WO2017103052A1

WO2017103052A1 - Cosmetic composition based on white pigments and spherical titanium dioxide aggregates

Info

Publication number: WO2017103052A1
Application number: PCT/EP2016/081362
Authority: WO
Inventors: Olfa BCHIR; Ludovic Thevenet; Gaëtan Chevalier
Original assignee: L'oreal
Priority date: 2015-12-16
Filing date: 2016-12-16
Publication date: 2017-06-22
Also published as: FR3045330A1; FR3045330B1

Abstract

The present invention relates to a composition, especially a cosmetic composition, for caring for and/or making up keratin materials, comprising, in a physiologically acceptable medium, at least: - white pigments of the titanium dioxide type; and - spherical titanium dioxide aggregates with a mean aggregate size of less than 0.50 µm said composition being non-pulverulent. The invention also relates to a cosmetic process for caring for and/or making up keratin materials, especially the skin, comprising at least one step which consists in applying to said keratin materials a composition as defined above.

Description

COSMETIC COMPOSITION BASED ON WHITE PIGMENTS AND SPHERICAL TITANIUM DIOXIDE AGGREGATES

The present invention relates to the field of cosmetic compositions more particularly intended to be applied to the face.

The search for novel effects is an ongoing endeavor in the field of makeup, and most particularly of the face. In particular, there is a user expectation for a natural effect on the complexion. In particular, users are in search of makeup compositions that can afford good homogenization of the complexion, while at the same time maintaining transparency and the natural look of the skin.

A certain number of foundation formulations have already been developed in an attempt to satisfy these needs.

These formulations are based especially on the use of a high content of pigments for masking the color and relief imperfections of the face. Unfortunately, these pigments are opaque and accumulate in the pores and wrinkles of the skin, thus creating a color and opacity contrast that make them stand out even more. Thus, these formulations have the drawback of giving the skin a "mask" effect, contrary to the desired natural finish.

It is moreover known practice to increase the back-scattered red light to boost the natural result afforded by makeup compositions. This technique exploits an intrinsic property of the skin: red light is the one which penetrates most deeply into the skin, i.e. it is the least absorbed, and is the most back-scattered.

Specifically, when light reaches the skin, it first encounters the cornified layer {stratum corneum). This layer absorbs very little visible light and said light is transmitted with a slight change in direction due to refraction. From an optical viewpoint, the cornified layer thus behaves like a very thin transparent layer with an irregular outer surface.

Under the cornified layer is the epidermis, whose thickness ranges from 30 to 150 microns. It is formed from cells colored with melanin. The epidermis is too thin to scatter light sufficiently, and the ray arriving from the cornified layer is transmitted without changing direction, it is partly absorbed by the melanin and becomes slightly ochre- colored. From an optical viewpoint, it thus behaves like an ochre-tinted transparent filter which is more or less dark depending on the amount of melanin present. The upper dermis which lies immediately below the epidermis (papillary dermis) is made of collagen fibers and is highly irrigated with blood capillaries. Once again, it is too thin to be able to scatter light. The ray arriving from the epidermis is transmitted without changing direction, but it is partly absorbed by the hemoglobin contained in the blood capillaries and becomes pink-ochre colored. From an optical viewpoint, this layer thus behaves like a red-tinted transparent film which is more or less dark depending on the dilation of the blood capillaries which may arise in the case of heat, effort or emotion.

The final layer explored by visible light is the deep dermis (reticular dermis). This layer, formed from bundles of collagen fibers and of elastin fibers parallel to the surface of the skin, contains very few blood vessels and nerves. No pigment absorbs light or modifies the color. However, it contains numerous collagen fibers which scatter light. The ray arriving from the preceding layers changes direction very often, such that the beam invades a large volume around this point and appears as a halo of light. This diffuse light source illuminates the surface of the skin through the upper layers, which further enriches its pink and yellow color: this is the back-scattered light.

Red light is the one which penetrates most deeply into the skin, it is the one which is the least absorbed and which back-scatters the most relative to the other colors of the spectrum. This effect may be observed directly when a lamp is placed in direct contact with the skin. A red halo is uniformly back-scattered to the surface.

By increasing the proportion of red light transmitted in the skin through a cosmetic composition, the back-scattered red light is increased. This light re-emerges at the surface, illuminating the pores and wrinkles, which reduces the shadow areas and improves the attenuation of the relief imperfections. For the color imperfections, the back-scattered light reduces the color contrast with the surrounding skin color and thus reduces the visibility of the color imperfections.

Thus, patent applications JP2012131783 and JP2006265134 exploit these optical properties and describe cosmetic compositions for affording the skin a transparent and natural finish. However, these formulations cannot correctly camouflage skin imperfections or afford homogenization of the complexion desired by users. Specifically, these compositions have the drawback of reducing the initial opacity of the foundation, thus impairing the basic properties desired for this type of composition. US 2009/060856, US 2010/189666, FR 2 944 701 and JP 2002/121116 describe cosmetic compositions comprising white pigments. However, these compositions do not permit to camouflage skin imperfections with a natural effect as desired by the consumer.

There is thus still a need for cosmetic formulations, more particularly devoted towards caring for and/or making up facial skin, which are capable of affording a natural effect but which are free of the abovementioned drawbacks.

More precisely, there is still a need for cosmetic formulations for affording homogenization of the complexion and for camouflaging skin imperfections, desired by consumers, combined with a natural effect, and which are free of a "mask" effect on the skin.

The object of the present invention is, precisely, to satisfy these expectations.

Thus, the present invention describes a composition, especially a cosmetic composition, for caring for and/or making up keratin materials, comprising, in a physiologically acceptable medium, at least:

- white pigments; and

- spherical titanium dioxide aggregates with a mean aggregate size of less than

0.50 μιη.

According to a first of its aspects, the present invention relates to a composition for caring for and/or making up keratin materials, comprising, in a physiologically acceptable medium, at least:

- white pigments of the titanium dioxide type; and

- spherical titanium dioxide aggregates with a mean aggregate size of less than

0.50 μιη,

said composition being non-pulverulent. The term "keratin materials" especially means the skin, the lips, the eyebrows and/or the eyelashes, in particular the skin and/or the eyebrows, preferably the skin and especially facial skin. The term "spherical titanium dioxide aggregates" means a lump or agglomerate of titanium dioxide particles linked together so as to form an assembly of spherical shape, that is to say having a sphericity index, i.e. the ratio between its longest diameter and its shortest diameter is between 0.8 and 1.2.

The present invention is thus based on the combined use of at least one white pigment of the titanium dioxide type, and of aggregates of titanium dioxide particles of specific mean size.

Contrary to all expectation, the combination under consideration according to the invention makes it possible to significantly increase the back-scattered red light, and thus to improve the homogenization of the complexion and the natural result. The initial opacity of the cosmetic composition is not decreased, which would be detrimental to the camouflaging of skin imperfections. In addition, no additional opacity is moreover provided to the cosmetic formulation, which would also be harmful with respect to the desired natural finish, since excessive opacity would then lead to a "mask" effect on the skin, which is precisely to be avoided.

These properties are especially demonstrated in the examples below. The cosmetic compositions according to the invention also have very good cosmetic properties, and especially good coverage.

The coverage measurements may especially be taken using the protocol described below. The coverage (contrast ratio) of the compositions is evaluated by preparing a 25 μιη film on a contrast card (such as a Byk Chart PA-2814) having a white part and a black part, using an automatic spreader. The film is left to dry for 1 hour at room temperature (20-25°C). Color measurements are taken using a Minolta CM600d spectrocolorimeter. The colorimeter gives numerical data representing the absolute value and the color difference between a reference sample and a sample to be controlled. The absolute values of each film sample on the white background for the color by integrating the black background are used to calculate the coverage. The operating conditions are as follows: standard observer CIE 1964 10°, illuminant CIE type D65, diffuse measuring geometry/8° and observation D65/10⁰, mode: specular component included (SCI), mean aperture (10 mm) on the black and white backgrounds. The apparatus is equipped with an optical device that produces scattered light, placed in a spherical cavity lined with a white coat, which induces multiple reflection of the light. An anti-glare trap can remove the glare effects from the surface of the sample. The spectra are expressed as colorimetric coordinates in the Commission Internationale de l'Eclairage CIELab76 space according to recommendation 15:2004. The contrast ratio is calculated by taking the arithmetic mean of the Y values on the black background, divided by the mean value of Y on the white background, multiplied by 100.

According to a preferred embodiment variant, the composition according to the invention comprises white pigments of the titanium dioxide type and spherical titanium dioxide aggregates with a mean aggregate size of less than 0.50 μιη.

Advantageously, the composition according to the invention also comprises colored pigments, and in particular colored metal oxide pigments.

According to the invention, a composition according to the invention may be in the form of an emulsion, and in particular in the form of a water-in-oil emulsion, also known as an inverse emulsion.

A composition according to the invention is non-pulverulent, and in particular the composition is in liquid form.

A composition according to the invention may more particularly be a foundation, a face powder, an eyeshadow, or alternatively a body makeup product, a skin coloring product or a care product such as a care cream or a tinted cream, and is preferably a foundation.

According to another aspect, the present invention relates to a cosmetic process for making up and/or caring for keratin materials, especially the skin, and in particular facial skin, comprising at least one step which consists in applying to said keratin materials a composition according to the invention.

WHITE PIGMENTS

The white pigment(s) denote a mineral or organic particle, which is insoluble in an aqueous solution, said particle being white, and porous or non-porous.

In particular, said pigments are in the form of a white powder.

The term "white" especially means white and derivatives thereof (off-white, alabaster white, silver-white, etc.), as opposed to primary colors and derivatives. In particular, the "white" pigments may be defined by a lightness L* of greater than 95 and by a saturation c* of less than or equal to 3 in the CIE L a b 1976 colorimetric space, measured with a Minolta CM600d^® colorimetric chromameter according to the following protocol:

The white pigment is, in a first stage, dispersed in the following cosmetic support in an amount sufficient to make said support opaque (for example 5% by weight of pigment relative to the total weight of the composition):

and the pigment dispersion is then placed in a 15 ml flask (aperture diameter: 1.9 cm; depth: 1.8 cm). The surface of the cosmetic support is smoothed off by leveling with a glass slide. The colorimeter cell is then placed in contact with said surface and the colorimetric parameters are determined. The CM600d^® colorimetric chromameter is calibrated with, on the one hand, a white reference (white calibration standard of the Spectralon^® type) on values of lightness L* = 100 and saturation c* = 0, and, on the other hand, a light trap. The white pigments may be chosen especially from titanium dioxide, zinc oxide, mica, guanine, sericite, talc, kaolin, corn starch esterified with octenylsuccinic anhydride, and salts thereof such as aluminum salts (such as the commercial product sold under the name Dry Flo Plus^® from National Starch (INCI name: Aluminum Starch Octenylsuccinate).

According to the present invention, the white pigments are of the titanium dioxide type.

According to a particularly preferred embodiment, the white pigments of the titanium dioxide type, are non-spherical.

The term "non- spherical" means particles/aggregates in three dimensions (length, width and thickness or height) for which the ratio of the greatest dimension to the smallest dimension is greater than 1.2. The dimensions of the particles/aggregates of the invention are evaluated by scanning electron microscopy and image analysis.

In particular, the titanium dioxide (Ti0₂) may be in rutile and/or anatase form and/or in an amorphous form.

According to a preferred form of the invention, the white pigments of the titanium dioxide type have a mean size ranging from 0.10 μιη to 1.00 μιη.

According to a particular form of the invention, the white pigments of the titanium dioxide type have a size characterized by a D[50] ranging from 0.10 μιη to 1.00 μιη and preferably ranging from 0.20 μιη to 0.70 μιη.

The sizes of the titanium dioxides are measured by static light scattering using a commercial MasterSizer 3000 particle size analyser from Malvern, which makes it possible to determine the particle size distribution of all of the particles/aggregates over a wide range which may extend from 0.01 μιη to 1000 μιη. The data are processed on the basis of the standard Mie scattering theory. This theory is the one most suitable for size distributions ranging from submicron to multimicron; it allows an "effective" particle/aggregate diameter to be determined. This theory is especially described in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957.

D[50] represents the maximum size that 50% by volume of the titanium dioxide particles have.

According to a particular form of the invention, the white pigments of the titanium dioxide type used in the compositions according to the invention may have an untreated surface. As example of an untreated titanium dioxide in accordance with the present invention, mention may be made of titanium dioxide in anatase form such as the commercial product sold under the name HOMBITAN FF PHARMA^® (D[50] = 0.57 μιη) by the company Sachtleben.

According to a particular form of the invention, the white pigments may or may not be surface-treated, totally or partially, with at least one hydrophilic or hydrophobic treating agent.

For the purposes of the invention, the surface treatment of a titanium dioxide according to the invention generally denotes the total or partial surface treatment with a surface agent, absorbed, adsorbed or grafted onto said pigment.

The surface-treated titanium dioxide may be prepared according to surface treatment techniques of chemical, electronic, mechanochemical or mechanical nature that are well known to those skilled in the art. Commercial products may also be used.

The surface agent may be absorbed, adsorbed or grafted onto the pigments by evaporation of solvent, chemical reaction and creation of a covalent bond.

The surface treatment may represent from 0.1% to 50% by weight and in particular from 0.5% to 5% by weight relative to the total weight of the coated pigment.

The surface treatment may be performed, for example, by adsorption of a liquid surface agent onto the surface of the solid particles by simple mixing with stirring of the titanium dioxide and of said surface agent, optionally with heating, prior to the incorporation of the titanium dioxide into the other ingredients of the makeup or care composition.

The surface treatment may be performed, for example, by chemical reaction of a surface agent with the surface of the titanium dioxide and creation of a covalent bond between the surface agent and the particles. This method is especially described in patent US 4 578 266. The chemical surface treatment may consist in diluting the surface agent in a volatile solvent, dispersing the pigments in this mixture and then slowly evaporating off the volatile solvent, so that the surface agent is deposited at the surface of the pigments. This volatile solvent may be water.

Hydrophilic treating agent

According to a particular embodiment, the titanium dioxides may be surface- treated with at least one hydrophilic treating agent chosen from biological polymers, carbohydrates, polysaccharides, polyacrylates and polyethylene glycol derivatives. Mention may also be made of mineral agents such as silica, silicates, alumina and mixtures thereof (e.g.: silica/alumina).

As examples of biological polymers for coating the materials to be dissolved according to the invention, mention may be made of polymers based on monomers of carbohydrate type, in particular those derived from algae, from terrestrial plants, from fungi or from biotechnologies, from plankton or from arthropod shells. More particularly, mention may be made of guar gum, locust bean gum, xanthan gum, gum arabic, sclerotium gum, konjac gum, carrageenans, alginates and derivatives thereof, pectins, agar-agar, glycogen, dextran, starch and derivatives thereof, cellulose and derivatives thereof, hyaluronic acid salts such as sodium hyaluronate and derivatives thereof, soluble proteoglycans, glycosaminoglycans, chitins, chitosans and derivatives thereof, and mixtures thereof.

C1-C20 alkylene glycols or C1-C20 alkylene glycol ethers, alone or used in combination with tri(Ci-C2o)alkylsilanes, may also be used as surface-treatment agents. Examples that may be mentioned include pigments surface-treated with PEG alkyl ether alkoxysilane, for instance pigments treated with PEG-8-methyl ether triethoxysilane sold by the company Kobo under the name SW pigments.

As examples of hydrophilic-treated titanium dioxide, mention may be made of rutile titanium dioxide surface-treated with alumina/silica/trimethylol propane sold under the name TlPAQUE PF671^® from ISHIHARA SANGYO (mean size = 0.21 μιη), and anatase titanium dioxide surface-treated with a polydimethylsiloxane sold under the name SA- TAO^® (INCI name: Titanium Dioxide (and) Dimethicone and D[50] = 0.90 - 0.97 μπι) by the company MYOSHI KASEI.

Lipophilic or hydrophobic treating agent

According to a particular embodiment of the invention, the titanium dioxides may be coated according to the invention with at least one compound chosen from silicone surface agents; fluoro surface agents; fluorosilicone surface agents; metal soaps; N- acylamino acids or salts thereof; lecithin and derivatives thereof; isopropyl triisostearyl titanate; isostearyl sebacate; natural plant or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and mixtures thereof.

Silicone surface agent

According to a particular embodiment, the titanium dioxides may be totally or partially surface-treated with a compound of silicone nature.

The silicone surface agents may be chosen from organopolysiloxanes, silane derivatives, silicone-acrylate copolymers, silicone resins, and mixtures thereof.

The term "organopolysiloxane compound" means a compound having a structure comprising an alternance of silicon atoms and oxygen atoms and comprising organic radicals linked to silicon atoms. i) Non- elastomer ic organopolysiloxane

Non-elastomeric organopolysiloxanes that may especially be mentioned include polydimethylsiloxanes, polymethylhydrogenosiloxanes and poly alkoxy dimethy lsilo xanes .

The alkoxy group may be represented by the radical R-O- such that R represents methyl, ethyl, propyl, butyl or octyl, 2-phenylethyl, 2-phenylpropyl or 3,3,3- trifluoropropyl radicals, aryl radicals such as phenyl, tolyl or xylyl, or substituted aryl radicals such as phenylethyl.

One method for surface-treating pigments with a polymethylhydrogenosiloxane consists in dispersing the pigments in an organic solvent and then in adding the silicone compound. On heating the mixture, covalent bonds are created between the silicone compound and the surface of the pigment. According to a preferred embodiment, the silicone surface agent may be a non- elastomeric organopolysiloxane, especially chosen from polydimethylsiloxanes.

According to a particular form, use may be made of triethoxysilylethyl polydimethylsiloxyethyl dimethicone, such as the commercial product sold under the name KF9908^® from Shin-Etsu. ii) Alkylsilanes and alkoxysilanes

Silanes containing alkoxy functionality are especially described by Witucki in "A silane primer, chemistry and applications of alkoxy silanes", Journal of Coatings Technology, 65, 822, pages 57-60, 1993.

Alkoxysilanes such as the alkyltriethoxysilanes and the alkyltrimethoxysilanes sold under the references Silquest A- 137 (OSI Specialities) and Prosil 9202 (PCR) may be used for coating the pigments.

The use of alkylpolysiloxanes bearing a reactive end group such as alkoxy, hydroxyl, halogen, amino or imino is described in patent application JP H07- 196946. They are also suitable for treating the pigments.

Hi) Silicone-acrylate polymers

Grafted silicone-acrylic polymers having a silicone backbone as described in patents US 5 725 882, US 5 209 924, US 4 972 037, US 4 981 903, US 4 981 902 and US 5 468 477 and in patents US 5 219 560 and EP 0 388 582 may be used.

Other silicone-acrylate polymers may be silicone polymers comprising in their structure the unit of formula (I) below:

i †i G,

( -Si— 0-), (— Si-0 - )_b (— Si -o— )_c

(G₂) -S -G₃ G, (G₂)— S-G₄

(I)

in which the radicals Gi, which may be identical or different, represent hydrogen or a Ci- Cio alkyl radical or alternatively a phenyl radical; the radicals G₂, which may be identical or different, represent a Ci-Cio alkylene group; G₃ represents a polymeric residue resulting from the (homo)polymerization of at least one ethylenically unsaturated anionic monomer; G₄ represents a polymeric residue resulting from the (homo)polymerization of at least one ethylenically unsaturated hydrophobic monomer; m and n are equal to 0 or 1; a is an integer ranging from 0 to 50; b is an integer that may be between 10 and 350, c is an integer ranging from 0 to 50; with the proviso that one of the parameters a and c is other than 0.

Preferably, the unit of formula (I) above has at least one, and even more preferentially all, of the following characteristics:

- the radicals Gi denote an alkyl radical, preferably a methyl radical;

- n is non-zero, and the radicals G₂ represent a divalent C₁-C3 radical, preferably a propylene radical;

- G3 represents a polymeric radical resulting from the (homo)polymerization of at least one monomer of the ethylenically unsaturated carboxylic acid type, preferably acrylic acid and/or methacrylic acid;

- G₄ represents a polymeric radical resulting from the (homo)polymerization of at least one monomer of the (Ci-Cio)alkyl (meth)acrylate type, preferably such as isobutyl or methyl (meth)acrylate.

Examples of silicone polymers corresponding to formula (I) are especially polydimethylsiloxanes (PDMS) onto which are grafted, via a connecting chain unit of thiopropylene type, mixed polymer units of the poly(meth)acrylic acid type and of the polymethyl (meth)acrylate type.

Other examples of silicone polymers corresponding to formula (I) are especially polydimethylsiloxanes (PDMS) onto which are grafted, via a connecting chain unit of thiopropylene type, polymer units of the polyisobutyl (meth)acrylate type. iv) Silicone resins

The silicone surface agent may be chosen from silicone resins.

The term "resin" means a three-dimensional structure.

The silicone resins may be soluble or swellable in silicone oils. These resins are crosslinked polyorganosiloxane polymers.

The nomenclature of silicone resins is known under the name "MDTQ", the resin being described as a function of the various siloxane monomer units that it comprises, each of the letters "MDTQ" characterizing a type of unit. The letter M represents the mono functional unit of formula (CH3)3SiOi/₂, the silicon atom being bonded to only one oxygen atom in the polymer comprising this unit.

The letter D means a difunctional unit (CH₃)₂Si0_2/2 in which the silicon atom is bonded to two oxygen atoms.

The letter T represents a trifunctional unit of formula (CH₃)SiC"3/₂.

In the units M, D and T defined above, at least one of the methyl groups may be substituted with a group R other than a methyl group, such as a hydrocarbon-based radical (especially alkyl) containing from 2 to 10 carbon atoms or a phenyl group, or alternatively a hydroxy 1 group.

Finally, the letter Q means a tetrafunctional unit Si0_4/2 in which the silicon atom is bonded to four hydrogen atoms, which are themselves bonded to the rest of the polymer.

Various resins with different properties may be obtained from these different units, the properties of these polymers varying as a function of the type of monomers (or units), of the type and number of substituted radicals, of the length of the polymer chain, of the degree of branching and of the size of the side chains.

Examples of these silicone resins that may be mentioned include:

- silo xy silicates, which may be trimethyl siloxysilicates of formula [(CH₃)₃XSiXO]xX(Si0_4/2)_y (MQ units) in which x and y are integers ranging from 50 to 80;

- polysilsesquioxanes of formula (CH₃Si03/₂)_x (T units) in which x is greater than 100 and at least one of the methyl radicals of which may be substituted with a group R as defined above;

- polymethylsilsesquioxanes, which are polysilsesquioxanes in which none of the methyl radicals is substituted with another group. Such polymethylsilsesquioxanes are described in document US 5 246 694.

As examples of commercially available polymethylsilsesquioxane resins, mention may be made of those sold:

- by the company Wacker under the reference Resin MK^®, such as Belsil PMS

MK^®: polymer comprising CH₃Si03/₂ repeating units (T units), which may also comprise up to 1% by weight of (CH₃)₂Si02/2 units (D units) and having an average molecular weight of about 10 000;

- by the company Shin-Etsu under the references K -220L^®, which are composed of T units of formula CH₃Si0₃/₂ and contain Si-OH (silanol) end groups, under the reference K -242A, which comprise 98% of T units and 2% of dimethyl D units and contain Si-OH end groups, or also under the reference KR-251, comprising 88% of T units and 12% of dimethyl D units and contain Si-OH end groups.

Siloxy silicate resins that may be mentioned include trimethyl siloxy silicate (TMS) resins, optionally in the form of powders. Such resins are sold under the references SRI 000^®, E 1170-002^® or SS 4230^®, by the company General Electric or under the references TMS 803^®, Wacker 803^® and 804^® by the company Wacker Silicone Corporation.

Mention may also be made of trimethyl siloxy silicate resins sold in a solvent such as cyclomethicone, sold under the name KF-7312J^® by the company Shin-Etsu or DC 749^® and DC 593^® by the company Dow Corning.

Fluoro surface agent

The titanium dioxide may be totally or partially surface-treated with a compound of fluoro nature.

The fluoro surface agents may be chosen from perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoropolyethylenes (PTFE), perfluoroalkanes, perfluoroalkyl silazanes, polyhexafluoropropylene oxides, and polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups.

The term "perfluoroalkyl radical" means an alkyl radical in which all the hydrogen atoms have been replaced with fluorine atoms.

Perfluoropolyethers are in particular described in patent application EP 0 486 135, and sold under the trade name Fomblin^® by the company Montefluos.

Perfluoroalkyl phosphates are in particular described in patent application JP H05-86984. The perfluoroalkyl diethanolamine phosphates sold by Asahi Glass under the reference AsahiGuard AG530^® may be used.

Among the linear perfluoroalkanes that may be mentioned are perfluorocycloalkanes, perfluoro(alkylcycloalkanes), perf uoropolycycloalkanes, aromatic perfluoro hydrocarbons (perfluoroarenes) and hydrocarbon-based perfluoro organic compounds comprising at least one heteroatom.

Among the perfluoroalkanes, mention may be made of the linear alkane series such as perfluorooctane, perfluorononane or perfluorodecane.

Among the perfluorocycloalkanes and perfluoro(alkylcycloalkanes), mention may be made of perfluorodecalin sold under the name Flutec PP5 GMP^® by the company Rhodia, perfluoro(methyldecalin) and perfluoro(C3-C5 alky Icy clohexanes) such as perfluoro(butylcyclohexane).

Among the perfluoropolycycloalkanes, mention may be made of bicyclo[3.3.1]nonane derivatives such as perfluorotrimethylbicyclo[3.3.1]nonane, adamantane derivatives such as perfluorodimethyladamantane, and hydrogenated perfluorophenanthrene derivatives such as tetracosafluorotetradecahydrophenanthrene.

Among the perfluoroarenes, mention may be made of perfluoronaphthalene derivatives, for instance perfluoronaphthalene and perfluoromethyl-1 -naphthalene.

As examples of commercial references of titanium dioxide particles surface- treated with at least one f uoro compound, mention may be made of:

titanium dioxide coated with perfluoroalkyl phosphate (INCI name: Titanium Dioxide (and) C9-15 Fluoroalcohol Phosphate), sold under the reference PF 5 Ti0₂ A 100^® by the company DAITO KASEI (D[50] = 0.54 μπι);

titanium dioxide coated with perfluoroalkyl phosphate (INCI name: Titanium Dioxide (and) C9-15 Fluoroalcohol Phosphate), sold under the reference PFX 5 Ti0₂ CR 50^® by the company DAITO KASEI (D[50] = 0.706 μπι). Fluorosilicone surface agent

The titanium dioxides may be totally or partially surface-treated with a compound of fluorosilicone nature.

The fluorosilicone compound may be chosen from perfluoroalkyl dimethicones, perfluoroalkyl silanes and perfluoroalkyl trialkoxysilanes.

Perfluoroalkyl silanes that may be mentioned include the products LP-IT^® and

LP-4T^® sold by Shin-Etsu Silicone.

The perfluoroalkyl dimethicones may be represented by the following formula:

in which:

- R represents a linear or branched divalent alkyl group containing from 1 to 6 carbon atoms, preferably a divalent methyl, ethyl, propyl or butyl group;

- Rf represents a perfluoroalkyl radical containing 1 to 9 carbon atoms and preferably 1 to 4 carbon atoms;

- m is chosen between 0 and 150 and preferably from 20 to 100; and

- n is chosen between 1 and 300 and preferably from 1 to 100.

As examples of commercial references of titanium dioxide particles treated with a fluorosilicone compound, mention may be made of titanium dioxide/fluorosilicone sold under the reference Fluorosil Titanium dioxide 100TA^® by the company Advanced Dermaceuticals International Inc. Other lipophilic surface agents

The hydrophobic treating agent may also be chosen from:

i) metal soaps such as aluminum dimyristate and the aluminum salt of hydrogenated tallow glutamate.

Metal soaps that may especially be mentioned include metal soaps of fatty acids containing from 12 to 22 carbon atoms and in particular those containing from 12 to 18 carbon atoms.

The metal of the metal soap may especially be zinc or magnesium. Metal soaps that may be used include zinc laurate, magnesium stearate, magnesium myristate and zinc stearate, and mixtures thereof;

ii) fatty acids such as lauric acid, myristic acid, stearic acid and palmitic acid; iii) N-acylamino acids or salts thereof, which may comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group.

The amino acid may be, for example, lysine, glutamic acid or alanine. The salts of these compounds may be the aluminum, magnesium, calcium, zirconium, zinc, sodium or potassium salts.

Thus, according to a particularly preferred embodiment, an N-acylamino acid derivative may especially be a glutamic acid derivative and/or a salt thereof, and more particularly a stearoyl glutamate, for instance aluminum stearoyl glutamate. It is, for example, the NAI surface treatment sold by Miyoshi;

iv) lecithin and derivatives thereof, such as hydrogenated lecithin, for instance the HLC surface treatment sold by LCW;

v) isopropyl triisostearyl titanate.

As examples of titanium dioxide particles treated with isopropyl titanium triisostearate (ITT) (INCI name: Titanium Dioxide (And) Isopropyl Titanium Triisostearate), mention may be made of those sold by the company KOBO under the commercial reference BTD-401^® (D[50] = 0.630 μιη);

vi) isostearyl sebacate;

vii) natural plant or animal waxes or polar synthetic waxes;

viii) fatty esters, in particular jojoba esters;

ix) phospholipids; and

x) mixtures thereof.

The waxes mentioned in the compounds mentioned previously may be those generally used in cosmetics, as defined hereinbelow.

They may especially be hydrocarbon, silicone and/or fluoro waxes, optionally comprising ester or hydroxyl functions. They may also be of natural or synthetic origin.

The term "polar wax" means a wax containing chemical compounds comprising at least one polar group. Polar groups are well known to those skilled in the art; they may be, for example, alcohol, ester or carboxylic acid groups. Polyethylene waxes, paraffin waxes, microcrystalline waxes, ozokerite and Fischer-Tropsch waxes are not included among polar waxes.

In particular, the polar waxes have a mean Hansen solubility parameter 5a at 25°C such that 5a > 0 (J/cm³)^1/2 and better still 5a > 1 (J/cm³)^1/2:

in which δρ and 5h are, respectively, the polar contributions and contributions of interaction types specific to the Hansen solubility parameters.

The definition of solvents in the three-dimensional solubility space according to Hansen is described in the article by C. M. Hansen: "The three-dimensional solubility parameters", J. Paint Technol. 39, 105 (1967):

- 5h characterizes the specific interaction forces (such as hydrogen bonding, acid/base, donor/acceptor, etc.);

- δρ characterizes the Debye interaction forces between permanent dipoles and also the Keesom interaction forces between induced dipoles and permanent dipoles.

The solubility parameters are calculated with the HSPiP v4.1 software.

The parameters δρ and 5h are expressed in (J/cm³)^1/2.

A polar wax is especially formed from molecules comprising, besides carbon and hydrogen atoms in their chemical structure, heteroatoms (such as O, N and P).

Non-limiting illustrations of these polar waxes that may especially be mentioned include natural polar waxes, such as beeswax, lanolin wax, orange wax, lemon wax and Chinese insect waxes, rice bran wax, carnauba wax, candelilla wax, ouricury wax, cork fiber wax, sugarcane wax, Japan wax, sumac wax and montan wax.

According to one particular embodiment, the titanium dioxides may be coated with at least one compound chosen from N-acylamino acids or salts thereof, isopropyl triisostearyl titanate; silicone surface agents; natural plant or animal waxes; hydrogenated lecithin, fatty esters; and mixtures thereof.

According to a more particularly preferred embodiment, the titanium dioxides may be coated with an N-acylamino acid and/or a salt thereof, in particular with a glutamic acid derivative and/or a salt thereof, especially a stearoyl glutamate, for instance aluminum stearoyl glutamate.

According to a more particularly preferred embodiment, use will be made of titanium dioxides coated with aluminum stearoyl glutamate (INCI name: Titanium Dioxide (and) Disodium Stearoyl Glutamate (and) Aluminum Hydroxide), for example sold under the reference NAI-TAO-77891^® (D[50] = 0.796 μπι) by MIYOSHI KASEI.

According to a preferred embodiment variant, the white pigment(s) are present in a content of between 1% and 25% by weight, in particular between 5% and 20% by weight and preferably between 6% and 18% by weight, relative to the total weight of the composition.

SPHERICAL TITANIUM DIOXIDE AGGREGATES

The spherical titanium dioxide aggregates in accordance with the invention have a mean aggregate size of less than 0.50 μιη, and more preferentially a mean aggregate size ranging from 0.12 μιη to 0.40 μιη and more preferentially from 0.20 μιη to 0.30 μιη.

The mean size of the titanium dioxide aggregates is measured by static light scattering using a commercial MasterSizer 3000 particle size analyser from Malvern, which makes it possible to determine the particle size distribution of all of the particles/aggregates over a wide range which may extend from 0.01 μιη to 1000 μιη. The data are processed on the basis of the standard Mie scattering theory. This theory is the one most suitable for size distributions ranging from submicron to multimicron; it allows an "effective" particle/aggregate diameter to be determined. This theory is especially described in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957.

In particular, the titanium dioxide (Ti0₂) of these aggregates may be in rutile and/or anatase form and/or in an amorphous form.

The titanium dioxide particles of these spherical aggregates may or may not be totally or partially surface-treated, with at least one hydrophilic or hydrophobic treating agent such as those mentioned previously.

Among the spherical titanium dioxide aggregates that may be used according to the invention, mention may be made especially of:

- TITANIUM DIOXIDE TREATED WITH ALUMINUM HYDROXIDE AND STEARIC ACID AND SODIUM SULFATE REFLECT BLUE (mean aggregate size = 200 nm) sold under the reference MICROMARIMO FA2^® from TAYCA;

- the reference TITANIUM DIOXIDE ST 710 EC^® (mean aggregate size = 300 nm) from TITAN KOGYO;

- the reference LMT-C^® (mean aggregate size = 140 nm) from TAYCA;

- the reference TITANIUM DIOXIDE ST 705 SA^® (mean aggregate size = 250 nm) from TITAN KOGYO. Preferably, mention may be made especially of TITANIUM DIOXIDE TREATED

WITH ALUMINUM HYDROXIDE AND STEARIC ACID AND SODIUM SULFATE REFLECT BLUE

(mean aggregate size = 200 nm) sold under the reference MlCROMARlMO FA2 from TAYCA, the reference TITANIUM DIOXIDE ST 710 EC (mean aggregate size = 300 nm) from TITAN KOGYO, the reference LMT-C (mean aggregate size = 140 nm) from TAYCA, and the reference TITANIUM DIOXIDE ST 705 SA (mean aggregate size = 250 nm) from TITAN KOGYO.

According to a preferred embodiment variant, the spherical titanium dioxide aggregates are present in a content of between 0.05% and 10%> by weight, in particular between 0.05%> and 7% by weight and preferably between 0.1 % and 6%> by weight, relative to the total weight of the composition.

COMPOSITION ACCORDING TO THE INVENTION

Needless to say, the compositions according to the invention comprise a physiologically acceptable medium.

The term "physiologically acceptable medium" is intended to denote a medium that is particularly suitable for applying a composition of the invention to keratin materials, especially the skin and more particularly to facial skin, the lips and the nails. The physiologically acceptable medium is generally suited to the nature of the support onto which the product is to be applied.

They also contain ingredients usually selected for the formulation of cosmetic compositions intended for care and/or makeup.

Fatty phase

A composition according to the invention may also comprise a fatty phase.

The fatty phase of a composition of the invention may especially comprise at least one fatty substance that is liquid at room temperature and/or a fatty substance that is solid at room temperature, such as waxes, pasty fatty substances and gums, and mixtures thereof.

For the purposes of the invention, the term "room temperature" means a temperature equal to 25°C. The fatty phase of the composition according to the invention may especially comprise, as liquid fatty substance, at least one volatile or non- volatile oil or a mixture thereof.

For the purposes of the invention, the term "volatile oil" means any oil that is capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure.

The term "non- volatile oil" means an oil that remains on the skin at room temperature and atmospheric pressure for at least several hours, and that especially has a vapor pressure of less than 0.01 mmHg (1.33 Pa).

These volatile or non- volatile oils may for example be hydrocarbon-based oils or silicone oils, or mixtures thereof. The term "hydrocarbon-based oil" means an oil mainly containing hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur or phosphorus atoms.

Volatile hydrocarbon-based oils may be chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially branched Cs-Ci6 alkanes, for instance Cs-Ci6 isoalkanes of petroleum origin (also known as isoparaffms), for instance isododecane (also known as 2,2,4,4, 6-pentamethylheptane), isodecane and isohexadecane, for example the oils sold under the trade names Isopar^® or Permethyl^®, branched Cs-Ci6 esters such as isohexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon- based oils, for instance petroleum distillates, especially those sold under the name Shell Solt^® by the company Shell, may also be used.

Volatile oils that may also be used include volatile silicones, for instance volatile linear or cyclic silicone oils, especially those with a viscosity≤ 8 centistokes (8 x 10^"6 m²/s) and especially containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made especially of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethy locty ltrisilo xane, hexamethy ldisilo xane, o ctamethy ltrisilo xane , decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof. The volatile oil may be present in a composition according to the invention in a content ranging from 0.1% to 50% by weight, especially from 1% to 40% by weight and in particular from 1% to 35% by weight relative to the total weight of the composition.

The non-volatile oils may be chosen in particular from non-volatile hydrocarbon-based, fluoro and/or silicone oils.

Non-volatile hydrocarbon-based oils that may especially be mentioned include:

- hydrocarbon-based oils of animal origin,

- hydrocarbon-based oils of plant origin, such as triglycerides consisting of fatty acid esters of glycerol, the fatty acids of which may have varied chain lengths from C₄ to C₂₄, these chains possibly being linear or branched, and saturated or unsaturated; these oils are in particular wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil and musk rose oil; shea butter; or alternatively caprylic/capric acid triglycerides such as those sold by the company Stearineries Dubois or those sold under the names Miglyol^® 810, 812 and 818 by the company Dynamit Nobel,

- synthetic ethers containing 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, and squalane, and mixtures thereof,

- synthetic esters such as oils of formula RiCOOR₂ in which Ri represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R₂ represents an in particular branched hydrocarbon-based chain containing from 1 to 40 carbon atoms, on condition that Ri + R₂ > 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C₁₂ to C₁₅ alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, alkyl or polyalkyl heptanoates, octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate and diisostearyl malate; polyol esters and pentaerythritol esters, - fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2- undecylpentadecano 1,

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

- mixtures thereof.

The non-volatile silicone oils that can be used in the composition according to the invention may be non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups that are pendent and/or at the end of a silicone chain, these groups each containing from 2 to 24 carbon atoms, phenylsilicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, and 2-phenylethyltrimethyl siloxysilicates, and mixtures thereof.

The non-volatile oils may be present in a composition according to the invention in a content ranging from 0.1% to 50% by weight, especially from 1% to 40% by weight and in particular from 1% to 35% by weight relative to the total weight of the composition.

Dyestuffs

Besides the dyestuffs, the white pigments and the aggregates described above, the compositions according to the invention may also comprise one or more dyestuffs.

The dyestuffs that are suitable for use in the invention may be water-soluble dyes, but may also be liposoluble.

For the purposes of the invention, the term "water-soluble dyestuf ' means any natural or synthetic, generally organic compound, which is soluble in an aqueous phase or water-miscible solvents and which is capable of coloring in primary colors or derivatives.

As water-soluble dyes that are suitable for use in the invention, mention may be made in particular of synthetic or natural water-soluble dyes, for instance FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanine (beetroot), carmine, copper chlorophylline, methylene blue, anthocyanins (enocianin, black carrot, hibiscus and elder), caramel and riboflavin.

The water-soluble dyes are, for example, beetroot juice and caramel.

For the purposes of the invention, the term "liposoluble dyestuf ' means any natural or synthetic, generally organic compound, which is soluble in an oily phase or solvents that are miscible with a fatty substance and which is capable of coloring in primary colors or derivatives.

As liposoluble dyes that are suitable for use in the invention, mention may be made especially of synthetic or natural liposoluble dyes, for instance DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan red, carotenes (β-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow, annatto and curcumin.

Among the dyestuffs, mention may also be made of colored pigments.

The term "colored pigments" should be understood as meaning colored, mineral or organic particles, which are insoluble in an aqueous solution, and which are intended to color the composition containing them with primary colors and derivatives.

As colored mineral pigments that may be used in the invention, mention may be made especially of iron oxide or chromium oxide, ferric blue, manganese violet, ultramarine blue and chromium hydrate, and mixtures thereof.

It may also be a pigment having a structure that may be, for example, of sericite/brown iron oxide/titanium dioxide/silica type. Such a pigment is sold, for example, under the reference Coverleaf NS or JS by the company Chemicals and Catalysts, and has a contrast ratio in the region of 30.

They may also be pigments having a structure that may be, for example, of silica microsphere type containing iron oxide. An example of a pigment having this structure is the product sold by the company Miyoshi under the reference PC Ball PC-LL- 100 P, this pigment consisting of silica microspheres containing yellow iron oxide.

Materials with an optical effect

Besides the dyestuffs, the white pigments and the aggregates described above, the compositions according to the invention may also comprise one or more materials with an optical effect. Among the materials with an optical effect, mention may be made of nacres, particles with a metallic glint, and mixtures thereof.

The term "nacres" should be understood as meaning colored particles of any form, which may or may not be iridescent, especially produced by certain molluscs in their shell, or alternatively synthesized, and which have a color effect via optical interference.

The nacres may be chosen from nacreous pigments such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye and also nacreous pigments based on bismuth oxychloride. They may also be mica particles at the surface of which are superposed at least two successive layers of metal oxides and/or of organic dyestuffs.

Examples of nacres that may also be mentioned include 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 the nacres Timica, Flamenco and Duochrome (based on mica) sold by the company Engelhard, the Timiron nacres sold by the company Merck, the Prestige mica-based nacres, sold by the company Eckart, and the Sunshine synthetic mica-based nacres, sold by the company Sun Chemical.

The nacres may more particularly have a yellow, pink, red, bronze, orangey, brown, gold and/or coppery color or glint.

Advantageously, the nacres in accordance with the invention are micas coated with titanium dioxide or with iron oxide, and also bismuth oxychloride.

For the purposes of the present invention, the term "particles with a metallic glint" means any compound whose nature, size, structure and surface finish allow it to reflect the incident light, especially in a non- iridescent manner.

The particles with a metallic glint that may be used in the invention are in particular chosen from:

- particles of at least one metal and/or of at least one metal derivative,

- particles comprising a monomaterial or multimaterial organic or mineral substrate, at least partially coated with at least one layer with a metallic glint comprising at least one metal and/or at least one metal derivative, and

- mixtures of said particles. Among the metals that may be present in said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te and Se, and mixtures or alloys thereof. Ag, Au, Cu, Al, Zn, Ni, Mo and Cr, and mixtures or alloys thereof (for example bronzes and brasses) are preferred metals.

The term "metal derivatives" denotes compounds derived from metals, especially oxides, fluorides, chlorides and sulfides.

Illustrations of these particles that may be mentioned include aluminum particles, such as those sold under the names Starbrite 1200 EAC^® by the company Siberline and Metalure^® by the company Eckart and glass particles coated with a metallic layer, especially those described in documents JP-A-09188830, JP-A-10158450, JP-A- 10158541, JP-A-07258460 and JP-A-05017710.

Hydrophobic treatment of the dyestuffs

The dyestuffs, nacres and particles with a metallic glint as described previously may be totally or partially surface-treated, with a hydrophobic agent, to make them more compatible with the lipophilic phase of the composition of the invention, especially so that they have good wettability with oils. Thus, these treated pigments are well dispersed in the oily phase.

Hydrophobic-treated pigments are described especially in document EP-A-

1 086 683.

The hydrophobic treating agent may be chosen from silicones such as methicones, dimethicones and perfluoroalkylsilanes; fatty acids, such as stearic acid; metal soaps, such as aluminum dimyristate, the aluminum salt of hydrogenated tallow glutamate; perfluoroalkyl phosphates, polyhexafluoropropylene oxides; perfluoropolyethers; amino acids; N-acylamino acids or salts thereof; lecithin, isopropyl triisostearyl titanate, isostearyl sebacate, and mixtures thereof.

The term "alkyl" mentioned in the compounds cited above especially denotes an alkyl group containing from 1 to 30 carbon atoms and preferably containing from 5 to 16 carbon atoms.

Advantageously, the composition according to the invention also comprises at least colored pigments, and in particular colored metal oxide pigments.

According to an embodiment variant, the colored pigments are present in a content of between 1% and 15% by weight, in particular between 1% and 10% by weight and preferably between 1% and 7% by weight, relative to the total weight of the composition.

According to one embodiment variant, the total content of pigments represents from 1% to 25% by weight, more particularly from 1.5% to 20% by weight and preferably ranges from 3% to 18% by weight, relative to the total weight of the composition.

Advantageously, the composition according to the invention also comprises at least one material with an optical effect, chosen in particular from nacres, particles with metallic glints, and mixtures thereof.

According to one embodiment variant, the content of nacres and/or pigments with metallic glints may represent from 0.1% to 5% by weight, more particularly from 0.2% to 4.5% by weight and preferably from 0.3% to 4% by weight, relative to the weight of the composition.

Other ingredients

According to a first variant of the invention, the composition used according to the invention contains less than 5% by weight, in particular less than 2% by weight and more particularly less than 1% by weight of water, or even is free of water, i.e. anhydrous.

According to a second variant of the invention, the composition of the invention is an emulsion, and comprises an aqueous phase.

The aqueous phase (water and optionally the water-miscible solvent) may be present in a content ranging from 0.1% to 70% by weight and preferably from 0.2% to 60% by weight relative to the total weight of the composition.

The continuous aqueous phase may be formed essentially from water. It may also comprise a mixture of water and of water-miscible solvent (miscibility with water of greater than 50% by weight at 25°C), for instance lower monoalcohols containing from 1 to 5 carbon atoms such as ethanol or isopropanol, glycols containing from 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol and dipropylene glycol, C3-C4 ketones and C₂-C4 aldehydes, and mixtures thereof.

Preferably, if the aqueous phase comprises one or more water-miscible solvents, the water-miscible solvent(s)/water weight ratio ranges from 0.06 to 0.6 and preferably from 0.1 to 0.5. According to a preferred embodiment, the composition according to the invention, especially when it is in the form of an emulsion, may also comprise at least one surfactant.

These surfactants may be chosen from nonionic, anionic, cationic and amphoteric surfactants, and mixtures thereof. Reference may be made to Kirk-Othmer's Encyclopedia of Chemical Technology, Volume 22, pp. 333-432, 3rd Edition, 1979, Wiley, for the definition of the emulsifying properties and functions of surfactants, in particular pp. 347-377 of this reference, for the anionic, amphoteric and nonionic surfactants.

According to a first embodiment, the composition comprises at least one hydrocarbon-based surfactant.

The composition according to the invention may thus comprise at least one surfactant, in particular a nonionic surfactant.

The nonionic surfactants may be chosen especially from alkyl and polyalkyl esters of poly(ethylene oxide), oxyalkylenated alcohols, alkyl and polyalkyl ethers of poly(ethylene oxide), optionally polyoxyethylenated alkyl and polyalkyl esters of sorbitan, optionally polyoxyethylenated alkyl and polyalkyl ethers of sorbitan, alkyl and polyalkyl glycosides or polyglycosides, in particular alkyl and polyalkyl glucosides or polyglucosides, alkyl and polyalkyl esters of sucrose, optionally polyoxyethylenated alkyl and polyalkyl esters of glycerol, and optionally polyoxyethylenated alkyl and polyalkyl ethers of glycerol, and mixtures thereof.

Thus, according to a second embodiment, the composition may comprise at least one silicone surfactant.

The term "silicone surfactant" means a silicone compound that contains a hydrophilic chain and that is capable of emulsifying an aqueous phase in an oily phase. This silicone surfactant may be chosen from a group comprising emulsifying silicone elastomers, dimethicone copolyols, alkyl dimethicone copolyols, and mixtures thereof.

According to a preferred embodiment, the silicone surfactant is chosen from the group of dimethicone copolyols and alkyl dimethicone copolyols.

As dimethicone copolyols that are particularly suitable for use in the present invention, examples that may be mentioned include dimethicone copolyols comprising oxyethylene groups and oxypropylene groups such as the products comprising 18 oxyethylene groups and 18 oxypropylene groups, for instance the mixture of cyclomethicone and of dimethicone copolyol sold under the names Dow Corning 3225 C and Dow Corning 5225 C (INCI name: cyclopentasiloxane/PEG/PPG18/18 dimethicone) by the company Dow Corning, and the product comprising 14 oxyethylene groups and 14 oxypropylene groups, for instance the mixture of dimethicone copolyol and of cyclopentasiloxane (85/15) sold under the name Abil EM-97 by the company Goldschmidt (INCI name: Bis-PEG/PPG-14/14 Dimethicone/Cyclopentasiloxane). Use may also be made of dimethicone copolyols comprising only oxyethylene groups, such as the products sold under the trade names KF-6015 (INCI name: PEG-3 dimethicone) or KF-6017 (INCI name: PEG- 10 dimethicone) by the company Shin-Etsu.

Examples of alkyl dimethicone copolyols that may be used include those comprising a C10-C22 alkyl group, such as lauryl dimethicone copolyol, for instance the product sold under the name Q2-5200 by the company Dow Corning, cetyl dimethicone copolyol, for instance the product sold under the name Abil EM 90 by the company Goldschmidt or the polyglyceryl-4 isostearate/cetyl dimethicone copolyol/hexyl laurate mixture sold under the name Abil WE 09 by the company Goldschmidt, oleyl dimethicone copolyol, for instance the product sold under the name KF-6026 by the company Shin- Etsu, and stearyl dimethicone copolyol, for instance the product sold under the name X-22- 904 by the company Shin-Etsu. It is preferably cetyl dimethicone copolyol.

According to a particular embodiment of the invention, use is made, as silicone surfactants, of an alkyl dimethicone copolyol bearing an alkyl radical comprising from 10 to 22 carbon atoms, such as cetyl dimethicone copolyol, for instance the product sold under the name Abil EM-90 by the company Goldschmidt and the mixture of dimethicone copolyol and cyclopentasiloxane (85/15) sold under the name Abil EM-97 by the company Goldschmidt, lauryl dimethicone copolyol, for example the mixture of about 91% lauryl dimethicone copolyol and about 9% isostearyl alcohol, sold under the name Q2-5200 by the company Dow Corning, and mixtures thereof.

In a preferred embodiment, the silicone surfactant is chosen from the group of compounds of INCI name: PEG- 10 dimethicone (such as the product sold under the reference KF-6017 by the company SHIN-ETSU) and Bis-PEG /PPG-14/14 Dimethicone/Cyclopentasiloxane (such as the product sold under the reference ABIL EM 97 by the company EVONIK GOLDSCHMIDT), and mixtures thereof. When it is present in the composition, the content of surfactant(s) ranges from 0.1% to 7% by weight relative to the total weight of the composition. The cosmetic composition of the invention may also contain auxiliary coloring agents, which are especially water-soluble or liposoluble, fillers, water-soluble active agents, resistance agents, especially film-forming polymers, humectants, silicone elastomers, gelling agents, thickeners, preserving agents, fragrances, flavorings, liposoluble UV-screening agents, bactericides, odor absorbers, plant extracts, salts, antioxidants, basic agents, for instance calcium carbonate, or acidic agents, for instance citric acid or lactic acid.

It is a matter of routine operations for those skilled in the art to adjust the nature and the amount of the additives present in the compositions in accordance with the invention such that the desired cosmetic properties thereof are not thereby affected.

GALENICAL FORM

More precisely, the compositions according to the invention may be cosmetic compositions for making up keratin materials, in particular the skin, preferably of the type such as foundations, makeup bases, face powders, eye shadows, concealer products or blushers, and especially foundations.

Preferably, the composition according to the invention is a makeup base or a foundation, and in particular a foundation.

Likewise, the compositions according to the invention may be skincare products, and preferably a composition for protecting, treating or caring for the face, for example a day cream, night cream, antisun composition, protective or care body milk or after-sun milk, and more preferably a facial care composition.

In addition, the compositions under consideration according to the invention may be more or less fluid and may have the appearance of a white or colored cream, an ointment, a milk or a paste. Throughout the description, including the claims, the term "comprising a" should be understood as being synonymous with "comprising at least one", unless otherwise specified.

The terms "between... and..." and "ranging from... to..." should be understood as being inclusive of the limits, unless otherwise specified.

In the description and the examples, the percentages are percentages by weight, unless otherwise indicated. The percentages are thus given on a weight basis relative to the total weight of the composition. Unless otherwise specified, the ingredients are mixed in the order and under conditions that are readily determined by a person skilled in the art.

The invention is illustrated in greater detail by the non-limiting examples presented below.

EXAMPLES

Foundation formulations in accordance with the invention are prepared as described below.

The formulations are prepared using the weight proportions described below. The percentages are given on a weight basis relative to the total weight of the composition.

y rox e an stearc ac an so um sulfate reflect blue (mean aggregate size

= 200 nm) (Micromarimo FA2 from

Tayca)

Titanium dioxide (mean aggregate size =

300 nm) (Titanium Dioxide ST 710 EC / 4.00 / / from Titan Kogyo)

Titanium dioxide (mean aggregate size =

/ / 4.00 /

140 nm) (LMT-C from Tayca)

Titanium dioxide (mean aggregate size =

250 nm) (Titanium Dioxide ST 705 SA / / / 4.00 from Titan Kogyo)

Preparation process

The components of phase Al are mixed with stirring for 30 minutes at 1000 rpm using a Turbolab 2500 from the company Guerin, equipped with a shaft of the rotor- stator type, at room temperature.

Phase A3 is weighed out and mixed with phase Al, and the pigments are then dispersed using a three-roll mill (three treatments).

Phase A2 is then added to the preceding mixture. The mixture is homogenized for 20 minutes, at room temperature.

Phase Bl is prepared and added in a gentle stream to the preparation. Emulsification is performed for 10 minutes at 4000 rpm, at room temperature.

Phase B2 is added and the mixture is homogenized for 5 minutes at 1000 rpm, at room temperature.

Evaluation of the compositions

The back-scattering of the formulations was evaluated using a TLS850 translucimeter from Diastron.

This measuring machine quantifies the amount of light transmitted into the skin and then back-scattered to a certain distance from the source point as a function of the wavelength and the distance to the source point.

Principle of the machine

An RGB LED source delivers a light beam which illuminates the sample (the formulation according to the invention spread onto the skin). The light then continues its path within the various constituent layers of the skin via a combination of refraction, absorption and scattering. Part of this back-scattered light in the skin re-emerges and is then recovered and analysed by the machine. A photodiode array collects the light back- scattered by the skin and produces a graph describing the amount of light returned as a function of the distance to the point of illumination of the sample. Method used

50 μΐ of the formulation according to the invention to be analysed are taken up with a micropipette and then spread onto the skin over a defined area. After drying, the machine is placed on the made-up skin and the measurements are started.

Results

With the translucimeter, it is very clearly seen that the compositions according to the invention allow very good back-scattering of red light. In particular, formulation 1 according to the invention shows very good performance.

In addition, the four foundations according to the invention have very good cosmetic qualities. In particular, by means of their capacity for increasing the red light back-scattered through the skin, they allow good homogenization of the complexion while at the same time maintaining a natural finish. In addition, the foundations according to the invention have good covering power.

Claims

1. Composition for caring for and/or making up keratin materials, comprising, in a physiologically acceptable medium, at least:

- white pigments of the titanium dioxide type; and

- spherical titanium dioxide aggregates with a mean aggregate size of less than

0.50 μιη,

said composition being non-pulverulent.

2. Composition according to claim 1, characterized in that the white pigments are present in a content of between 1% and 25% by weight, in particular between 5% and

20%) by weight and preferably between 6%> and 18% by weight, relative to the total weight of the composition.

3. Composition according to any one of the preceding claims, characterized in that the white pigments of the titanium dioxide type, are non-spherical.

4. Composition according to any one of the preceding claims, characterized in that the white pigments of the titanium dioxide type have a mean size ranging from 0.10 μιη to 1.00 μιη.

5. Composition according to any one of Claims 1 to 3, characterized in that the white pigments of the titanium dioxide type have a size characterized by a D[50] ranging from 0.10 μιη to 1.00 μιη and preferably ranging from 0.20 μιη to 0.70 μιη.

6. Composition according to any one of the preceding claims, characterized in that said spherical titanium dioxide aggregates have a mean aggregate size ranging from 0.12 μιη to 0.40 μιη and preferably ranging from 0.20 μιη to 0.30 μιη.

7. Composition according to any one of the preceding claims, characterized in that said spherical titanium dioxide aggregates are present in a content of between

0.05%) and 10%> by weight, in particular between 0.05%> and 7% by weight and preferably between 0.1% and 6% by weight, relative to the total weight of the composition.

8. Composition according to any one of the preceding claims, characterized in that it also comprises colored pigments, and in particular colored metal oxide pigments.

9. Composition according to the preceding claim, characterized in that the colored pigments are present in a content of between 1% and 15% by weight, in particular between 1% and 10% by weight and preferably between 1% and 7% by weight, relative to the total weight of the composition.

10. Composition according to any one of the preceding claims, characterized in that it also comprises at least one material with an optical effect, in particular chosen from nacres, particles with metallic glints, and mixtures thereof.

11. Composition according to any one of the preceding claims, characterized in that it is in the form of an emulsion, in particular in the form of a water-in-oil emulsion.

12. Composition according to any one of the preceding claims, characterized in that it is in liquid form.

13. Composition according to any one of the preceding claims, characterized in that it is a cosmetic composition for making up keratin materials, in particular the skin, and preferably a foundation.

14. Cosmetic process for making up and/or caring for keratin materials, especially the skin, comprising at least one step which consists in applying to said keratin materials a composition as defined according to any one of Claims 1 to 13.