FR3008312A1 - THREE-PHASE COSMETIC COMPOSITIONS COMPRISING ENCAPSULATED PIGMENTS - Google Patents

Abstract

The present invention relates to a cosmetic composition comprising a physiologically acceptable medium containing: (1) an aqueous phase; (2) an oil phase of lower density than that of the aqueous phase; and (3) encapsulated pigment particles dispersed in the aqueous phase; the number average diameter of said encapsulated pigment particles being between 200 microns and 3000 microns, said aqueous and oily phases not being in the form of a stable emulsion.

Description

The present invention relates to three-phase cosmetic compositions comprising encapsulated pigments. BACKGROUND OF THE INVENTION The present invention relates to three-phase cosmetic compositions comprising encapsulated pigments. More particularly, the subject of the present invention is compositions comprising an oily phase, an aqueous phase and encapsulated pigment particles, in the form of three superimposed layers at rest.

It is known to one skilled in the art to disperse pigments or fillers in an aqueous phase in order to produce a make-up or care product which is characterized by a very important freshness. By way of example, mention may be made of the products sold in Japan under the name "Mizu-oshiroi", whose fresh effect, felt on application, is particularly appreciated when the ambient temperature is high. The absence of oily phase in these products, however, may limit its use, because it can make the application of the product difficult, causing feelings of dryness and discomfort after application and during the day.

The person skilled in the art therefore seeks, by formulating this class of product, a means of introducing an oily phase, to improve the application properties and to increase hydration and comfort. One of the well known ways to coexist an oily phase and an aqueous phase is to use surfactants to form an emulsion, but these can cause skin irritation. The cosmetic companies that market this class of products therefore seek to avoid them and wish to put forward the tolerance for the skin of this type of product in relation to the minimalist character of their compositions. But in the absence of surfactants, it is observed most often after stirring, when the product is at rest, that some of the pigments or fillers adhere along the walls of the bottle above the liquid, or station at the interface of the oily phase and the aqueous phase, which reduces its aesthetic appearance. This defect is particularly visible when the filling of the bottle with the liquid is only partial and the walls of the bottle are made of glass.

Shiseido has proposed, in its patent application JP 2002-234815, to coat pigments and fillers with kaolinite. But this treatment, which is based on the reaction of sodium silicate with aluminum chloride in aqueous solution and in the presence of an ion exchange resin, is a long and complex reaction and the particles thus coated can subsequently release aluminum ions in the products, which is undesirable.

It therefore remains necessary to find pigments which do not have these disadvantages after shaking and which remain confined in the liquid medium within a single phase. It therefore remains necessary to find a means of obtaining a dispersion of pigments in a liquid medium, transparent or translucent, not exhibiting a phenomenon of adhesion of the pigments on the walls in the container containing said dispersion, and which leads to a product which has good application properties, freshness and comfort over time. The present invention therefore aims to provide a cosmetic composition comprising encapsulated pigments, which has satisfactory application properties, freshness, hydration and comfort over time. The present invention also aims to provide a cosmetic composition comprising encapsulated pigments, which has an attractive visual appearance.

The present invention also aims to provide a cosmetic composition having no agglomeration phenomenon of encapsulated pigments at rest. Thus, the present invention relates to a cosmetic composition comprising a physiologically acceptable medium containing: (1) an aqueous phase; (2) an oil phase of lower density than that of the aqueous phase; and (3) encapsulated pigment particles dispersed in the aqueous phase; the number average diameter of said encapsulated pigment particles being between 200 μm and 3000 μm, said aqueous and oily phases not being in the form of a stable emulsion. Unexpectedly, it has been found by the inventors that it is possible to obtain a product meeting the desired criteria for application properties, freshness and comfort over time and which has an attractive visual appearance, dispersing pigments encapsulated in an aqueous phase in the presence of an oily phase incompatible with this aqueous phase. When the product is at rest, it is in the form of at least two distinct superposed layers, the oily phase constitutes the upper layer and the aqueous phase, containing the encapsulated pigments, constitutes the lower layer. Under agitation, the oily phase, the aqueous phase and the encapsulated pigments intimately mix to form a homogeneous product which can then be applied. Then, at rest, the aqueous and oily phases are progressively separated and the encapsulated pigments sediment in the aqueous phase without adhering to the walls of the bottle containing them. The compositions according to the invention are thus triphasic compositions at rest, in which the encapsulated pigments remain confined in the liquid medium after stirring. The presence of these three distinct phases is clearly visible to the naked eye. In the context of the present invention, the compositions are at rest in the form of a three-phase composition, comprising the oily phase, the aqueous phase and the encapsulated pigments and may, with stirring, form a homogeneous mixture of these three phases. However, they do not form a stable emulsion. Thus, after stirring, the compositions according to the invention do not remain in the form of a stable intimate mixture, but the three phases separate again to form the three-phase compositions described above. The compositions of the invention do not form a stable emulsion, i.e. this form of emulsion is not maintained long enough.

According to the invention, the stability of the emulsion is less than or equal to 48 hours, preferably less than or equal to 24 hours, more preferably less than or equal to 12 hours, and even more preferably less than or equal to 6 hours. These limits correspond to the time after which, after stirring according to the protocol below, the oily phase and the aqueous phase are completely separated into two distinct phases and superimposed. The non-stability of the emulsion is evaluated according to the following protocol: A sample of 20 g of the composition is introduced into a glass flask of about 30 ml (diameter 2.5 cm, height 8 cm). In order to ensure that the sample taken is true to the composition, it is conditioned after homogenizing the composition with stirring. It is thus possible to take the sample just after manufacture.

The bottle is left standing for 24 hours in a vertical position, before being evaluated. 10 successive rotations of the bottle, a rotation consisting in reversing the bottle to 1800, then to reverse it again to 180 °, which amounts to return to its original position. These successive rotations cause stirring of the composition which leads to the mixing of the phases. The bottle is then left standing in an upright position to assess stability.

According to the invention, it is necessary to observe, after 48 hours maximum, a complete separation of the oily phase and of the aqueous phase which overlap, the oily phase constituting the upper layer and the aqueous phase, the lower layer. Depending on the viscosity of the aqueous phase, the encapsulated pigments may remain more or less in suspension in this phase after 48 hours or be at the bottom of the bottle after having completely sedimented. This concept of stable emulsion is well known to those skilled in the art and is for example defined in the article by Rudolf Heusch in Ullmann's Encyclopedia of Industrial Chemistry "Emulsions" of June 15, 2000.

Furthermore, according to the invention, the dispersion of encapsulated pigments described above (dispersion of the encapsulated pigments in the aqueous phase) does not form a pickering emulsion able to stabilize the aqueous and oily phases in the form of emulsion. The encapsulated pigments according to the invention therefore do not make it possible to stabilize the emulsion formed by the phases in the presence and are therefore not found at the interface of the two aqueous and oily phases. Preferably, the compositions according to the invention do not comprise an emulsifier (s) in a content capable of stabilizing the aqueous and oily phases in the form of a stable emulsion. When the compositions of the invention optionally comprise one (or more) emulsifier (s), it is present in a small amount and therefore insufficient to obtain a stable emulsion as defined above. According to one embodiment, the compositions according to the invention do not comprise a reflective particle (s) pre-dispersed in an oil. According to one embodiment, the compositions according to the invention do not comprise dispersion of nacre particles based on mica and titanium dioxide in ethylhexyl hydroxystearate.

According to one embodiment, the compositions according to the invention do not comprise particles of bismuth oxychloride. According to one embodiment, the compositions according to the invention do not comprise particles of bismuth oxychloride dispersed in ethylhexyl hydroxystearate.

According to one embodiment, the compositions according to the invention are not in the form of a foam. Encapsulated Pigments The cosmetic compositions according to the invention comprise particles of encapsulated pigments, dispersed in the aqueous phase, these particles possibly being identical or different. The compositions according to the invention may therefore comprise mixtures of encapsulated pigment particles of different nature. These particles of encapsulated pigments are in the form of a dispersion of particles in the aqueous phase, and, as indicated above, once the composition is stirred, they form with the aqueous and oily phases a homogeneous product, easy to be applied on keratin surfaces, especially on the skin or hair. In the context of the present invention, the encapsulated pigment particles are defined by their average size which is measured by particle size. The average size of these particles corresponds to their apparent diameter because they are assimilated, during the measurement, to spheres. The average size is characterized by the D50 which corresponds to the average particle size of half of the population. The particle size is measured by sieving.

The encapsulated pigments of the invention have a number average diameter that can preferably range from 300 μm to 1500 μm, and preferably from 400 μm to 1400 μm. According to the invention, the term "encapsulated pigments" means pigments which are contained in (micro) capsules constituting a shell around the pigment, the shell being ruptible in response to a certain pressure exerted on the application of the composition. incorporating. Thus, the microcapsule constituting a shell around the encapsulated pigment is broken during the displacement of the application member impregnated with said composition, on the surface of the keratin material.

The capsules or microcapsules may consist of one or more concentric layers around a core. The pigment (s) may be present in the core and / or the layers around the core. The microcapsules may contain, for example, only one kind of pigment corresponding to a single color, or several kinds of pigments. An encapsulated pigment is different from a coated pigment commonly used in make-up products. Indeed, while the coated pigments comprise a chemical coating intended to improve the dispersion in the composition, the encapsulated pigments comprise a physical layer constituted by the shell of the capsule, this layer being relatively homogeneous and sealingly isolating the encapsulated pigment, so that each encapsulated pigment is well individualized in the composition, which is not the case of coated pigments. An encapsulated pigment has the advantage of being little or not visible in the composition thanks to its encapsulation, while being easily released from the microcapsule during the application of the composition incorporating it.

According to one embodiment, the pigments, that is to say the pigments that are encapsulated (in the microcapsule), are selected from the group consisting of inorganic pigments, organic pigments, interference pigments, surface-treated or otherwise treated, metal powders and their mixtures. The encapsulated pigments according to the invention can therefore be chosen from the pigments as defined above, contained in a microcapsule as defined above. Among the inorganic pigments, mention may be made of titanium dioxide, iron oxides, zinc oxide, chromium oxide, manganese violet, ultramarine blue and Prussian blue.

Among the organic pigments, mention may be made of D & C type pigments, cochineal carmine lacquers and carbon black. Among the metal powders, mention may be made of aluminum powder and copper powder. Preferably, the encapsulated pigments according to the invention are encapsulated inorganic pigments. The pigments are preferably encapsulated in microcapsules both resistant to the other raw materials present in the composition and flexible enough to be able to break under shear during application to thereby deliver the expected color.

Thus, the encapsulated pigments are "activated" during the application of the composition. In other words, after activation, the pigments provide the composition applied to the keratin material, a coloration, distinct from that of the composition under conditioning. Before application, the composition may in particular have, in its packaging, any shade, for example white, gray, associated with the other ingredients of the composition, while once the pigments activated on application, it advantageously reveals a desired coloration by the user. The revelation of the color by the pigments may also be partly the result of variations in pH or temperature between the cosmetic composition in its packaging and once it is applied to the keratin material. Contacting the encapsulated pigments, when the composition is applied to the skin, with water or other fluids present on the surface of the skin may also promote the development of the coloring. According to one embodiment, the encapsulated pigments according to the invention are pigments in capsules made of a material chosen from the group consisting of hot-melt compounds whose melting point is between 30 ° C. and 70 ° C., polymers or copolymers based on polyacrylates or methacrylates, copolymers based on styrene / acrylate, polymers based on polyesters, polyaminomethacrylates or polyvinylpyrrolidone, polysaccharides, proteins and mixtures thereof.

Thus, the shells of the microcapsules can be made of materials selected for example from the materials as defined above. As hot-melt compounds whose melting temperature is between 30 ° C and 70 ° C, preferably between 37 ° C and 45 ° C, mention may be made of microcapsules consisting of jojoba esters, sold under the reference Florasome by the company Floratech. Mention may also be made of the microcapsules described in application US 2006/0292193 or the microcapsules described in documents US Pat. No. 6,432,428 and WO2006081351. As polymers or copolymers based on polyacrylates or methacrylates, mention may be made of the microcapsules based on acrylate / ammonium methacrylate copolymer sold by the company Tagra Biotechnologies Ltd and described in application WO 01/35933, such as for example the reference YELLOWCAP1 for yellow iron oxide, REDCAP1 for red iron oxide and BLACKCAP1 for black iron oxide. It is also possible to mention the encapsulated pigments marketed by TAGRA BIOTECHNOLOGIES under the name BLACKCAP3, YELLOWCAP3, REDCAP3 by INCI name composed of several ingredients: titanium dioxide (and) iron oxide (and) isopropyl myristate (and) acrylates / ammonium methacrylate copolymer (and) Triethyl citrate. Examples of copolymers based on styrene / acrylate include, for example, the microcapsules sold under the name Coloursphere by the company Créations Couleurs. Examples of polymers based on polyesters, polyaminomethacrylates or polyvinylpyrrolidone include those described in Biogenics US Application 2011/0165208 and in particular the capsules marketed under the name Magicolor by Biogenics.

As polysaccharides, mention may in particular be made of cellulose derivatives, such as, for example, methylcellulose, ethylcellulose and carboxymethylcellulose, starch, algin and alginates, agars and agaroses, pectins and polypectates. or even carrageenans. As examples of pigments encapsulated by cellulose derivatives, mention may be made of the spheres comprising mannitol, cellulose, hydroxypropylmethylcellulose, sold by the company Lnduchem under the name of United Bicolor WNRM-621 SBI. As proteins, mention may in particular be made of gelatin, casein, zein, soya proteins and albumin.

In a particular embodiment, the core of the microcapsules as mentioned above may comprise the pigment and be surrounded by layers formed of a polymeric material. In another particular embodiment, the core does not comprise pigment and is surrounded by layers comprising at least one pigment.

The nucleus may be surrounded by one or more layers. According to one particular embodiment, it will be possible to use microcapsules comprising at least two concentric layers around the core; we will talk about multi-layer microcapsules. Such multilayer microcapsules are described below.

First type of multilayer microcapsules According to a particular embodiment, the microcapsules comprise a core and at least two concentric layers (outer layer and inner layer (s)) around said core; we are talking about 'multilayer' microcapsules. In a particular embodiment, the outermost layer comprises at least one pigment. The pigments are described above. According to a preferred embodiment, the pigments are inorganic pigments, in particular chosen from metal oxides, and in particular iron oxides, titanium dioxide and mixtures thereof. The microcapsules can be prepared by various methods known in the field of coating or encapsulation, including the formation of pellets, granulation, coating .... By way of example, the microcapsules can be prepared by mixing of the compounds (active agents, pigments, polymers, solvents) and drying to form the capsules (eg W001 / 35933 and WO2011 / 027960), or by granulation and formation of the layers by spraying and drying (eg FR2841155), or by the fluidized bed technology, used in the food and pharmaceutical industry. For example, the application W008139053 describes the preparation of multilayer spheroids comprising a sugar core and concentric layers containing pharmaceutical active ingredients. The actives are fixed by impregnation or spraying or projection on the core, then the first layer is dried before the application of a second. Fluidized bed technology is described for example in Teunou et al. (FluidBed Coating, Poncelet, 2005, D. Food Science and Technology (Boca Raton, FL, United States), Volume 146 Issue Encapsulated and Powdered Foods, Pages 197-212). A characteristic of this technology is that it leads to particles in which the core is well encapsulated, especially in comparison with atomization technology which leads to obtaining a randomly dispersed core in a polymer. According to a preferred embodiment, the microcapsules are obtained by a fluidized bed process. According to this embodiment, preferably at least one layer of the microcapsules is obtained by a fluidized bed process. In a particular embodiment, the outer layer of the microcapsules is obtained by a fluidized bed process. In another particular embodiment, at least one inner layer of the microcapsules is obtained by a fluidized bed process. Preferably, all the layers are obtained by a fluidized bed process. The skilled person knows how to adjust the amount of air, the amount of liquid and the temperature to reproduce a capsule according to the invention. Preferably, a fluidized bed process implemented according to the invention comprises a Würster method and / or a tangential spraying method. Such a method makes it possible, unlike a granulation process, to prepare spherical capsules with a core surrounded by one or more circumferential layers. When the entire process for preparing the layers surrounding the core of the microcapsules according to the invention is carried out by a fluidized bed process, the microcapsule layers are advantageously regular, concentric and have a uniform thickness. Various examples of capsule preparation according to the invention will be given later in this description. The core of said multilayer microcapsules comprises an organic material. Preferably, the ring is in a solid or crystalline form at room temperature. In particular, the organic material is chosen from soluble or dispersible organic materials. In a particular embodiment, the core essentially consists of said organic material. Preferably, the nucleus is a sugar alcohol, preferably a monosaccharide alcohol, advantageously chosen from mannitol, erythrol, xylitol, or sorbitol. In a preferred mode, the core is made of mannitol. The core is generally from 1% to 50% by weight, preferably from 5% to 30% by weight, and more preferably from 10% to 20% by weight of the microcapsules.

The mannitol is preferably contained in an amount ranging from 2% to 100% by weight, preferably from 5% to 100% by weight, and in particular at 100% by weight relative to the total weight of the core of the microcapsules. The mannitol is preferably contained in an amount ranging from 1% to 50% by weight, preferably from 4% to 40% by weight, and in particular from 5% to 30% by weight, and especially from 10% to 20% by weight. by weight relative to the total weight of the microcapsule. As described above, the core is advantageously coated with one or more concentric outer layers with respect to the core, preferably at least one or more inner layers and an outer layer.

In a particular embodiment, the inner and / or outer layers comprise at least one polymer, preferably a hydrophilic polymer. Said hydrophilic polymer is soluble or dispersible in water or alcoholic compounds, in particular compounds selected from lower alcohols, glycols, or polyols.

By "hydrophilic polymer" according to the invention is meant in particular a (co) polymer capable of forming hydrogen bonds with water or said alcoholic compounds. Particularly concerned are the O-H, N-H and S-H bonds. According to one particular embodiment, said hydrophilic polymer can swell in contact with water or said alcoholic compounds. The hydrophilic polymer may be chosen from: homo or copolymers of acrylic or methacrylic acids or their salts and esters, and in particular the products sold under the names "VERSICOL F" or "VERSICOL K" by the company ALLIED COLLOID , "UTRAHOLD 8" by the company CIBA-GEIGY, polyacrylic acids of the SYNTHALEN K type, and the salts, in particular of sodium, of polyacrylic acids (answering the name INCI sodium acrylate copolymer) and more particularly a crosslinked sodium polyacrylate ( the INCI name sodium acrylate copolymer (and) caprylic / capric triglyceride) sold under the name "LUVIGEL EM" by the company BASF; copolymers of acrylic acid and of acrylamide sold in the form of their sodium salt under the names "RETEN" by the company HERCULES, sodium polymethacrylate sold under the name "DARVAN No. 7" by the company VANDERBILT, and the sodium salts of polyhydroxycarboxylic acids sold under the name "HYDAGEN F" by Henkel; the polyacrylic acid / alkyl acrylate copolymers, preferably the modified or unmodified carboxyvinyl polymers, the copolymers acrylate / C10-C30-alkylacrylate (INCI name Acrylates / C10-30 Alkyl Acrylate Crosspolymer) are particularly preferred according to the present invention; that the products sold by Lubrizol under the trade names Pemulen TR1, Pemulen TR2, Carbopol 1382, Carbopol Etd 2020 and even more preferably Pemulen TR-2; - AMPS (polyacrylamidomethyl propane sulfonic acid partially neutralized with ammonia and highly crosslinked) marketed by Clariant; the AMPS / acrylamide copolymers of SEPIGEL or SIMULGEL type marketed by the company SEPPIC, in particular a copolymer of INCI name POLYACRYLAMIDE (and) C13-14 ISOPARAFFIN (and) LAURETH-7; - AMPS copolymers / polyoxyethylenated alkyl methacrylates (cross-linked or otherwise) of the ARISTOFLEX HMS type marketed by CLARIANT; anionic, cationic, amphoteric or nonionic chitin or chitosan polymers; cellulose polymers, distinct from alkylcellulose, chosen from hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, as well as the quaternized derivatives of cellulose; vinyl polymers, such as polyvinylpyrrolidones, copolymers of methylvinyl ether and of malic anhydride, the copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate; copolymers of vinylpyrrolidone and caprolactam, polyvinyl alcohol; starches and derivatives, optionally modified; polymers of natural origin, which may be modified, such as: galactomannans and their derivatives, such as Konjac gum, Gellane gum, Carob gum, Fennugrec gum, Karaya gum, gum Tragacanth, gum arabic, acacia gum, guar gum, hydroxypropylguar, hydroxypropylguar modified with sodium methylcarboxylate groups (Jaguar XC97-1, Rhodia), hydroxypropyltrimethylammonium guar chloride, xanthan derivatives; alginates and carrageenans; glycoaminoglycans, hyaluronic acid and its derivatives; muccopolysaccharides such as hyaluronic acid, chondroitin sulphate; - and their mixtures.

Preferably, the hydrophilic polymer is chosen from polysaccharides and derivatives, (homo) or (co) polymers of acrylic and methacrylic acid and their esters, and mixtures thereof. Said polymers are advantageously chosen from the group consisting of (poly) (alkyl) (meth) acrylic acid and its derivatives, especially (poly) (alkyl) (meth) acrylate and its derivatives, and in particular copolymers alkylacrylic acid / alkylmethacrylic acid and their derivatives. Preferentially, this hydrophilic polymer is a copolymer of ethyl acrylate, methyl methacrylate and a low content of methacrylic acid ester with quaternary ammonium groups, sold under the brand name EUDRAGIT RSPO by Evonik Degussa.

Said polysaccharides and derivatives are preferably chosen from polymers of chitosan, chitin, cellulose, starch, galactomannans, alginates, carrageenans, mucopolysaccharides and their derivatives, and mixtures thereof. According to one particular embodiment, the polysaccharides and derivatives are preferably chosen from those including one or more monosaccharides, in particular those with a D-glucose unit, such as starches, celluloses and their mixtures. In a preferred embodiment, the polymer is starch or a derivative thereof. The starch which can be used in the context of the present invention is usually derived from vegetable raw materials such as rice, soya, potatoes or maize. The starch can be modified or not. Preferably, it is unmodified.

According to a preferred embodiment, the outer layer of the microcapsules according to the invention does not comprise microcrystalline cellulose. The cellulose derivatives include, for example, alkyl celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. In a particular embodiment, the cellulose is a carboxymethyl cellulose (CMC). According to a preferred embodiment, the microcapsule contains at least one hydrophilic polymer chosen from the group consisting of starch and its derivatives, in particular corn starch, cellulose and its derivatives, homo- and / or copolymers of methacrylic acid and / or methacrylic acid ester or co-polymers of (alkyl) acrylic acid and / or (alkyl) methacrylic acid and their derivatives, preferably their salts and their esters. Preferably, the microcapsules contain polymethyl methacrylate. Preferred homo- and / or co-polymers of methacrylic acid and / or methacrylic acid ester are those in which the methyl methacrylate / ethyl acrylate copolymer has a molecular weight of 750 kDa to 850 kDa. According to a preferred embodiment, the capsule contains at least one starch derivative, in particular corn starch, polymethyl methacrylate, a copolymer of (alkyl) acrylic acid and / or (alkyl) acid. methacrylic acid and their derivatives, preferably their salts and esters, and / or cellulose derivatives.

Preferably, the microcapsules according to the invention contain polymers which are not crosslinked. These polymers may be present in one or more layers. In another embodiment, they may be in the core. The microcapsule may contain one or more polymers in the core and / or in the layers. According to one embodiment, these polymers are in the core and in the layer (s).

The polymer may be in one or more layers and represent from 0.5% to 20% by weight of the microcapsule, in particular from 2% to 10% by weight of the microcapsule. According to one particular embodiment, the microcapsules comprise a mixture of 2 or more pigments, individually encapsulated in microcapsules and / or in layers of the same microcapsule. Preferably, each layer of the microcapsule comprises at least one pigment or a mixture of pigments. The composition of the invention advantageously comprises at least 2 microcapsules of different colors. Examples of pigments are described above. The pigments may represent from 20% to 90% by weight, preferably from 30% to 80% by weight, in particular from 50% to 75% by weight relative to the total weight of the microcapsule.

According to one embodiment, the microcapsules according to the invention preferably contain at least titanium dioxide and / or iron oxides in their coating, and preferably at least titanium dioxide. In a preferred embodiment, the microcapsules of the invention preferably contain at least titanium dioxide and iron oxides in their coating. According to a particular embodiment, the outer layer of said microcapsules contains titanium dioxide and preferably as a coloring matter. According to these particular embodiments, the outer layer of said microcapsules contains titanium dioxide as the only coloring material and the composition according to the invention is a non-colored composition, the term "non-colored" referring to a transparent or white composition . According to a preferred embodiment, the composition according to the present invention comprises unstained microcapsules, the outer layer of which is white or transparent. When the outer layer is transparent, the visible inner layer is white. For the purposes of the present invention, the term "transparent composition" refers to a composition which transmits at least 40% of the light at a wavelength of 750 nm, without dispersion, ie a composition in which the angle light scattering is less than 5 ° and even better about 00.

The transparent composition can transmit at least 50%, especially at least 60% and in particular at least 70% of the light at a wavelength of 750 nm. The transmission measurement is carried out with a UV-Visible Cary 300 Scan spectrophotometer from the company Varian, according to the following protocol: the composition is poured into a spectrophotometer tank with a side length of 10 mm; the sample of the composition is then kept in a thermostatically controlled enclosure at 20 ° C. for 24 hours; the light transmitted through the sample of the composition is then measured on the spectrophotometer by wavelengths ranging from 700 nm to 800 nm of scanning, the measurement being made in the transmission mode; and the percentage of light transmitted through the sample of the composition at a wavelength of 750 nm is then determined.

The transparent compositions, when they are placed at 0.01 m in front of a black line of 2 mm in diameter drawn on a sheet of white paper, make it possible to see this line; on the other hand, an opaque composition, ie a non-transparent composition, does not make it possible to see the line. In a particular embodiment, the microcapsules contain metal oxides chosen from iron oxides, titanium oxides, and mixtures thereof, present in an amount ranging from 20% to 90% by weight, preferably from 30% to 85% by weight. by weight, more preferably from 50% to 85% by weight relative to the total weight of the microcapsule. In particular, the titanium oxide may be present from 28% to 80% by weight, preferably from 30% to 75% by weight, and more preferably from 30% to 50% by weight, relative to the total weight of the microcapsule. In particular, the iron oxides may be present from 5% to 75% by weight, preferably from 8% to 65% by weight relative to the total weight of the microcapsule. In a particular embodiment, the iron oxides are present in an amount greater than 15% by weight, preferably greater than 30% by weight, and in particular from 40% to 65% by weight relative to the total weight of the microcapsule. The layers of said microcapsules may also advantageously comprise at least one lipid material. The lipid material may have amphiphilic properties, that is to say an apolar part and a polar part.

Said lipid materials may comprise at least one or more 0-12-022 fatty chains as chosen from: stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, and mixtures thereof. Optionally, these fatty acid chains may be the apolar portion of the lipid material. Said lipid material is preferably chosen from phospholipids, more preferably from phosphoacylglycerols, in particular lecithins, and preferably hydrogenated lecithins. The lipid material may represent from 0.05% to 5% by weight, in particular from 0.1% to 10% by weight of the microcapsule. By combining 2 or 3 compounds of different hardnesses and / or solubilities in water (ex: sugars-alcohols, polymers, lipidic materials) in the microcapsule, it is possible to modulate the time that the microcapsule has to break on the skin ; thus, by varying the method or the intensity of application to the skin, it is possible to adjust the color or degree of color. In a preferred embodiment, the multilayers comprise at least starch as a polymer and at least lecithin as a lipid material. In a preferred embodiment, the microcapsule comprises a core comprising monosaccharide derivatives and a coating (layers) comprising polysaccharides (or derivatives thereof) including monosaccharides. According to a particularly preferred embodiment, the microcapsules include a nucleus comprising a polyol monosaccharide, preferably chosen from mannitol, erythritol, xylitol, or sorbitol, and a coating comprising polysaccharides (or derivatives) including as doses D units. -glucose.

In a preferred embodiment, the microcapsules include 3 or 4 dyes in different layers. According to one embodiment, the microcapsules according to the invention may comprise: i) a core (A), preferably having a diameter of between 500 nm and 150 μm, which does not contain a colorant preference, and comprising at least an organic nucleus preferably chosen from at least one sugar-alcohol, preferably a monosaccharide-polyol advantageously chosen from mannitol, erythritol, xylitol, sorbitol, and mixtures thereof; a first layer (B) surrounding said core comprising: at least one pigment, preferably iron oxides, and a binder selected from at least one polymer, at least one lipid-based material, and mixtures thereof, and preferably a mixture thereof; a second layer (C) surrounding the layer (B), preferably having a thickness of from 5 μm to 500 μm, comprising: particles of titanium dioxide, and a binder selected from at least one polymer, at least one lipid material, and mixtures thereof, and preferably a mixture thereof; optionally a third layer (D) surrounding the layer (C) comprising: - at least one dye, especially a pigment, and - a binder selected from at least one polymer, at least one lipid material, and mixtures thereof, and preferably a mixture of these; y) optionally a fourth layer (E) surrounding the layer (D) if it is present, or surrounding the layer (C), and comprising: - at least one membrane polymer chosen from polysaccharides such as cellulose derivatives, in particular cellulose ethers and esters, (poly) (alkyl) (meth) acrylic acids and derivatives thereof, in particular (poly) (alkyl) (meth) acrylates and their derivatives, and preferably alkylacrylic acid / alkylmethacrylic acid copolymers and their derivatives.

Thus, according to a particular embodiment of the invention, the microcapsule comprises a core consisting of a sugar alcohol and multilayers around said core comprising at least one pigment, a polymer chosen from polymers or copolymers of methacrylates, polysaccharides and derivatives comprising D-glucose units, and mixtures thereof, and further preferably at least one lipid material. In particular, the microcapsule comprises a core consisting of mannitol and multilayers around said core comprising at least one pigment, a polymer chosen from starches or derivatives or celluloses or derivatives and mixtures thereof, and advantageously also at least one hydrogenated lecithin.

According to a particularly preferred embodiment, the composition of the invention comprises at least pigments encapsulated in microcapsules based on acrylate / ammonium methacrylate copolymer, and are more particularly chosen from titanium dioxide, yellow iron oxides, red iron oxides, black iron oxides, encapsulated in microcapsules based on acrylate / ammonium methacrylate copolymer, in particular those marketed by TAGRA Biotechnologies.

According to another particularly preferred embodiment, the composition of the invention comprises at least pigments encapsulated in microcapsules made of cellulose derivatives, in particular in microcapsules comprising mannitol, cellulose, hydroxypropyl methylcellulose, such as those marketed by the company Lnduchem under the name Unisphère, INCI name: mannitol, cellulose, hydroxypropyl methylcellulose (and) titanium dioxide (and) iron oxides. According to another preferred embodiment, the composition of the invention comprises at least pigments encapsulated by microcapsules of sugars and polysaccharides, in particular the encapsulated pigments marketed by DAITO under the name Sugarcapsules. Second type of multilayer microcapsules Among the 'multilayer' microcapsules, mention may also be made of the microcapsules hereinafter. According to one embodiment, the pigments according to the invention may be contained in microcapsules comprising: a core comprising at least one 'colored' core and optionally at least one colored inner layer, and - an envelope (or wall) having at least least one layer surrounding said core, ruptible in response to a certain pressure, a possibly colored outer layer and a possibly outermost envelope. In preferred embodiments, the microcapsules comprise pigments selected from inorganic pigments, preferably selected from metal oxides, such as iron oxides and titanium oxide. Preferably, the 'colored' nucleus comprises at least one inorganic pigment advantageously chosen from metal oxides, more advantageously chosen from iron oxides. Preferably, the ruptible wall comprises at least one inorganic pigment advantageously chosen from at least one metal oxide, more advantageously chosen from at least one titanium oxide. Preferably, these iron oxides are located at least in the core and the titanium oxides are located at least in a ruptible layer surrounding said core.

These microcapsules comprise at least 70% by weight of pigments, preferably of inorganic pigments, preferably of a mixture of inorganic pigments, preferably metal oxides, such as iron oxides and titanium oxides, relative to the total weight of the microcapsules. . These microcapsules can be obtained according to various methods as described above such as granulation, pelletization, coating, etc. Preferably, as described above, they are obtained according to a fluidized bed process. According to a particular aspect of the invention, more than 60%, preferably more than 70%, in particular more than 80%, and more particularly more than 90% of these microcapsules will be broken to release the internal pigment in 1 minute, of preferably from 1 to 40 seconds, in particular from 1 to 30 seconds, more particularly from 1 to 20 seconds after pressing, rubbing, wiping and / or washing by hand or with a tool. However, this quantity and this delay are not critical in the context of the present invention. The core of these microcapsules comprises a colored core containing at least one pigment and advantageously at least one binder. The pigment is preferably selected from iron oxides. The binder is preferably as defined above for the first type of 'multilayer' microcapsules. The core may be prepared in the form of a particle, a powder, a granule, a microsphere or a microcapsule, in particular by atomization or by fluidized bed from a solution comprising at least one pigment, at least one polymer as a material for forming the wall and at least one lipid material in a solvent. The size of the colored nucleus, and more generally of the nucleus, is not particularly limited and may be suitably chosen depending on the microcapsule finally desired. For example, the size of the colored core may be greater than 20 μm or more, in particular 30 μm or more, preferably 40 μm or more, preferably 50 μm or more, and less than 800 μm or less, particularly 700 μm or less, preferably 600 μm or less, preferably 500 μm or less. The core radius is greater than 50%, especially 60%, preferably 70% and more preferably 80%, based on the total radius of the microcapsule. For example, the ratio between the core radius and the shell thickness is between 1: 0.05 and 1: 0.5.

Alternatively, the content of the core is more than 30% by weight, in particular 40%, preferably 50% and more preferably 60%, relative to the total weight of the microcapsule. The core may include one or more internal colored layers surrounding said colored core. These colored inner layers may be any layers between the core and the ruptible wall layer.

The inner color layers include, for example, the first inner color, the second inner color layer and the third inner color layer, etc., wherein the colorants and binders contained in each of the inner color layers are the same or different from each other. other. In a preferred embodiment, the colored core may comprise one or two internal colored layers, preferably a single internal colored layer. The thickness of an inner colored layer is not particularly limited and may be suitably chosen depending on the ultimately desired microcapsule. For example, the inner colored layer may comprise from 20% to 80% by weight, in particular from 30% to 70% by weight, preferably from 40% to 60% by weight relative to the total weight of the core. According to a preferred embodiment, the pigment (s), preferably the iron oxide (s), is (are) present in the core in an amount of at least 70% by weight, in particular at least 75% by weight, preferably at least 80% by weight, more preferably at least 85% by weight, preferably 80% to 99% by weight, based on the total weight of the core. According to a preferred embodiment, the pigment (s), preferably the iron oxide (s), is (are) present in the core in an amount of at least 30% by weight, more particularly at least 35% by weight, preferably at least 40% by weight, preferably from 40% to 60% by weight, relative to the total weight of the microcapsule. The content of iron oxide (s) particles in the microcapsule is preferably selected from 20% to 60% by weight, preferably from 25% to 55% by weight, preferably from 30% to 50% by weight, relative to the total weight of the microcapsule. More preferably, the content of iron oxide (s) particles in the microcapsule is preferably selected from 30% to 58% by weight, preferably from 35% to 55% by weight, preferably from 40% to 50% by weight. % by weight, based on the total weight of the microcapsule. As indicated above, these microcapsules comprise a ruptible wall comprising at least one dye, preferably at least one pigment. Preferably, this ruptible wall comprises at least one inorganic pigment selected from metal oxides and preferably comprises particles of titanium dioxide. Preferably, the pigment contained in the layer of the ruptible wall is distinct from the pigment contained in the colored core, for example, both are metal oxides distinct from each other.

According to a preferred embodiment, the titanium dioxide particles are preferably dispersed in the layer discontinuously and connected to each other by a binder. A rupturable layer of titanium dioxide particles may comprise titanium dioxide particles and a binder, and said binder may comprise a material to form the wall. For example, the rupturable wall layer may be formed by the following method: (a) dissolving or dispersing titanium dioxide particles and a binder in a suitable solvent to obtain a solution comprising titanium dioxide particles and a binder, (b) coating particles with the inner colored layer with the solution obtained in step (a) above, and (c) optionally drying the resulting particles obtained in step (b). The coating can be carried out for example using a fluidized bed process.

Suitable solvents include water or a low-boiling solvent such as methylene chloride, methanol or ethanol. The layer of titanium dioxide particles, the thickness of which can vary depending on the amount of titanium dioxide used and / or the type of binder, can be 10 μm or more thick, preferably 20 μm or more more preferably 30 μm or more, in particular 40 μm or more, usually 300 μm or less, preferably 250 μm or less, preferably 200 μm or less, particularly 150 μm or less. The content of titanium dioxide particles in the ruptible layer is preferably selected from 50% to 99% by weight, preferably from 60% to 98% by weight, preferably from 70% to 97% by weight, in particular from 80% to 95% by weight, based on the total weight of the ruptible layer. Preferably, the content of dye (s), and in particular of titanium dioxide particles, represents less than 100% of the ruptible layer. The content of titanium dioxide particles in the microcapsule is preferably selected from 20% to 60% by weight, preferably from 25% to 55% by weight, preferably from 30% to 50% by weight, based on the weight total of the microcapsule. The pigment (s) in the colored core, preferably the iron oxide, and the one (s) in the ruptible layer, preferably titanium dioxide particles, are both present in a total amount in the microcapsules such that the ratio between the weight of the pigments in the colored core, and preferably iron oxide, and the weight of the pigments in the ruptible layer, preferably particles of titanium dioxide, is greater than or equal to 1. Iron oxide (or oxides) and titanium dioxide particles are present in a total amount in the microcapsules such that the weight ratio of iron oxide / titanium dioxide particles is greater than or equal to 1. The average diameter of the titanium dioxide particles is not specifically limited, but these particles preferably have an average diameter of generally 10 nm to 20 μm, preferably 50 nm to 10 μm, preferably 100 nm to 10 μm. 5 lm and in part from 150 nm to 5 μm.

As indicated above, these multilayer microcapsules may optionally comprise a colored outer layer on the ruptible layer of titanium dioxide particles. This additional layer may comprise a dye and a binder, and is for example obtained by a fluidized bed process. The dye and the binder can be here identical or different to those present in the internal colored layer. As indicated above, these multilayer microcapsules may optionally comprise an additional protective layer on the ruptible layer of titanium dioxide particles or an additional colored outer layer for example to protect the microcapsules from water.

This outermost shell may be made from at least one polymer, and preferably may be made from at least one polymer selected from the group consisting of polysaccharides and derivatives, homopolymers of acrylic or methacrylic acid or copolymers or salts and esters thereof, of polystyrene-maleic anhydride copolymers, and mixtures thereof, such as in particular poly (meth) acrylate, cellulose ethers, cellulose esters and their derivatives, and mixtures thereof. Other examples of polymers which can be used for this layer are those indicated above in the description of the binder for the first type of multilayer microcapsules. Thus, the binder can be for example a lipid material as defined above. The aforementioned polymer is preferably a hydrophilic polymer as defined above for the first type of multilayer microcapsules. According to a particularly preferred embodiment, the encapsulated pigments are pigments in double layer capsules comprising three or more of the following ingredients: mannitol, hydrogenated lecithin, polymethyl methacrylate, starch and shellac. In particular, mention may be made of the encapsulated pigments marketed by Korea Particle Technology (KPT). By way of example, mention may be made of references MAGIC60-BPP 12-00 and MAGIC60-BPP 12-02 marketed by this company.

According to a particularly preferred embodiment, the compositions of the invention comprise encapsulated pigments comprising mannitol, cellulose, hydroxypropylmethylcellulose, marketed by Lnduchem under the name of BNBM-621 SBI. According to another particularly preferred embodiment, the compositions of the invention comprise MAGIC60-BPP 12-02 encapsulated pigments as defined above marketed by Korea Particle Technology (KPT). According to one embodiment, the encapsulated pigments are present in the compositions according to the invention in an amount ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, and still more preferably more preferentially from 2 to 15% by weight, relative to the total weight of said composition. Aqueous phase The cosmetic compositions according to the invention comprise an aqueous phase in which the particles of encapsulated pigments are dispersed.

According to one embodiment, the aqueous phase is present in a proportion of 10% to 90% relative to the total weight of the composition and preferably 40% to 70% relative to the total weight of the composition. According to one embodiment, the aqueous phase comprises from 10% to 80% by weight of water relative to the total weight of the composition.

More particularly, this aqueous phase may comprise from 15% to 60% by weight of water relative to the total weight of the composition. According to one embodiment, the compositions according to the invention comprise at least 45% by weight of water relative to the total weight of the composition. According to one embodiment, the compositions according to the invention comprise less than 70% by weight of water relative to the total weight of the composition.

Water suitable for the invention may also be natural spring water or floral water. In particular, a water that is suitable for the invention may be a floral water such as cornflower water and / or mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water. / or thermal water.

According to one embodiment, the aqueous phase of the compositions of the invention may further comprise at least one organic solvent miscible with water. This organic solvent, miscible with water, may be chosen from: - monoalcohols comprising from 1 to 8 carbon atoms, and especially from 2 to 5 carbon atoms, such as ethanol and isopropanol, - the glycols comprising from 2 to 8 carbon atoms, such as propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol and caprylyl glycol, polyethylene glycols, polyhydric alcohols comprising from 2 to 8 carbon atoms, carbon such as glycerol, and - mixtures thereof. In particular, the aqueous phase of the compositions of the invention may comprise ethanol. The aqueous phase may also contain any water-soluble or water-dispersible compound compatible with an aqueous phase. Among these compounds, mention may be made of active agents, dyes, salts such as sodium chloride and magnesium sulphate, gelling agents, preservatives and any other water-soluble additive commonly used in cosmetic products. Hydrophilic gelling agent According to a preferred embodiment of the invention, the aqueous phase contains at least one hydrophilic gelling agent. This may make it possible to better homogenize the oily, aqueous and pigmented phases if the product is agitated before use and thus to facilitate its removal from the flask. It also makes it possible to modulate the sedimentation rate of the encapsulated pigments when the product is at rest again and to increase its aesthetic appearance. Preferably, the gelling agents are devoid of emulsifying properties, that is to say that they do not produce emulsion of the oily phase in the aqueous phase by stirring the product.

According to one embodiment, the hydrophilic gelling agent is chosen from the group consisting of polymers comprising at least one monomer containing a sulfonic group, carboxyvinyl polymers, cellulose derivatives, polysaccharides, superabsorbent polymers and mixtures thereof. In particular, there may be mentioned carbopols (carbomers) among carboxyvinyl polymers, hydroxyethylcellulose among cellulose derivatives and gums such as xanthan gum and guar gum among polysaccharides.

Preferably, the hydrophilic gelling agent is a crosslinked sodium polyacrylate or a 2-acrylamido-2-methylpropane sulfonic acid polymer. Among these hydrophilic agents, superabsorbent polymers can also be mentioned here. The term "superabsorbent polymer" means a polymer which is capable of being dry in its spontaneous absorption at least 20 times its own weight of aqueous fluid, in particular water and in particular distilled water. Such superabsorbent polymers are described in the book "Absorbent Polymer Technology, Studies in Polymer Science 8" by L. BRANNON-PAPPAS and R. HARLAND, Elsevier edition, 1990.

These polymers have a high capacity for absorption and retention of water and aqueous fluids. After absorption of the aqueous liquid, the polymer particles so imbibed with aqueous fluid remain insoluble in the aqueous fluid and thus retain their individualized particulate state. The superabsorbent polymer can have a water absorption capacity ranging from 20 to 2,000 times its own weight (ie 20 g to 2,000 g of absorbed water per gram of absorbent polymer), preferably from 30 to 1,500 times , and better 50 to 1,000 times. These water absorption characteristics are defined under normal conditions of temperature (25 ° C) and pressure (760 mm Hg or 100,000 Pa) and for distilled water.

The value of the water absorption capacity of a polymer can be determined by dispersing 0.5 g of polymer (s) in 150 g of a water solution, while waiting for 20 minutes, filtering the non-aqueous solution. absorbed on a 150 μm filter for 20 minutes and weighing the unabsorbed water. The superabsorbent polymer used in the composition of the invention is in the form of particles. Preferably, the superabsorbent polymer has, in the dry or non-hydrated state, an average size of less than or equal to 100 μm, preferably less than or equal to 50 μm, for example from 10 μm to 100 μm, preferably from 10 μm to 100 μm. lm at 50 11m, and better from 20 lm to 30 11m. The average particle size corresponds to the mean diameter by mass (D50) measured by laser particle size distribution or other equivalent method known to those skilled in the art. These particles, once hydrated, swell to form soft particles having an average size ranging from 10 μm to 1000 μm, preferably from 20 μm to 500 μm, and even more preferably from 50 μm to 400 μm. Preferably, the superabsorbent polymers used in the present invention are in the form of spherical particles. Absorbent polymers chosen from: crosslinked sodium polyacrylates, for example those sold under the names Octacare X100, X110 and RM100 by Innospec Active Chemicals, those marketed under the names Flocare GB300 and Flosorb 500 by the method SNF company, those marketed under the names Luquasorb 1003, Luquasorb 1010, Luquasorb 1280 and Luquasorb 1110 by the company BASF, those marketed under the names Water Lock G400 and G430 (INCI name: Acrylamide / Sodium acrylate copolymer) by the company Grain Processing, or the AQUAKEEP® 10 SH NF proposed by the company Sumitomo Seika, - the starches grafted with an acrylic polymer (homopolymer or copolymer) and in particular with sodium polyacrylate, such as those sold under the name Sanfresh ST-100 ™ by the Sanyo Chemical Industries or Makimousse 25, Makimousse 12 by the company Daito Kas ei (INCI name Sodium polyacrylate Starch), - hydrolysed starches grafted with an acrylic polymer (homopolymer or copolymer) and especially acryloacrylamide / sodium acrylate copolymer, such as those sold under the names Water Lock A-240, A-180, B204 , D-223, A-100, C-200, D-223, by Grain Processing (INCI name: Starch / acrylamide / sodium acrylate copolymer), - polymers based on starch, gum and cellulose derivative , such as that containing starch, guar gum and sodium carboxymethyl cellulose, sold under the name Lysorb 220 by Lysac, and mixtures thereof.

The superabsorbent polymers used in the present invention may be crosslinked or uncrosslinked. They are preferably chosen from crosslinked polymers. The superabsorbent polymers used in the present invention are preferably crosslinked, preferably neutralized acrylic homo- or copolymers, which are in particulate form. Preferably, the superabsorbent polymer is chosen from crosslinked sodium polyacrylates, preferably in the form of particles having a mean size (or average diameter) less than or equal to 100 microns, more preferably in the form of spherical particles. These polymers preferably have a water absorption capacity of 0.9% (3% NaCl) of 10 to 100 g / g, preferably 20 to 80 g / g and more preferably 30 to 80 g / g. According to an advantageous embodiment, the compositions according to the invention comprise, as superabsorbent polymer, crosslinked sodium polyacrylate, for example that marketed by the company Sumitomo Seika under the reference AQUAKEEP 10 SH-NFC. hydrophilic, preferably a poly (2-acrylamido-2-methylpropanesulphonic acid) polymer crosslinked and neutralized to at least 90 %.These polymers are generally characterized in that they comprise, distributed randomly: a ) from 90% to 99.9% by weight of units of the following general formula (I): ## STR2 ## in which X + denotes a cation or a mixture cation, at most 10 mol% of the X + cations may be H + protons; and b) from 0.01% to 10% by weight of crosslinking units originating from at least one monomer having at least two olefinic double bonds, the proportions by weight being defined relative to the total weight of the polymer. The more particularly preferred homopolymers according to the invention comprise from 98% to 99.5% by weight of units of formula (1) and from 0.2% to 2% by weight of crosslinking units. (1) As a polymer of this type, mention may be made in particular of the crosslinked and neutralized homopolymer of 2-acrylamido-2-methylpropanesulphonic acid marketed by the company Clariant under the trademark "Hostacerin AMPS" (CTFA name: ammonium polyacryldimethyltauramide).

According to one embodiment, the content of hydrophilic gelling agent (s) in the compositions according to the invention ranges from 0.01% to 10%, preferably from 0.03% to 2%, and still more preferably from 0.05% to 1% by weight relative to the total weight of said composition.

Oily phase The compositions according to the invention also comprise an oily phase whose density is lower than that of the aqueous phase. Thus, at rest, the oily phase is above the aqueous phase and constitutes the upper layer of the composition according to the invention. According to one embodiment, the oily phase represents from 5% to 85%, preferably from 20% to 70%, and preferably from 30% to 60%, by weight relative to the total weight of said composition. The oily phase (or fatty phase) of the compositions according to the invention comprises at least one oil. It may consist of a single oil or a mixture of several oils. The term "oil" means any fatty substance in liquid form at ambient temperature (20-25 ° C.) and at atmospheric pressure. These oils can be of animal, vegetable, mineral or synthetic origin. According to one embodiment, the oils are selected from the group consisting of hydrocarbon oils, silicone oils, fluorinated oils and mixtures thereof. For the purposes of the present invention, the term "hydrocarbon oil", an oil containing mainly hydrogen and carbon atoms. The term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group. The term "fluorinated oil" means an oil comprising at least one fluorine atom. The oils may optionally comprise oxygen, nitrogen, sulfur and / or phosphorus atoms, for example in the form of hydroxyl or acid radicals.

According to one embodiment, the oily phase of the compositions of the invention comprises at least one volatile oil and / or at least one non-volatile oil.

Volatile oils According to one embodiment, the oily phase of the compositions of the invention comprises at least one volatile oil. The oily phase of the compositions of the invention may comprise a mixture of several volatile oils.

By "volatile oil" is meant any non-aqueous medium that can evaporate from the skin or lips in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic oil, liquid at room temperature. More specifically, a volatile oil has an evaporation rate of between 0.01 and 200 mg / cm 2 / min, inclusive.

To measure this evaporation rate is introduced into a crystallizer, with a diameter of 7 cm, placed on a scale located in a large enclosure of about 0.3 m3 temperature-controlled, at a temperature of 25 ° C., and in hygrometry at a relative humidity of 50%, 15 g of oil or oil mixture to be tested. The liquid is allowed to evaporate freely, without stirring, providing ventilation by a fan (PAPST-MOTOREN, reference 8550 N, rotating at 2700 revolutions per minute) arranged in a vertical position above the crystallizer containing said oil or said mixture, the blades being directed to the crystallizer and at a distance of 20 cm from the bottom of the crystallizer. The mass of oil remaining in the crystallizer is measured at regular intervals. The evaporation rates are expressed in mg of evaporated oil per unit area (cm2) and per unit of time (minute). The volatile oils may be hydrocarbon, silicone or fluorinated. The volatile oils may be chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially branched C8-C16 alkanes (also known as isoparaffins or isoalkanes), such as isododecane (also called 2,2,4,4 , 6-pentamethylheptane), isodecane, isohexadecane, and, for example, the oils sold under the trade names ISOPARS® or PERMETHYLS®. As hydrocarbon-based volatile oils, mention may also be made of linear C9-C17 alkanes, such as dodecane (C12) and tetradecane (C14), sold respectively under the references PARAFOL® 12-97 and PARAFOL® 14-97 (Sasol) and as the alkanes obtained according to the process described in international application WO2007 / 068371 A1, such as the mixture of undecane (011) and tridecane (013) sold under the reference of CETIOL® UT (Cognis). As volatile silicone oils, it is also possible to use volatile silicones, such as, for example, volatile linear or cyclic silicone oils, especially those having a viscosity less than or equal to 8 centistokes (cst) (8 × 10 -6 m 2 / s). ), and having, in particular, from 2 to 10 silicon atoms, and in particular from 2 to 7 silicon atoms, these silicones optionally containing alkyl or alkoxyl groups having from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made, in particular, of dimethicones of viscosity 5 and 6 cst, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof. More particularly, as silicone volatile oil, mention may be made of linear or cyclic silicone oils having from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms.

As the volatile fluorinated oil, there may be mentioned for example nonafluoromethoxybutane or perfluoromethylcyclopentane, and mixtures thereof. Non-volatile oils According to one embodiment, the oily phase of the compositions of the invention comprises at least one non-volatile oil. The oily phase of the compositions of the invention may comprise a mixture of several non-volatile oils. "Non-volatile oil" means an oil remaining on the skin or keratin fiber at room temperature and atmospheric pressure. More specifically, a non-volatile oil has an evaporation rate strictly less than 0.01 mg / cm 2 / min. The non-volatile oils may, in particular, be chosen from hydrocarbon oils, fluorinated oils and / or non-volatile silicone oils. Non-volatile hydrocarbon oils that may especially be mentioned include: - hydrocarbon-based oils of animal origin, such as perhydrosqualene; - hydrocarbon-based oils of vegetable origin, such as phytostearyl esters, such as phytostearyl oleate, or isostearate of physostearyl and lauroyl glutamate / octyldodecyl / phytostearyl (AJINOMOTO, ELDEW PS203), triglycerides consisting of esters of fatty acids and glycerol, in particular, whose fatty acids may have chain lengths ranging from 036, and especially from 018 to 036, these oils may be linear or branched, saturated or unsaturated; these oils may, in particular, be heptanoic or octanoic triglycerides, shea, alfalfa, poppy, pumpkin, millet, barley, quinoa, rye, bancoulier, passionflower oil, shea butter, aloe oil, sweet almond oil, peach almond oil, peanut oil, argan oil, avocado oil, oil of baobab, borage oil, broccoli oil, calendula oil, camelina oil, canola oil, carrot oil, safflower oil, hemp oil , rapeseed oil, cottonseed oil, coconut oil, pumpkin seed oil, wheat germ oil, jojoba oil, lily oil, oil macadamia, corn oil, prairie pearl oil ('meadowfoam'), St. John's wort oil, monoi oil, hazelnut oil, apricot kernel oil, l walnut oil, olive oil, evening primrose oil, palm oil, blackcurrant seed oil, kiwifruit seed oil, grape seed oil, pistachio oil, pumpkin oil, pumpkin oil, rose hip oil, sesame oil, soybean oil, sunflower oil, lemon castor oil, and watermelon seed oil, and mixtures thereof, or triglycerides of caprylic / capric acids, such as those sold by Stearineries Dubois or those sold under the names MIGLYOL 810®, 812® and 818® by DYNAMIT NOBEL, - linear or branched hydrocarbons of mineral or synthetic origin, such as paraffin oils and their derivatives, petroleum jelly, polydecenes, polybutenes, hydrogenated polyisobutene such as Parleam ; synthetic ethers having from 10 to 40 carbon atoms; synthetic esters, such as oils of formula R1000R2, in which R1 represents a residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms, and R2 represents a hydrocarbon chain, in particular, branched, containing from 1 to 40 carbon atoms provided that the sum of the number of carbon atoms of the R1 and R2 chains is greater than or equal to 10. The esters may be, in particular, chosen from alcohol and fatty acid esters, for example: cetostearyl octanoate, esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, stearate or isostearate. isostyle, isostearyl isostearate, octyl stearate, hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, and especially heptanoate. isostearyl, octanoates, decanoates or ricinoleate alcohols or polyhydric alcohols, such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 4-diheptanoate and 2-hexyl ethyl palmitate, alkyl benzoate, diheptanoate, polyethylene glycol, propylene glycol diethyl 2 -hexanoate, and mixtures thereof, 0-12-015 alcohol benzoates, hexyl laurate, esters of neopentanoic acid, such as isodecyl neopentanoate, neopentanoate of isotridecyl, isostearyl neopentanoate, octyldocecyl neopentanoate, esters of isononanoic acid, such as isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, hydroxyl esters, and the like. isostearyl lactate, diisostearyl malate; branched-chain and / or unsaturated carbon-chain liquid fatty alcohols having from 12 to 26 carbon atoms, such as 2-octyldodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol and 2-undecylpentadecanol; higher 0-12-022 fatty acids, such as oleic acid, linoleic acid, linolenic acid, and mixtures thereof; di-alkyl carbonates, the 2 alkyl chains being identical or different, such as dicaprylyl carbonate sold under the name CETIOL CC®, by COGNIS; fluorinated oils that may be partially hydrocarbon-based and / or silicone-based, such as fluorosilicone oils, fluorinated polyethers or fluorinated silicones, as described in document EP-A-847,752; silicone oils, such as non-volatile, linear or cyclic polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates; and - their mixtures.

Among the linear or branched hydrocarbons of mineral or synthetic origin, paraffins oils or vaseline oil are preferably used.

Among the hydrocarbon oils of vegetable origin, mention may preferably be made of vegetable oils, such as sweet almond oil, jojoba oil or macadamia oil. According to one embodiment, the oily phase comprises at least one non-volatile hydrocarbon oil. Preferably, this non-volatile hydrocarbon oil is chosen from fatty alcohols that are liquid at room temperature and synthetic esters as defined above, as well as mixtures thereof. According to one embodiment, the oily phase comprises isononyl isononanoate.

The oily phase is preferably clear and transparent. The oily phase may also contain any fat-soluble compound. Among these liposoluble compounds, there may be mentioned perfumes, dyes, active agents, or gelling agents.

Physiologically acceptable medium In addition to the compounds indicated above, a composition according to the invention comprises a physiologically acceptable medium. By "physiologically acceptable medium" is meant a medium that is particularly suitable for applying a composition of the invention to the skin. The physiologically acceptable medium is generally adapted to the nature of the support to which the composition is to be applied, as well as to the appearance under which the composition is to be packaged.

Dyestuffs The compositions of the invention may also comprise, in addition to the encapsulated pigment particles, an additional dyestuff or a mixture of additional dyestuffs. According to a preferred embodiment, the content of additional dyestuffs ranges from 0% to 1% by weight, in particular from 0.00001% to 0.5% by weight, relative to the total weight of said composition. According to one embodiment, the compositions according to the invention comprise at least one dye, different from the encapsulated pigments defined above. They may comprise a dye or a mixture of several dyes, these dyes may be present in the aqueous phase and / or oily.

According to one embodiment, the compositions according to the invention comprise a dye in the aqueous phase and another dye in the oily phase. By "dyes", it is necessary to include generally organic compounds that are soluble in fatty substances such as oils or in a hydroalcoholic phase.

The cosmetic composition according to the invention may therefore also comprise water-soluble or fat-soluble dyes. Liposoluble dyes are, for example, Sudan Red, DC Red 21, DC Red 27, DC Green 6, (3-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, orange DC 5 and yellow quinoline.

The water-soluble dyes are, for example, beet juice and caramel, or also DC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, FDC Yellow dyes. 5, FDC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5 and FDC Blue 1.

Additives A cosmetic composition according to the invention may also comprise any additive usually used in the field concerned, for example chosen from gums, resins, semi-crystalline polymers, antioxidants, essential oils, preservatives, perfumes, neutralizers, antiseptic agents, UV protective agents, cosmetic active agents, such as vitamins, moisturizers, emollients or collagen protectors, and mixtures thereof. It falls within the routine operations of those skilled in the art to adjust the nature and quantity of the additives present in the compositions according to the invention, so that the desired cosmetic properties and stability properties thereof are not affected. Applications The compositions of the invention may be packaged in bottles of any kind and in all forms commonly used for cosmetic products and more preferably in transparent glass or plastic bottles such as polyethylene terephthalate (PET). The cosmetic compositions covered by the invention may be skincare or make-up products for the face or body.

These compositions are therefore intended to be applied to the skin.

The present invention also relates to a non-therapeutic cosmetic method for making up and / or caring for keratinous substances, in particular the skin, comprising a step of applying to said keratin materials at least one layer of a composition according to the invention .

The present invention also relates to a method of non-therapeutic cosmetic treatment of the skin comprising a step of applying to the skin at least one layer of a composition according to the invention. The present invention also relates to a non-therapeutic method of makeup and / or care of the skin comprising a step of applying to the skin at least one layer of a composition according to the invention. The present invention also relates to a process for coating keratin materials comprising a step of applying to said keratin materials a cosmetic composition according to the invention. Throughout the application, the wording "comprising a" or "comprising a" means "comprising at least one" or "comprising at least" one unless the contrary is specified. Throughout the above description, unless otherwise stated, the term "inclusive between x and y" corresponds to an inclusive range, i.e. the x and y values are included in the range. EXAMPLES Pigment behavior evaluation test A sample of 20 g of the composition is introduced into a glass flask of about 30 ml (diameter 2.5 cm, height 8 cm). In order to ensure that the sample taken is true to the composition, it is conditioned after homogenizing the composition with stirring. It is thus possible to take the sample just after manufacture.

The bottle is left standing for 24 hours in a vertical position, before being evaluated. The cleanliness of the walls of the flask and of the interface between the upper oily phase and the lower aqueous phase is then judged: if all the pigments are sedimented in the aqueous phase, that the walls of the flask are clean and that the interface between the two liquid phases is devoid of pigments, the composition is in accordance with the invention, - If a part of the pigments is attached to the walls of the flask, and / or if pigments are retained at the interface between the two phases liquids, then the composition is not in accordance with the invention.

Examples 1 to 3: Influence of the nature of the pigment Examples 1 to 3 show the influence of the nature of the pigment on their adhesion to the walls of the flask and their presence at the interface of the oily phase and the aqueous phase . % by mass A Water Qsp 100 (49.9998) Ethanol absolute 15.00 D & C Red No. 4 0.0001 B Isononyl isononanoate 30.00 D & C Purple No. 2 0.0001 C pigments 5.00 TOTAL 100% 25 Procedure On separately prepared each of the A and B phases by homogenizing them with magnetic stirring at room temperature. The aqueous phase A and then the pigments were introduced into a transparent plastic bottle which could be sealed. The bottle was closed and then stirred manually (10 vertical strokes) in order to homogenize the pigments in the aqueous phase. Phase B was then added and the bottle was closed and the formula was again manually homogenized (10 vertical blows). Adhesion of the pigments to the walls and presence at the interface Examples Pigments Aspect Example 1 Sphere consisting of mannitol, hydrogenated lecithin, The encapsulated pigments sedimented in the (invention) corn starch, cellulose, titanium dioxide, phase lower aqueous, they do not adhere to the wall of the flask and the interface between the lower aqueous phase and the upper oily phase is clear and fluorphlogopite, tin oxide, red30 lacquer and oxide does not understand of pigments. iron sold under the trade name MAGIC60-BPP 12-02 by Korea Particle Technology (KPT) Example 2 Sphere consisting of mannitol, cellulose, hydroxypropyl methylcellulose, titanium dioxide, iron oxides sold under the name trade name UNISPHERES BICOLOR WNRM-621 SBI by the company Induchem The encapsulated pigments sedimented in the lower aqueous phase, they do not adhere to the (invention) wall of the bottle and the interface between the lower aqueous phase and the oily phase upper is clean and does not include pigments Example 3 Pigment mixture consisting of: 4.3% titanium dioxide, 0.5% yellow iron oxide, 0.15% red iron oxide, 0, 05% black iron oxide. Pigments distributed between the lower aqueous phase (Comparative) and the upper oily phase and present at the interface of the two phases. It has thus been found that pigment particles as described above in the description make it possible to obtain a composition in accordance with the invention, that is to say a three-phase resting composition in which the pigment particles are sedimented. in the liquid phase and do not adhere to the walls of the bottle containing them. When the pigments used are not encapsulated pigments according to the invention, the compositions are not satisfactory insofar as the pigment particles are then present at the interface of the aqueous and oily phases. EXAMPLE 4 Influence of Encapsulated Pigment Size The comparison of Examples 1 and 4 shows the influence of the size of the encapsulated pigment on its adhesion to the walls of the flask and its presence at the interface of the oily phase and of the aqueous phase. % by mass A Water Qsp 100 (49.9998) Ethanol absolute 15.00 D & C Red No. 4 0.0001 B Isononyl isononanoate 30.00 D & C Purple No. 2 0.0001 C Pigments 5.00 TOTAL 100% Procedure We have used the procedure described above for Examples 1 to 3.

Adhesion of pigments to the walls and presence at the interface Examples Pigments Size Appearance (Pm) Example 1 Sphere made of mannitol, lecithin 840-1200 The encapsulated pigments have sedimented in the lower aqueous phase, they do not adhere to the wall of the bottle and the interface between the hydrogenated phase (Invention), maize starch, cellulose, lower aqueous and the upper oily phase is clear and does not include titanium dioxide, fluorophlogopite, oxide pigments. tin, lacquer of Red30 and iron oxide sold under the trade name MAGIC60-BPP 12-02 by the company Korea Particle Technology (KPT) Example 4 Sphere consisting of mannitol, lecithin 50-200 Pigments distributed between the phase lower aqueous phase and the upper oily phase and present at the interface of the two phases. (Comparative) Hydrogenated, Corn Starch, Titanium Dioxide, Red30 Lacquer and Iron Oxide sold under the trade name MAGIC50-BP 905 by Korea Particle Technology (KPT) Examples 5 and 6: The Examples 5 and 6 illustrate the use of a hydrophilic gelling agent. % by mass A Water Qsp 100 (64,6999) Hydrophilic gelling agent 0,20 B Ethanol absolute 13,00 C Sphere consisting of mannitol, hydrogenated lecithin, 2,60 corn starch, cellulose, titanium dioxide, fluorphlogopite , of tin oxide, of Red30 lacquer and of iron oxide sold under the trade name MAGIC60-BPP 12-02 by Korea Particle Technology (KPT) D Isononyl isononanoate 19.50 D & C Purple No. 20 , 0001 TOTAL 100% Procedure Phase A was prepared beforehand at a temperature of 65 ° C. and homogenized using a Rayneri-type stirrer equipped with a deflocculator (500 rpm), then cooled to 50.degree. ambient temperature.

Phase D was previously prepared by mixing the isononyl isonanoate and the dye, homogenizing with magnetic stirring. In the main beaker, cooled phase A, phase B and phase D were introduced, then the beaker was stirred with the Rayneri type equipped with a propeller rotating at 500 rpm.

When the liquid phase was homogeneous, phase C was introduced while maintaining stirring until homogenization without, however, exceeding a time of 5 minutes, then the product was packaged just afterwards in order to guarantee the composition of the formula in the samples. Examples Hydrophilic gelling Aspect Example 5 Ammonium polyacryldimethyltauramide The encapsulated pigments sedimented in the lower aqueous phase, they do not adhere to the wall of the flask and (Invention) sold under the trade name the interface between the lower gelled aqueous phase and the upper oily phase is clean and does not include Hostacerin AMPS by Clariant. pigments. EXAMPLE 6 Sodium Acrylates Crosspolymer -2 + Water + The encapsulated pigments sedimented in the lower aqueous phase, they do not adhere to the wall of the flask and (Invention) silica sold under the name the interface between the lower gelled aqueous phase and the upper oily phase is clear and does not include commercial Aquakeep 10 SH-NFC by the pigments. Sumitomo Seika company. Sensory evaluation A panel of 4 women, aged 25 to 50, was asked to make up the example 5 on the face. The product exhibits at rest a playful and attractive appearance, in the form of three superimposed phases, constituted from top to bottom of the oily phase, of the aqueous phase, and encapsulated pigments. The women shake the product before use, in order to intimately mix the three phases. Then they take it and apply it on the face. The encapsulated pigments fragment during spreading and release a light beige color that leads to a natural makeup result.

Following the test procedure described above relating to the non-stability of the emulsions, Examples 1 to 4 show a separation of the aqueous and oily phases after 3 hours, and Examples 5 and 6 show a separation of the phases at the end. 24 hours.

Claims (15)

REVENDICATIONS1. A cosmetic composition comprising a physiologically acceptable medium containing: (1) an aqueous phase; (2) an oil phase of lower density than that of the aqueous phase; and (3) encapsulated pigment particles dispersed in the aqueous phase; the number average diameter of said encapsulated pigment particles being between 200 μm and 3000 μm, said aqueous and oily phases not being in the form of a stable emulsion. 2. Cosmetic composition according to claim 1, characterized in that it does not comprise an emulsifier (s) in a content capable of stabilizing the aqueous and oily phases in the form of an emulsion. 3. Cosmetic composition according to claim 1 or 2, wherein the pigments are selected from the group consisting of mineral pigments, organic pigments, interferential pigments, surface-treated or untreated, metal powders and mixtures thereof. 4. Cosmetic composition according to any one of claims 1 to 3, wherein the encapsulated pigments are pigments in capsules of a material selected from the group consisting of hot melt compounds whose melting temperature is between 30 ° C and 70 ° C. ° C, polymers or copolymers based on polyacrylates or methacrylates, copolymers based on styrene / acrylate, polymers based on polyesters, polyaminomethacrylates or polyvinylpyrrolidone, polysaccharides, proteins and mixtures thereof. A cosmetic composition according to any one of claims 1 to 4, wherein the encapsulated pigments are pigments in double layer capsules comprising three or more of the following ingredients: mannitol, hydrogenated lecithin, polymethyl methacrylate, starch and shellac. 6. Cosmetic composition according to any one of claims 1 to 5, wherein the encapsulated pigments are present in an amount ranging from 0.1% to 30% by weight relative to the total weight of said composition. 7. Cosmetic composition according to any one of claims 1 to 6, wherein the aqueous phase contains at least one hydrophilic gelling agent. The cosmetic composition of claim 7, wherein the hydrophilic gelling agent is selected from the group consisting of polymers comprising at least one sulfonic group-containing monomer, carboxyvinyl polymers, cellulosic derivatives, polysaccharides, superabsorbent polymers and their mixtures. 9. Cosmetic composition according to claim 7 or 8, wherein the hydrophilic gelling agent is a crosslinked sodium polyacrylate or a 2-acrylamido-2-methylpropanesulphonic acid polymer. 10. Cosmetic composition according to any one of claims 7 to 9, wherein the content of gelling agent (s) hydrophilic (s) ranges from 0.01% to 10% by weight relative to the total weight of said composition. 11. Cosmetic composition according to any one of claims 1 to 10, wherein the aqueous phase comprises from 10% to 80% by weight of water relative to the total weight of said composition. 12. Cosmetic composition according to any one of claims 1 to 11, wherein the oily phase comprises at least one oil selected from the group consisting of hydrocarbon oils, silicone oils, fluorinated oils and mixtures thereof. 13. Cosmetic composition according to any one of claims 1 to 12, comprising from 5% to 85% by weight of oily phase relative to the total weight of said composition. 35 14. Non-therapeutic cosmetic process for making up and / or caring for keratin materials, comprising a step of applying to said 30-keratinic materials at least one layer of a composition according to any one of Claims 1 to 13. 15. A method for coating keratin materials comprising a step of applying to said keratin materials a cosmetic composition according to any one of claims 1 to 13.