monodisperse particles after drying.

15. Composition according to claim 14, the larger particles being chosen from effect pigments.

16. Composition according to any one of the preceding claims, comprising a film-forming polymer.

17. Composition according to any one of the preceding claims, the mass content of monodisperse particles ranging from 1 to 70%.

18. A makeup process comprising the step of applying to a support to make up a cosmetic composition as defined in any one of the preceding claims.