FR2956028A1 - COSMETIC COMPOSITION INCLUDING AT LEAST ONE FLUOROPHORE COMPOUND. - Google Patents

Abstract

The present invention relates to a cosmetic composition comprising: - a first fluorophore compound having an absorption spectrum, - a second fluorophore compound having an emission spectrum straddling the absorption spectrum of the first fluorophore compound, at least one of the two fluorophore compounds having increased luminescence by a proximity interaction effect with at least one metal, the metal and the fluorophore compound belonging to the same particle.

Description

The present invention relates to the cosmetic compositions to be applied to the skin, the lips or the integuments and more particularly, but not exclusively, the cosmetic compositions intended to lighten the skin or to modify its hue. It is common to note that people with colored or even dark skin, wish to lighten the color of their skin and use for this purpose cosmetic or dermatological compositions containing bleaching agents such as hydroquinone and its derivatives , kojic acid and its derivatives, azelaic acid, arbutin and its derivatives, or alpha-hydroxyaeides. Some people also use these bleaching agents to reduce or even eliminate skin discolouration occurring either with age, or following exposure to UV radiation, during pregnancy or following skin conditions. These bleaching agents act by altering the biological activity of the melanocytes and by limiting pigmentation due to melanin formation. As a result, the effects of such whitening agents appear only slowly after having used them iteratively and prolonged. On the other hand, acting only on the endogenous biosynthesis of melanin, these bleaching agents do not allow to modulate the hue of lightening. In addition, some of these agents, such as hydroquinone or its derivatives, are to a certain extent cytotoxic. More broadly, these bleaching agents induce phenomena of allergy or skin irritation sometimes severe. It is also common to see people, wanting to lighten the color of their skin or to reduce dyschromias, use cosmetic compositions that make skin tone even and give it an immediate white appearance. These compositions contain diffusing white pigments, giving them the opacity and coverage necessary to obtain the desired effect. However, this covering power creates an opacity that causes the skin to lose its natural makeup, transparency and clarity. It generates in particular a greyish and dull effect. Furthermore, technical solutions employing emitting compounds such as organic, semi-organic or inorganic fluorescent molecules or materials in cosmetic compositions are limited by several effects making the lightening of the skin color barely perceptible. The effects due to emission intensities under natural light excitation which are too low due to their intrinsic molecular structures can be mentioned; effects due to the photo-degradation of the fluorophores and their chemical reactivity with the formulation environment lowering the level of fluorescent materials in the compositions containing them; the effects due to the wavelength absorption phenomenon of the visible range dominating the emission phenomenon and thus conferring colors that are unsuitable for lightening the complexion of the skin; the effects due to limited loading levels of these emitting compounds in organic, semisorganic or inorganic matrices intended to protect them from their chemical and / or photochemical interactions with their environment and leading to emission intensities which are too low. There is therefore a real need to benefit from emitting materials that emit light in the visible range after excitation by natural light, whose emission intensity 1.5 is high enough to make perceptible the lightening of the skin color by the cosmetic compositions containing them, and which have sufficient stability under natural light irradiation and vis-à-vis the ingredients of the cosmetic compositions containing them. There is also an interest for these emissive materials to be sufficiently transparent to impart to the skin on which these cosmetic compositions containing them are applied a natural, clear, non-opaque or over-covering appearance. There is furthermore a utility for the lightening effect of the color of the skin to be immediately perceived, to persist if desired from one to a few days, and to be of a variable hue according to the different types. of complexions treated. The problem of lightening the complexion has been the subject of numerous publications. The publication FR 2 778 561 proposes the use of optical brighteners, optionally in combination with skin whitening agents, UV filters, anti-wrinkles and moisturizing agents. The chemical families of these optical brighteners are more particularly those of stilbene, coumarin, oxazole, benzoxazole and imidazole. More precisely, the Tinopal SOP and the Uvitex OB are proposed.

However, the lightening effect of the skin is not entirely satisfactory, and does not make it possible to modulate as much as desirable the hue depending on the different complexions. In addition, in general, organic optical brighteners exhibit instability with light which results in a decrease in the lightening effectiveness of the cosmetic compositions containing them. They also exhibit a certain reactivity with the components of the cosmetic compositions which denature their molecular structure, thereby inducing a decrease in the fluorescence of the brightener and thus the lightening effect.

The publication WO10143714 discloses polymeric particles, in particular based on starch or cellulose, doped with optical brighteners. The mass content of the fluorescent agent in the matrix is limited by the solubility and diffusion properties in the matrix, to be around a value of 1.5%. The intensity of the fluorescence is thus limited and the lightening effect consequently. The publication FR 2 810 881 proposes to lighten the color of the skin by applying a composition containing optical brighteners included in inorganic particles such as titanium oxide aluminas. Here again, the limit levels of fluorescent active agents in the inorganic matrix make the lightening effect hardly perceptible.

The publication FR 2 857 254 proposes cosmetic compositions containing mineral microparticles having a high degree of porosity where the organic optical brightener is immobilized there and thus protected from possible chemical reactions which would decrease the fluorescence intensity. However, the concentration of brightener in these mineral matrices remains relatively limited and the lightening effect diminished.

The publication FR 2 885 520 proposes, to remedy this, cosmetic compositions containing a mixture of at least two photoluminescent agents optionally coated with a transparent matrix of average size less than 1.00 nm, such as the Luminux Effect Blue A compounds, Lurninux Effect Red A, Green Lurninux Effect A, marketed by Honeywell. However, these photoluminescent agents exhibit phosphorescence and low fluorescence, which makes them luminescent in the dark and faintly under daylight. The visibility of the lightening effect of the skin color is therefore relatively low under daylight. Another solution proposed by the publication FR 2 885 521 relates to cosmetic compositions containing: photoluminescent nanoparticles comprising at least one rare earth and of average size less than 500 nnn. However, it is known that rare earths have a low extinction coefficient and a low quantum yield compared to organic fluorophores. The lightening effect of the skin thus remains relatively moderate. Publication US 2007/0221884 proposes compositions containing silica particles in which are included nanoparticles of inorganic fluorophores such as ZnS, ZnCdS, CdZnS: Ag, etc. Inorganic fluorophores, with the exception of quantum dots II / VI (QD II / VI) such as based on Cadmium or TelIerium, are well known to be less fluorescent than organic fluorophores, which goes in the direction of a decrease in the intensity of the effect of 'clarification. In the case of QD II / VI, the toxicity inherent in Cd2 + or Te3 + ions makes it moreover impossible for them to be used for cosmetic applications. The solution proposed by the publication FR 2 873 021 involves cosmetic compositions containing fluorescent silicon nanoparticles, such as those sold by the company NanoSi Inc. The photostability of these fluorescent agents is improved as well as their chemical stability, but the quantum fluorescence yields are relatively low, making the intensity of the desired effect hardly perceptible. Publication W00072808 discloses the use of compositions containing inorganic fluorescent compounds in glass matrices. The desired effect lies more in the perception of a decrease in the appearance of circles / dark lines than in the lightening of the skin. In addition to the solutions aimed at remedying the chemical and photon stability problems of fluorophores, another solution to increase the intensity of the radiation emitted by fluorescent compounds is proposed in publication FR 2 848 842 30 and is based on the presence within a cosmetic composition of at least one optical brightener and a fluorescent compound such that the emission wavelength of the optical brightener corresponds to the absorption wavelength of the fluorescent compound.

The optical brighteners proposed do not allow to achieve by themselves a lightening effect of the skin and are used in this context as a supplier of radiation energy to the associated fluorescent compound. These fluoresce in the wavelength range of 550 to 700 nm, that is to say in the range of oranges and reds. This results in a clearly insufficient lightening effect to which is added an orange-red color inappropriate. To overcome all the problems mentioned above, the publications FR 2 848 821 and FR 2 848 822 propose cosmetic compositions containing coloring agents and reflective particles whose color ranges from pinkish beige to orangey beige, characterized by a shade h between 50 ° and 70 ° and a saturation C between 20 and 50. The limit of this solution lies in the use of light absorbing coloring agents to give the desired hue. This results in dulling of the skin which can not be compensated for or corrected by the reflective particles. As a result, the brightness of these compositions remains relatively low and the lightening effect is not entirely satisfactory. Moreover, it is customary to use agents of. staining such as white mineral or opacifying white fillers, to try to bring a lightening of the skin color. However, they also create a greyish color effect particularly visible on dark skin, especially black. In order to compensate in part for this effect, the publication FR 2 872 032 proposes cosmetic compositions containing solid particles of refractive index between 1.2 and 1.5, derived from the family of organopolysiloxane crosslinked elastomers, a liquid binder of refractive index between 1.2 and 1.6, and a coloring agent capable of imparting to the composition a color so that h is between 40 and 70 ° and saturation C between 20 and 50. Although the skin color obtained after application of compositions containing these ingredients is less dull than with those described in publications FR 2 848 821 and FR 2 848 822, the lightening effect is still relatively difficult to perceive and not very flexible. The publication WO2009003996 teaches the use of cosmetic compositions containing, on the one hand, titanium oxide particles having a size of between 300 and 1000 nm and, on the other hand, biological bleaching agents such as vitamins B3 or its niacinamide derivatives. and nicotine. This combination confers an immediate bleaching effect ensured by the titanium oxide particles as well as a long-term effect due to the biological bleaching agents. However, here again, the skin color obtained is more akin to an opacifying whitening than to a luminous lightening of the complexion.

Summary There is a need to further improve the cosmetic compositions for example to lighten the skin, for example to increase its reflectance in the range 500-600 nm, 600-700 nm or 500-700 nm and / or to modify the hue, or to produce new makeup effects. 1.0 More generally, there is an interest in benefiting from new cosmetic compositions which may, depending on the desired result, be used for the makeup of human keratin substrates, such as the skin, in particular of the body, hands, neck, face , and lips, and / or such as keratinous fibers, in particular eyelashes, eyebrows or hair, for example to impart an immediate, lasting and flexible lightening of the hue of these keratin substrates while keeping a natural and / or to camouflage cutaneous dyschromias. According to one of its aspects, the subject of the invention is a cosmetic composition comprising: a first fluorophore compound, in particular having an absorption spectrum in the ultraviolet field or in the visible range; second fluorophore compound having a visible range emission spectrum overlapping the absorption spectrum of the first fluorophore compound, at least one of the two fluorophore compounds having a luminescence increased by a proximity interaction effect with at least one metal , the metal and the fluorophore compound whose fluorescence is increased being present within the same particle, that is to say the same particulate material. The invention makes it possible, for example, for the composition to absorb in a first wavelength range, in particular in blue and / or UV light, and to re-emit by luminescence in a second wavelength range relatively far from the first, especially in the red, which is not possible with a single fluorophore compound selected from conventionally used compounds.

It is particularly interesting to absorb in the blue and emit in the red, because the skin does not generally gain aesthetically to be illuminated with a light with a dominant blue, while its appearance can be magnified with a light having a dominant red.

The invention can thus make it possible to increase the intensity of luminescence in the red by exploiting the excitation energy of the light incident in the blue. The composition may comprise at least three different fluorophore compounds, as detailed below, at least two of these compounds may have fluorescence absorption and fluorescence excitation spectra located in the visible and also in the visible re-emitting. The first fluorophore compound may have increased luminescence within a first particulate material ie a same particle comprising the metal and the fluorophore. The second fluorophore compound may have increased luminescence within a second particulate material, ie a same particle comprising the metal and the fluorophore. The composition may comprise a third fluorophore compound. The third fluorophore compound may have increased luminescence within a third particulate material ie a same particle comprising the metal and the fluorophore. In the presence of three fluorophore compounds, the latter may be chosen so as to have emission spectra in red, green and blue, respectively, so as to generate additional synthesis of the white or substantially white light. Among these fluorophore compounds, that emitting in the red may further absorb in the green, if appropriate. The one emitting in the green can further absorb in the blue, if any. The emission spectrum of the first fluorophore compound may extend in the range from 580 to 700 rira, preferably with a width at half height of the emission curve of the first fluorophore compound of between 580 and 700 nm.

The emission spectrum of the second fluorophore may range in the range from 480 to 620 nm, preferably with a width at half height of the emission curve of the second fluorophore compound between 480 and 620 nm.

The first fluorophore compound may have an emission curve at mid-height between 580 and 700 nm and an absorption curve. in the visible mid-high between 480 and 620 microns, the second fluorophore compound having an emission curve between mid-height between 480 and 620 uni.

The coverage of the composition is preferably less than or equal to 70%, more preferably 65% or 60%. Thus, the composition is little or not opacifying and the natural appearance of the skin is preserved. The emission spectrum of the composition in the red may have an emission peak which substantially coincides with the maximum peak of sensitivity in the red of the human eye according to the CIE. All fluorophore compounds in the composition may be free of rare earths. The invention further relates, in another of its aspects, to a cosmetic treatment method in which a composition as defined above is applied to the skin. The subject of the invention is also a process for modifying the hue of the skin and / or lightening of the skin, in which a composition as defined above is applied to the skin, the hiding power of the composition being less than or equal to 70 better 65%, even better 60%.

The invention further relates, in another of its aspects, independently or in combination with the foregoing, to a process for lightening the complexion or modulating the hue of the skin, in which a composition is applied to the skin. cosmetic composition comprising at least one particulate material in which a fluorophore has an increased fluorescence, in particular particles having a nanometric metal core and a coating coating the court, this coating comprising at least one fluorescent molecule disposed on the surface of the coating or impregnating it and located at a distance from the metal court sufficiently low to increase its fluorescence. By "hue modulation" is meant a change in the color of the skin by means of a non-opacifying composition, or little opacifying, including coverage of less than or equal to 70%, better 65%, even better 60%. The invention further relates, in another of its aspects, independently or in combination with the above, to a method for increasing the reflectance of the skin in the wavelength range between 600 and 700 nm, comprising 1 step of applying to the skin a cosmetic composition comprising at least two fluorophore compounds F1 and F2 characterized in that the fluorophore compound F1 emits fluorescent light in the visible range such as the normalized emission curve of said fluorophore compound F1 and the relative luminous efficiency curve defined by the CIE overlap each other over the wavelength range between 600 and 700 nm; and in that the absorption curve of the fluorophore F1 and the emission curve of the fluorophore F2 overlap each other under irradiation with natural light. By "normalized curve" is meant a curve brought down to a scale. from 0 to 100%. The invention further relates, in another of its aspects, independently or in combination with the foregoing, to a method for increasing the reflectance of the skin in the wavelength range between 500 and 600 nm, comprising 1 step of applying to the skin a cosmetic composition comprising at least soft fluorophore compounds F3 and F4 characterized in that the fluorophore compound F4 emits fluorescent light in the visible range such as the standard emission curve of the fluorophore compound F4 and the relative luminous efficiency curve defined by the CIE overlap each other over the wavelength range between 500 and 600 nm and that the absorption curve of the fluorophore compound F4 and the curve of emission of the fluorophore compound F3 overlap each other under irradiation with natural light. The invention further relates, in another of its aspects, independently or in combination with the above, to a method for increasing the reflectance of the skin in the wavelength range between 500 and 700 nm, comprising 1 step of applying to the skin a cosmetic composition comprising at least three fluorophore compounds F5, F6 and F7 characterized in that the fluorophore compound F5 emits fluorescent light in the visible range such as the standard emission curve of the fluorophore compound F5 and the relative luminous efficiency curve defined by the CIE overlap each other over the range of wavelengths between 400 and 500 nm; in that the fluorophore F6 emits a fluorescent light in the visible range such that the normalized emission curve of said fluorophore compound F6 and the relative luminous efficiency curve defined by the CIE overlap each other on the domain wavelengths between 500 and 600 nm; in that the fluorophore F7 emits a fluorescent light in the visible range such that the normalized emission curve of the fluorophore F7 and the relative luminous efficiency curve defined by the CIE overlap each other over the range of lengths. wavelength between 600 and 700 nm; in that the absorption curve of the fluorophore F6 and the emission curve of the fluorophore F5 overlap each other and in that the absorption curve of the fluorophore F7 and the emission curve of the fluorophore F6 are cover each other under irradiation with natural light.

Preferably, and in general, in the case of the desired recovery between two spectra, for example as above, an emission spectrum of a fluorophore compound and an absorption spectrum of another fluorophore compound or between a spectrum emission of a fluorophore compound and the relative luminous efficiency curve, the overlap between the curves is such that twice the common area of the two overlapping curves represents at least 20%, 30%, 40%, 50%, 60%, 70% or better 80% of the sum of the areas of each of these curves. This value is referred to as the degree of overlap. The width at mid-height of the common area is for example more than 5 nm wide, even more than 10, 20 or 30 nrn wide. The invention further relates to the cosmetic composition as such, for the implementation of one of the methods defined above. By "visible range" is considered the range from 400 nm to 700 nm. The relative luminous efficiency curve corresponds to the day vision photopic vision curve as defined by the CIE on the site http: llwww.led-fr.netlefficacitelumineuse-rblative.htm, given in FIG. 6. However, this curve can be preferentially replaced for k> 550 nm by the curve CIE R 1964 XYZ CMFs, shown in Figure 7, after normalization. Each of the fluorophore compounds FI to F7 above is preferably enhanced fluorescence within a particulate material, namely the same particle comprising the metal and the fluorophore. Lightening of the skin A composition. according to the invention can be used for lightening the skin, according to implementation examples. The term "skin lightening" should be understood to mean a change in the reflectance of the masked skin relative to the bare skin, so that it is perceived by an observer more clearly, without losing his or her natural appearance. The lightening can be observed if the overall reflectance of the makeup skin is greater than the reflectance of the non-makeup skin. Reflectance of a material means the percentage of light reflected by this material in relation to that observed in the case of a perfectly white reference material and this for each wavelength considered, in accordance with the definition commonly adopted by the man of art. The increase in the reflectance due to the composition implies that the reflectance spectrum of the masked skin has, at least on a spectral window, higher reflectance values than the values observed on the same spectral window in the case of non-porous skin. makeup. This relative increase in reflectance is at least 5%, preferably greater than 10%. Preferably, the composition according to the invention increases the reflectance of the skin in the range 600-700 nm, preferably at least 0.05, more preferably 0.1, on a scale from 0 to 1, for minus one wavelength, and preferably for at least one 20 nm interval. wide, or even 50 nm wide, in this range 600-700 nm. Lightening Measurement Protocol Reflectances can be measured before and after makeup by means of an acquisition device as described in application US 2003/0067545 in FIG. 1, comprising a sphere inside which several white light sources are arranged, which are not visible, so that the light gaining its opening is as homogeneous as possible. The face of the person whose color is to be measured is placed in this opening and images are acquired by means of color cameras or digital cameras, the reflectance spectra being acquired by a spectroradiometer. Prior to the acquisition of the images, the acquisition chain is calibrated by placing reference colorimetric standards in the field of cameras, for example according to the method described in US Pat. No. 6,362,849, the content of which is incorporated herein. request by reference.

The color measurements can be performed for example on three regions of the face, for example a first region located on the forehead, a second region corresponding to the bags under the eyes and a third region between the nose and the lips. The color is measured before makeup on the skin previously cleaned and after makeup, for example 15 minutes after the end of it. For the measurement of lightening, the makeup compositions are applied in the usual manner directly to the skin, without deposition of a base beforehand, at the rate of about 0.5 to 1 mg per cm 2, preferably between 0, 7 and 0.8 mglcrnz. Preferably, the coverage of the composition is not too high, in order to maintain a natural look. Measurement of Coverage Case of liquid compositions at 25 ° C By "liquid composition" is meant a composition whose viscosity can be measured. A liquid composition can flow under the effect of its own weight.

The coverage of the liquid compositions is measured at a finite thickness of 50 μin for the liquid compositions to be applied to the lips, in particular liquid lipsticks, liquid lip glosses and liquid lip balms, for nail polishes and eye shadows. , liquid foundations, mascaras and other liquid make-up products not intended to be applied to the lips.

The composition is spread on matte black and matte white contrast cards, for example LENETA Forais WPI for the matte black card and Leneta 1A for the matte white card. The application can be performed with an automatic spreader. The measurements are carried out on the compositions thus spread.

Solid Compositions (at 25 ° C) Solid compositions are those whose viscosity can not be measured. It may be compositions cast in a stick or powder form, in the form of free or compact powders. a) For powdery, free or compact solid compositions, the composition is applied using the same contrast cards as above, coated with a transparent, slightly rough, eg branded adhesive tape.

BLENDERM & from the company 3M and reference 15025, glued by the adhesive side on the contrast cards. The composition is deposited on the adhesive tape so as to obtain a homogeneous deposition of 0.5 mg / cm 2 ± 0.02 mg / cm 2. It is possible to use to deposit a sponge loaded with the composition and mounted on a disintegrating device that makes predefined movements with the sponge. The sponge is for example a disposable sponge type "1. ANCOME Photogenic", used on the pink side. b) The stick compositions are melted, for example at 90 ° C., and then spread in the liquid state on matt black and matt white contrast cards, for example with the same references as above, not covered with BLENDERM`, The spreading bar is maintained at the same temperature as the composition, so as to avoid thermal shock. The stick compositions are thus deposited once melted with a thickness of 50 μm.

Measurements and calculations Reflectance spectra are acquired using a MINOLTA 3700-d spectrocolorilometer (diffuse / 8 ° measurement geometry and D65 / 10 ° observation, specular component excluded mode, small aperture (CREISS)) on the backgrounds black and white, the contrast cards being optionally covered with BLENDERM® as indicated above. The spectra are expressed in colorimetric coordinates in CIELab76 space within the meaning of the International Commission on Illumination according to Recommendation 15: 2004. The contrast ratio, or coverage, is calculated by averaging Y on a black background, divided by the average value of Y on a white background, multiplied by 100. To preserve the natural appearance of the skin with the cosmetic compositions of the skin. In the invention, the coverage values are preferably less than 70%, more preferably less than 65%, most preferably less than 60%. Choice of emission and absorption spectra FIG. 1 illustrates the overlap between the absorption spectrum A1 of a first fluorophore compound of an example of composition according to the invention and that of emission E2 of another compound fluorophore of the composition, these fluorophore compounds belonging for example both to respective particulate materials comprising a metal interacting with the fluorophore. The recovery of the spectra A1 and E2 may be such that twice the common area represented by the grayed common part, ie the degree of overlap, is at least 20% or more, for example 50%, of the sum of the areas of the spectra AI and E2. In one example, the emission E1 spectrum of the first fluorophore compound is included at mid-height between 580 and 700 min. The absorption spectrum AI is for example between 480 and 600 and the emission spectrum of the second fluorophore compound E2 between 480 and 600 nm. When the composition comprises at least a third fluorophore compound, the emission spectrum E3 thereof may overlap, for example with a degree of overlap greater than 0.2, 0.5 or more, the absorption spectrum AI and the absorption spectrum A3 of the third fluorophore compound can be shifted from the spectrum A2, for example shifted further towards shorter wavelengths, as illustrated in FIG. 2. The emission spectrum E3 can also overlap, for example with a degree of overlap greater than 0.2, 0.5 or more, the absorption spectrum A2, as illustrated in Figure 3. To increase the reflectance of the skin in the wavelength range between 600 and 700 nm, the cosmetic composition may comprise at least two fluorophore compounds F 1 and F 2 characterized in that the fluorophore compound F1 emits fluorescent light in the visible range such as the normalized emission curve of said fluorophore compound F i and the curve of relative luminous efficiency defined by the CIE overlap each other over the wavelength range between 600 and 700 nm for example with a degree of overlap greater than 0.2, 0, 5 or more; and in that the absorption curve of the fluorophore F1 and the emission curve of the fluorophore F2 overlap each other under irradiation with natural light, for example with a degree of overlap greater than 0.2, or even 0.5 or more. By "natural light" is meant a light having the characteristics of the illuminant D65.

To increase the reflectance of the skin in the wavelength range between 500 and 600 nm, the cosmetic composition may comprise at least two fluorophore compounds F3 and F4 characterized in that the fluorophore compound F4 emits a fluorescent light in the field. such that the normalized emission curve of the fluorophore compound F4 and the relative luminous efficiency curve defined by the CIE overlap each other over the range of wavelengths between 500 and 600 nm, for example with a degree of overlap greater than 0.2, 0.5 or more, and in that the absorption curve of the fluorophore compound F4 and the emission curve of the fluorophore F3 overlap each other under irradiation with natural light, for example with a degree of overlap greater than 0.2, or even 0.5 or more. To increase the reflectance of the skin in the wavelength range between 500 and 700 nm, the cosmetic composition may comprise at least three fluorophore compounds F5, F6 and F7, characterized in that the fluorophore compound F5 emits fluorescent light in the visible range such as the normalized emission curve of the fluorophore compound F5 and the relative luminous efficiency curve defined by the CIE overlap each other over the wavelength range between 400 and 500 nm, for example with a degree of overlap greater than 0.2, 0.5 or more; in that the fluorophore F6 emits a fluorescent light in the visible range such that the normalized emission curve of said fluorophore compound F6 and the relative luminous efficiency curve defined by the CIE overlap each other on the domain wavelengths between 500 and 600 nm; in that the fluorophore F7 emits a fluorescent light in the visible range such that the normalized emission curve of the fluorophore F7 and the relative luminous efficiency curve defined by the CIE overlap each other over the range of lengths. wavelength between 600 and 700 nm for example with a degree of overlap greater than 0.2, or even 0.5 or more; in that the absorption curve of the fluorophore F6 and the emission curve of the fluorophore F5 overlap each other and in that the absorption curve of the fluorophore F7 and the emission curve of the fluorophore F6 are cover each other under irradiation with natural light for example with a degree of overlap greater than 0.2, or even 0.5 or more. PARTICULATE MATERIALS COMPRISING AT LEAST ONE LUOROL HO INTERSTEM WITH AT LEAST ONE METAL By fluorophore compound, a fluorescent compound is to be understood. The absorption spectrum of such a compound is that which leads to an excitation giving rise to fluorescence.

The total mass content of fluorophore compounds in the composition according to the invention may range from 0.0001 to 90% by weight. In general, the particulate material may be in the form of particles that may have spherical or platelet fo inc.

The particulate material comprises at least one fluorophore and at least one metal, preferably a noble metal, and has a structure preferably corresponding to structures (1) and (II) described hereinafter. The increased fluorescence refers to the work of R.R. Chance J.Chem. Phys. 1974, 60, 2744 and K.H. Drexhage, J. Lumin. 1970, 1, 693 and according to the invention encompasses the MEF (metal-enhanced fluorescence) fluorescence as described in the publication Meta.1-Enhanced Fluorescence Chris D. Geddes and Joseph R. Lakowicz, Journal of Fluorescence, Vol 12, No. 2, Tune 2002 and the publication Plasmonic Enhancement: Molar Fluorescence NJ Halas, Llano Lett. 2007, 7, 2, 496-501, MEF fluorescence is sometimes sometimes referred to as SPCF (Plasmon coupled fluorescence surface) or by RDE (Radiative decay engineering).

The interaction between the fluorophore and the metal within the particulate material can take place thanks to the sufficiently small distance between the two, for example less than 300 nm, better still 200 nm, even more preferably 100 nm or even 50 nm or 40 nm, or even better between 2 and 30nm. The invention is not limited to the particulate material structures (1) and (II) illustrated below and encompasses the variants of these structures as well as other structures that can implement an amplification, for example a resonance effect. plasmonics. For example, the metal may be directly coated with a layer of a fluorophore compound. The metal and the fluorophore can both be contained in a matrix. A particulate material according to the present invention may also consist of an aggregate of at least two different materials, each of which may include, for example, a metal and a fluorophore interacting with the metal. The metals that can be used to increase the luminescence of the fluorophore include, for example, one or more metals selected from the group consisting of the following metals; aluminum (AI), palladium (Pd), platinum (Pt), silver (Ag), copper (Cu), gold (Au), zinc (Zn) and their alloys. Preferably, the metal of the plasmonic particles selected from the following metals: silver, aluminum, zinc, and gold and their alloys. Alloys of several metals may be stoichiometric or non-stoichiometric. When several metals are used, it may be a continuous phase of metals such as an alloy, that is to say a continuous phase in which the metals are no longer dissociable, or a discontinuous phase of metals. The metal surface may be of various excavations such as spherical, cylindrical, cubic, conical, ovoid, polyhedral, four to ten faces, such as for example a perfect or truncated tetrahedron, a perfect or truncated cube, platelet, in particular elliptical platelet, triangular, pyramidal, polyhedral. It can be smooth or rough. Preferably, the composition according to the invention comprises one or more particulate materials of structure (.1) or (II) as defined below, of average size given by the distribution D; 0 of between 10 nm and 1 micrometer. preferably between 30 and 500 nm. The composition according to the invention may thus comprise, in an exemplary embodiment, particulate materials of structure (1) or (II) in which the porosity of the outer bark is such that the pore size is between 1 and 50 nm and whose specific surface area is greater than 500 m 2 / g. The cosmetic composition may comprise at least three fluorophore and metal materials, preferably each of structure (1) or (II), such that at least three fluorescence emissions in the areas of blue, green and red are produced. to get a white or near white color. F1, F2, F3, F4, F5, F6, F7 described above may each be present within a particulate material structure (I) or (II) as defined below. In general, whatever the structure of the particulate material, the particulate fluorophore compound (s) may be chosen from any of the fluorescent compounds listed below, and more particularly from those listed as part B and in Examples 1 to 14 below. When the composition contains a fluorophore compound, for example in the free state or in a metal-free particulate material, the fluorophore can be any and for example selected from those listed as part B and in Examples 1 to 14. The structure (1) comprises or consists, as illustrated in FIG. 4, of three parts A, B and C, according to a specific organization such that part A is wrapped by part C in a thickness varying from 1 at 100 nm and such that part B is outside part A and inside part C possibly being covalently bonded to chemical functions of part C. Structure (II) comprises or consists, as illustrated in FIG. 5, of four parts D, E, C and B respecting a specific organization such that part D is enveloped by part E in a thickness varying from 1 to 100 nm, the assembly obtained D + E being himself me wrapped by part C to a thickness ranging from 1 to 100 nm and the part B being outside the set D + E and within Part C, being optionally connected to it by covalent bonding. Part A comprises, or even consists of, a metal particle, the metal being selected from group G1 below, whose size is between 3 am and 500 nm along any of the three axes of space , whose shape may be spherical, cylindrical, ovoid, conical, polyhedral, four to ten faces, such as for example a perfect or truncated tetrahedron, a perfect or truncated cube (as described in Y. Xia, Science, 2002, 298, 5601, 2176-2179), a rectangular parallelepiped, an octagonal cylinder (as described as Y. Xia, Angew.Chem.In.Ed., 2009, 48, 60-103), or a perfect or truncated octahedron ( as described in P. Yang, Angew.Chem.In.Ed., 2006, 45, 4597-4601, S. Schultz, J. Chem Phys 116, 15, 6755-6759;). Group G1 consists for example of silver, gold, platinum, copper, aluminum, palladium, zinc, nickel or an alloy thereof. The constitutive particles of part A are preferably selected from the group consisting of silver, gold, zinc, preferably silver, gold, and even more preferably silver. Their shape is preferentially spherical, cylindrical, pyramidal, ovoid; preferentially, spherical or ovoid; and still more preferably spherical. Their size is preferably between 3 nm and 300 nm; preferably between 3 and 160 nm; and even more preferably between 30 and 80 nm in the case of gold, or between 30 and 200 nm in the case of silver. Part B comprises, or even consists of, at least one fluorophore compound chosen independently from the list of the European Cosmetic Directive; 30 the EDA list; the "Fluorescent Whitening Agent, Encyclopedia of Chemical Technoogy", Kirk-Othmer, 4th.11: 227-241, 1994; the G4 group consisting of compounds belonging to the chemical families of xanthenes, benzo [a] xanthenes, benzo [b] xanthenes, benzo [c] xanthenes, coumarins, benzocoumarines, phenoxazines, benzo [a] phenoxazines, benzo [b] phenoxazines , benzo [c] phenoxazines, phenothiazines, benzo [b] thiazines, benzo [c] thiazines, naphthalimides, naphtholactams, lactaminiids, quinacridones, epindolines, thioepindolines, phta.limides, oxazolones, ben.zotriazoles, diphenylmaleimides, dibenzofurans, pyrimidines, triazines, 1,3,5-triazin-2-yl derivatives, pyrazines, triazoles, methines, distyrylbenzenes, distyryl.bi.phenyls, divinylstilbenes, tri.azi.nyla.mi: nosti.lben.es, stilbenyl-2H triazoles, benzoxazoles, benzofurans, benzimidazoles, 1,3-diphenyl-2-pyrazolines, diketopyrrolopyrroles (EP-A-01.33156, US4585878, WO9825927, WO003064558, WO004009710, WO005005571), perylenes, perylenemonoimides, 4,4-d.ifu. oro-4-bora-3a, 4a-diaza-in.dacene. The fluorophners of the family of xanthenes are represented by the formula (F-1) R 7 R 1 R 5 R 4 R 3 where XI represents an oxygen atom; a radical N-Z1, N'Z1Z2 X2 represents a hydroxyl radical; a radical NZ) Z2 Z), Z2, independently of one another, represent a radical chosen from the group Op1 constituted by a hydrogen atom; a linear or branched C1-C8 alkyl, optionally interrupted by one or more oxygen atoms, and optionally substituted with one or more radicals chosen from the group consisting of a radical OR8, a radical NR9R10, a radical carboxy, a radical COOM, a thiol radical, a cyano radical, a halogen, a sulfonic radical, a carboxamido radical CONR9R10, a sulfonamide radical SO2NR9R10; an aryl radical optionally substituted with one or more radicals selected from the group Gp4; a heteroaryl radical optionally substituted with one or more radicals selected from the group Gp4; The Cf-Cs alkyl chain as defined above may be optionally interrupted by one or more oxygen atoms.

Z 1 and Z 2 may form, with the nitrogen atom to which they are attached, a saturated or unsaturated 5- to 7-membered heterocycle, optionally substituted with one or more radicals selected from the group G p 2 consisting of halogen atoms; amino radicals; (di) (C1-C4) alkylamino; hydroxy; carboxy; carboxamido; (C1-C2) alkoxy; C1-C4 alkyl radicals optionally substituted with one or more hydroxyl, amino, (di) alkylamino, alkoxy, carboxy, sulfonyl radicals; the cycle having no peroxide bond, or di.azo or litroso radicals. X1 (respectively X2) may optionally be connected to R6 and / or to R7 (respectively to R1 or R2), to form together a 5- or 6-membered, optionally cationic, saturated or unsaturated carbocycle or heterocycle such as, for example, a cyclohexyl, cyclohexenyl, cyclopentyl, cyclopentenyl, piperidinyl, dehydropiperidinyl, pyrrolidinyl ring, whose anion or mixture of anions is selected from the group consisting of a halide such as chloride, bromide, fluoride, iodide, a hydroxide, a sulfate, a hydrogen sulphate, an alkyl sulphate for which the linear or branched alkyl moiety is C 1 -C 6, such as the methyl sulphate or ethyl sulphate ion; carbonates and hydrogen carbonates; salts of carboxylic acids such as formate, acetate, citrate, tartrate, oxalate; the alkylsulphonates for which the linear or branched alkyl part is C 1 -C 6 6 such as the methylsulphonate ion; arylsulphonates for which the aryl part, preferably phenyl, is optionally substituted by one or more C1-C4 alkyl radicals such as, for example, 4-tolylsulphonate. R1, R2, R3, R5, R6, R7, which may be identical or different, represent a radical chosen from the group Gp3 consisting of a hydrogen atom; a halogen, a C 1 -C 4 alkyl optionally substituted by one or more radicals selected from the group consisting of a radical OR 8, a radical SR 8, a radical NR 9 R 10, a carboxy radical, a sulfonic radical, a carboxamido radical CONR 9 R 10, a sulfonamido radical SO2NR9R1a; a carboxy radical; a cyano radical, a carboxamido radical (RCONH-); a (C1-C4) alkylsulphonyl radical (SO2R); an alkylsulphonamido (C 1 -C 4 alkyl) SO 3 NH-) radical; a sulfonic radical (-SOSH); a C1-C4 thioether radical; a (C1-C4) alkylsulfoxide (-SOR) radical; an aminosulfonyl radical (NH 2 -SO 2 -); a hydroxy radical; a C1-C4 alkoxy radical; a thioether radical; a C2-C4 hydroxyalkoxy radical; NR13R14 radical; an aryl radical optionally substituted with one or more radicals selected from the group Gp4; a heteroaryl radical optionally substituted with one or more radicals selected from the group Gp4; a cationic aza-heteroaryl radical optionally substituted with one or more radicals chosen from the group Gp4 R5 and R6, may form a 6-membered saturated or unsaturated carbocycle or heterocycle optionally substituted by one or more radicals selected from the group Cpt. R4 represents a hydrogen radical, halogen; cyano; trifluoromethyl; straight or branched C1-C8 alkyl; linear or branched C2-C8 akenyl; linear or branched C2-C8 alkynyl; aryl optionally substituted with one or more radicals selected from the group Gp4; heteroaryl optionally substituted with one or more radicals selected from the group Gp4; naphthyl optionally substituted with one or more radicals selected from the group Gp4; R8, R9 and R10, which may be identical or different, represent a hydrogen atom; linear or branched C1-C4 alkyl radical optionally substituted by one or more radicals selected from the group consisting of a hydroxy, a C1-C2 alkoxy, a carboxamido CONR11R12, a sulfonyl SO2R1 ,. R1I and R12, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C4 alkyl radical optionally substituted with one or more hydroxy or C1-C2 alkoxy; The group Gp4 consists of a halogen; cyano; hydroxy; C1-C4 alkoxy; carboxy; Carboxamido; (C1-C4) alkylsulphonyl (-SO2alkyl) optionally substituted with a sulfonic group (-SO3H); a sulfonate S03M 'where M' represents a lithium, sodium or potassium ion, sulfate (-OSO3H); alkylsulfoxide (-SO-alkyl); alkylsulfonamido (alkyl (CIC4I) SO2N .-); N13R14 nitro; optionally substituted phenyl; C1-C4 alkyl optionally substituted with one or more radicals chosen from hydroxyl, C1-C4 alkoxy, carboxy, carboxanlido, (C1-C4) alkylsulphonyl, sulphonic, alkylsulphoxide, alkylsulphonamido or N.R13RI4 radicals; and optionally their salts, and their solvates. Ru and R14 represent, independently of one another, a radical selected from the group IO Op '. They can form with the nitrogen atom which carries them a 5- to 7-membered ring. M represents a lithium, sodium, potassium, calcium, magnesium, ammonium cation, mono-, di-, tri- or tetrasubstituted by a C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl. The particular compounds of the formula (F-I) may in certain cases be represented by their isomeric forms according to the formula (F-F), where n represents an integer of 0 to 4. R7 R9 R7 RI o R5 Where

The fluorophores of the benzo [b] xanthenes and benzo [e] xanthenes family are represented respectively by formulas (F-11) and (F-1 '). R7 R6 R5 R4 R3 (F-11) (F-III) and their isomeric forms in a representation. Analogous to that of (FI) (FI), for example, these isomeric alkenes are represented by the following formulas: Ar HetAr HX HX1 Preferred Compounds of the Formula (-I): 3 Et ._._ And 0 D OH ~ + ~ And ~ N \ 4 N Etz Ô And ~ N \ N Etx CO H CQ H co, H zz COOH Fluorescein Rhodamine B SQ - SQ, - NH, SQ, H SQ, - me 50 - sq • H 3 NHieo \ ## EQU1 ##, ## STR4 ##, ## STR2 ##, ## STR1 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## , 1 -11 "- And SO, - Cl Cl Br Br 00 O 1OH 1". Cl CF MeO Br ~ CO2H ~ CoaH CO211 HO2C HOOC "L OH 0 Ô OH CO, HI CO, H COOH HOOC ## EQU1 ## - 1 ", NEt., Cl- SO, Er '" 021-1 SO2NHu (CH2) - COOH Solvent Orange 63 c- The fluorophores of the family of coumarins are respectively represented by the formulas (F-11l) FIELD [400 m-500 I. 2 R R4 R3 (F-III) where Ris is defined by the same radicals as ILr. X 'represents a hydroxy radical; a C1-C2 alkoxy radical; a radical NZ1Z2 with the proviso that Z1 and Z2 do not together represent a hydrogen atom. X'2 and R2 together may optionally form a 5- or 6-membered ring optionally unsaturated and optionally substituted with a radical of the group Gp3. Preferred Compounds of the Formula (F-III): ## STR2 ## ## STR2 ## where ###################################################### ## EQU1 ## ); ## STR1 ## wherein An- denotes a cosmetically acceptable anion. The fluorophores of the families of pheoxoxides, benzo [b] phenoxazines, henzo [c] phenoxazines and phenothiazines, henzo-pththiazoles, henzo [c] thiazines are respectively represented by the formulas (i - IV), (IV) , (F-III) and (F-VII), (F-VIII), (F-IX) R5 R3 R5 R3 (FV; X3-O) (F-VI; X3 = O) (F-VIII; X3) = S) (F-IX; X3 = S) R1 R7 R7 R1 R5 (F-IV; X3 = O) (F-VII; X3 = S) Preferred compounds of the formula (F-IV) and (F The fluorophores of the family of naphthalimides are represented by the formula (FX) 27 (R ') R7 R6 (FX) where R7 is a radical. radical. selected from the group Gp4 R'3 and R'5 represent radicals as defined by R3 and R5, and may optionally form a lactamic ring whose nitrogen atom is optionally substituted with a Z group; r represents an integer from 0 to 5. Preferred compounds of the formula (FX): () Me SO2CII, CH, QSO3H Me Me: 1 yY -Me o O IN NU, NU, 15 f- Fluorophores of the family naphtholactams are represented by the formula (F-XI) (F-XI) wherein X4 represents a radical as defined by XI; a heterocyclic radical; a C1-C4 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C1-C4 alkoxy and cyano radicals; carboxy, carboxamido, (C1-C4) alkylsulfonyl, sulfonic acid, alkylsulfoxide, alkylsulfonamid; aryl optionally substituted with one or more radicals selected from the group Gp4; a heteroaryl radical optionally substituted with one or more radicals selected from the group Gp4; The preferred compounds of the formula (F-XI): ## STR1 ## where R 9 and R 10 denote, independently of one another, a hydrogen atom, a C 1 -C 8 alkyl or a C1-C6 alkoxy radical. The fluorochemides of the lactamimide family are represented by the formula (F-XII) 4Ra (F-XII) wherein R [6 and RI7 represent radicals as defined by the radical R1; 20 m and p represent an integer between 0 and 2. g The fluorophores of the family of quinacridone, epi Joli e and thio-epi doline are respectively represented by the formulas (F-XIII), (F-XIV) and ( F-XV) R ~3y R3 R18 Y7 R5 (-XIII) X5 = N-Z1 (F-XIV) X5 = O (F-XV) X5 = S where X5 represents an oxygen atom, sulfur atom or a group h; -Z1 R18, R19, R20, and R21 represent radicals as defined by the radical RI. Compounds derived from quinacridone which can emit white are described in WO04039805. The fluorophores of the phthalide family are preferably represented by the formula (F-V), wherein the fluorophores of the oxazolone family are preferably represented by the formula (F-V). XVI) R23 (R22) q2) s (F-XVI) where R22 and R23 represent, independently of one another, a radical selected from the group Gp4. s represents an integer between 0 and 5. The fluorophores of the family of benzotriazoles are described in publications WO03105538 and EP2004053111. The fuuropholes of the family of pyrimidines, triazines, triazoles, pyrazines, dibenzofurans are described in publications WO04039786, EP2004050146, WO05023960, EP2004052984, EP2005051731, EP05103497, EP05104599. I-fluorophores of the family of stylbens are represented by the formula (F-XVII) R 7 R 38 (F-X VII) where i represents an integer equal to 0 or 1; k represents an integer equal to 1 or 2; A, b and c represent an integer equal to 0 or 1 and such that (a, b, c, k) = (0,0,1,1); (0,0,0,2), (1,0,0,1), (1,0,0,2), (1,1,0,2), or (1,1,1,1) . R34 and A2 represents an aryl radical optionally substituted with one or more radicals selected from the group Gp5; an aromatic heterocycle radical optionally substituted with one or more radicals chosen from the group Gp5; a cationic aromatic heterocycle radical optionally substituted with one or more radicals selected from the group Gp5; The group Gp5 is constituted by a hydrogen atom; a linear or branched C1-C4 alkyl optionally substituted by one or more radicals selected from the group consisting of a radical OR5, SR8, NR9R10, carboxy, sulfonic acid, carboxamido CONROR10, sulfonamido SO2NR9RI0; a radical -CH = CH-CN; a radical --CH 2 CH 2 CO 2: R 8; a radical ûCHûCH-Ar where Ar represents an aryl group optionally substituted by a nitrile; a carboxy radical; a C1-C3 alkoxycarbonyl radical; a cyano radical; a halogen radical; a carboxamido radical (RCONH-); a (C1-C4) alkylsulphonyl radical (SO2R); an alkylsulphonamido radical (C1-C4 alkyl) SO2N1-I-); a sulphonic radical (-SO3H); a sulphonate radical (-SO3M, where M represents a sodium, potassium, lithium ion); a C1-C4 thioether radical; a (C1-C4) alkylsulfoxide (-SOR) radical; an aminosulfonyl radical (NH 2 -SO 2 -); a hydroxy radical; a C1-C4 alkoxy radical; a C2-C4 hydroxyalkoxy radical; an NR30R40 radical; an aryl radical optionally substituted with one or more radicals selected from the group Gp4; a heteroaryl radical such as 1,2,3-triazole, 1,2,4-triazole, benzotriazole, be.nzoxazole, pyrazole, pyrazoline, pyrazolidine, indazole, imidazole, pyrrole, indole, pyrrolidine, indoline, oxadiazole, said radical being optionally substituted with one or more radicals selected from the group Gp4.

R39 and R40 represent, independently of one another, a radical selected from the group Gp, and in particular a triazinyl group optionally substituted with a radical selected from the group Opo consisting of a C1-C4 alkoxy radical; NR41R42; C1-C4 alkyl optionally substituted with one or more radicals selected from hydroxy, C1-C4 alkoxy, carboxy, carboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkylsulfoxide, alkylsulphonamido or NR43R44; R39 and R40 may together form a 5- or 7-membered carbocycle or heterocycle with the nitrogen atom carrying them.

R41, R42, R43 and R44 represent, independently of one another, a radical selected from the group Gp 1. R 41 and R 42, on the one hand, R 43 and R 44, on the other hand, can together form a 5 to 7-membered carbocycle or heterocycle with the nitrogen atom carrying them such as, but not limited to, a pyrrolidine ring, morpholine, thi.omorphohine. R35, Rat, R37 and R38 represent, independently of one another, a hydrogen radical; C 3 -C 4 alkyl optionally substituted with one or more radicals selected from the group consisting of an ORs radical, a carboxy radical, a sulfonic radical and the carbon chain of which may optionally be interrupted by one or more oxygen atoms; ; cyano. R.35 and R34 (in the case where i = 1) or R35 and R37 (where i = O) may be joined together to form a 5-membered heterocycle selected from furan, thiophene, pyrrole; a carbocyclic G or 10 member selected from aryl, naphthyl. R34 and R37 may together be joined to form a heterocycle selected from benzofuran, benzothiophene, indole, azaindole. L represents a linear or branched C 2 -C 10 alkyl radical, the carbon chain of which may optionally be interrupted by at least one oxygen atom, optionally substituted with a C 2 -C 6 alkoxy radical; the (di) alkyl- (C2-C8) amino radicals, R34 and A2 preferably represent, independently of one another, a phenyl, naphthyl, pyridine, pyrimidine, imidazole, pyrazole, pyrrole, triazole or benzoxazole radical, Benzimidazole, indole, azaindole, oxazolium, thiazolium, pyridinium, pyrimidinium, imidazolium, benzimidazolium, pyrazolium, pyrrolium, triazolium, oxazolium, thiazolium. Preferably, mention may be made of the derivatives of styrylstilbene, triazinostilene, hydroxycoumarin, aminocoumarin, oxazole, benzoxazole, iniidazole, triazole, pyrazoline, pyrene and porphyrin. The following compounds preferentially but nonlimitingly illustrate this family: R 2, R 2, CN (Position) (2,3), (2,4), (3,3), (3,4), (4,4). (R24, R25) (SO3Na (3), C1 (4) (OMe (2), II) i (SO3Na (2), H) NHPh X28 R2, R26 Rzs HR, where N SO, Na R7a NHPh N2 R27 NN-N R27 NN SQ, NaNN N NaSO, NH4SO4, R26 OMe, NHMe, NHEt, NH-CH2-R27 R28 R29 (position) CH20H, NH (CH3) (CH2-CH2) -OH), N (position) morpholinyl, NHPh, NH-CH2-CH2OH SO3Na (3) H N- (CH2-CH2OH) 2 SO3Na (3) H N- (CH2-CIF20H2 SO3Na (4) H N- ( CH 2 -CH 2 OH) 2 SO 3 Na (2) SO 3 Na (5) N-SO 3 Na (4) H (CH 2 CH (OF-1) CH 3 SO 3 Na (4) H) 2 SO 3 Na (2) SO 3 Na (5) N (CH 3) (CH 2 CH 2 SO 3 Na (2) SO3Na (5) OH) SO3Na (4) H N2 N-morpholinyl N (CH2CO2Na) 2 II 50, M, n SO, M. M = SO, M, SO, MI = Na, K (R30, R31) = (Me, COOMe) (H, m, ethyl oxalidazole) R32! ## STR1 ## ## STR1 ## wherein Y + N + MeCO2 + OCO2N MeO2 + MeO + MeO N ## STR2 ## ## STR1 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## t (CH 2 CH 2 OH) -N-Na and (C 2 H 2 CH 2 OH) Amin -NH-S 2 COQNa Ami -N 1 to -N + NaOH. Me (CH 2 CH 2 OH) Me CH 2 CH 2 OH) -N-Morpholino amine no. j _. . -N-mute gb6ilo 1 Na Amine -NM wCH-. k-NMyCH2- ~ _ COONa Amino COONa Na _ ~. A illol -NH- Am i no -Na-. CH 2 CH 2 CH 2 OH (NH 2 CH 2 OH) 2 (CH 2 CH 2 OH) 2 -N- / 20Aÿ -NH -NH- -NH- -N / -Na (CH 2 CH 2 OH) (CH 2 CH 2 OH (CH 2 CH 2 OH) (CH 2 CH 2 OH). (CH 2 CH 2 OH) -N, N-methylbiphenyl) (CH 2 CH 2 OH) -N-methyl-amino-NH 4 -alkylamino H2CH2COON Na (H2CH2CO2Na) a) Amitol -NH-Amine -N1-Na (CH2CH2OH) (CH2CH2OH) Amino-N-morpliolino Amino (CH, CH2OMe) Na N11-Amino-N-morpholino Amino (CH2CH2H) Na CH2- The following fluorophores are also preferred: ~ O, H ~ I 1 SOgHf ~ NNN S0, H ~ -J SO3H sO, H. C.1. Direct Yellow 96 Disperse Yellow 77 Ciba Lake O, CH, CH (CH2), CO2CH2CH (CH3), Solvent Green Fluorol 242 N 112 ZnCl 2 SC2CH2CH2SO3Na C1- (CH2) 2-NH HCO CH2-CHMe -N + HM e2, CH3CH (OH) COOEH c (HH - (CH2) ~ CONH-. (CH 2) 3-NHMe 2, Cl - (CH 2) 2 -R-CHMe-CH 2 -HHN-HMe 2, Cl-HH NH- (CH 2) 3 -N + Me 3, CH 3 SO 3 -HH 1 -Me 2 (C 2 H 2 CH 2 H The preferred compounds for B are: - DC Orange No. 4: Sodium 4 - [(2-hydroxy-1-naphthyl) azo] benzenesulphonate DC Red # 31: Calcium bis [3-hydroxy-4- ( phenylazo) -2-naphthoate-DC Red # 6 and DC Red 7 (DC Red 6 Ca salt): Disodium 3-hydroxy-4 - [(4-methyl-2-splphon atophenyl) azo] -2-naphthoate - DC Red No. 34: Calcium 3-hydroxy-4 - [(1-sulphonato-2-naphthyl) azo] -2-naphthoate - FDC Yellow No. 6: Disodium 6-hydroxy-5 - [(3-sulphonatopl) ] enyl) azo] naphthalene-2-sulphonate - FOC Red No. 40: - Disodium 6-hydroxy-5 - [(2-methoxy-4-sulphonato-m-tolyl) azo] naphthalene-2-sulphonate DC Red No. 33: Di-sodium 5-ammino-4-hydroxy-3- (phenylazo) naphtho-2,7-disulphonate FDC Yellow No. 5: Trisodium 5-hydroxy-1- (4-sulphophenyl) 4 - (4-sulphophenylazo) pyrazole-3-carboxylate - DC Red No. 17: 1- (4- (phenylazo) phenylazo) -2-naphthol - FDC Green No. 3: Dihydrogen (ethyl) [4-] [4- [ethyl (3-s uiphonatobenzyl) amino] (4-hydroxy-2-sulphonatobenzhydrylidene) cyclohexa-2,5-di-en-1-ylidene] (3-sulphonatobenzyl) ammonium disodium - FDC Blue No. 1: Dihydrogen (ethyl) 4- [4- [ethyl (3-sulphonatobenzyl)] ammino] -2'-sulphonatobenzhydryli. dene] cyclohexa-2,5-dien-1-ylidene] (3-sulphonatobenzyl) ammonium, disodium - DC Yellow No. 7 and 8: Disodium 2- (3-oxo-6-oxidoxanthen-9-yl) benzoate DC Orange No.5: 2- (4,5-Dibromo-6-oxido-3-oxoxanthen-9-yl) disodium benzoate - DC Red No. 21: 2- (2,4,5,7-tetrabromo- 6-oxido-3-oxoxanthen-9-yl) benzoic acid - DC Red No. 22: Disodium. 2- (2,4,5,7-Tetrabromo-6-oxido-3-oxoxanthen-9-yl) benzoate - DC Red No. 27: 3,4,5,6-tetrachloro-2- (1,4 , 5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl) benzoic acid - DC Red No. 28: 3,4,5,6-tetrachloro-2- (1,4,5,8-tetrabromide) Sodium 6-hydroxy-3-oxoxanthen-9-yl) benzoate. - DC Yellow No. 11: 1,3-isobenzofurandione, reaction product with methylquinoline and quinoline DC Yellow No. 10: 1H-Indene-1,3 (2H) -dione, 2- (2-quinolinyl) -, sulfonated, sodium salas - DC Green No. 8: Trisodium 8-hydroxypyrene-1,3,6-trisulphonate - DC Violet No. 2: 1-hydroxy-4- (p-toluidino) anthraquinone - DC, Purple No. 2: Sodium 4 - [(9,10-dihydro-4-hydroxy-9,10-dioxo -] anthryl) friend. DC Green No. 1,4-his (p-tolylarnino) anthraquinone - DC Green no. 5: Disodium 2,2 '- (9,10-dioxoanthracene-1,4-diyldiimino) bis (5- meth ylsu.lphonate) - DC Red # 30: 6-chloro-2- (6-chloro-4-methyl-3-oxobenzo [b] thien-2 (3H) -ylidene) -4-methylbenzo [b] thiophen. e-3 (2H) -one - Carminic acid 4,4'-bis [(4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino] stilbene-2 Disodium 2'-disulphonate Butyl 4- ({4- {[4- (butoxycarbonyl) phenyl] amino} -6 - [(3- {1,3,323-tetramethy-1-yl) [(triniethylsilyl) oxy] ] disiloxa.nyl} propyl) amino] -1,3,5-triazin-2, -yl} amino) benzoate - Methyl chloride 1-methyl-4 - [(methylphenylhydrazono) methyl] pyridinium sulphate 2- [ [4- (dimethylamino) phenyl] azo] -1,3-dimethyl-1H-imidazolium chloride (1E) -1- {4- [bis (2-hydroxyethyl) amino] benzylidene} -2,3 1-Dihydro-1H-indolizinium 15-Berberi.ne - Trisodiurn-2,7-bis-2- (5-hydroxy-1- (4-sulphophenyl) -4- (4-sulphophenylazo) pyrazole-3-carboxylate carboxyethyl) -5-carboxyfluorescein (BDECF) Rhod-2, sorting potassium 20 - Cascade Blue, trisodium - Cascade Yellow - 7-hydroxy-4-methylcoumari: ne - 5-ROX, 1 - [[[2 ', 3', 6`, 7 ', 12,13', 16 17'-octahydro-3-oxospiro [isobenzofuran-1 (3H), 9 '- [111., 514., 9H, 11R, 15H.] Xantheno [2,3,4-ij: 5,6, 7-i'j 'diquinolizin] -5 (or 6) -yl] carboxylic acid 25 - CY-3 cyanine

Benzophenone-1 (UVINUL 400); Benzophenone-2 (UVINUL D-50); Benzophenone-3 (UVINUL M-40); Benzophenone-4 (UVINUL MS-40); Benzophenone-8 (SPECTRA SORS UV, 24); Methoxycinnarnate (BERNEL HYDRO); Ethyl dihydroxypropyl-PABA 30 (AMERSCREEN P); Glyceryl PABA (NIPA GMPA); Homosalate (KEMESTER HMS); Methyl anthranilate (SUNAROME UVA); Octocrylene (UVINUL N-539); Octyl dimethyl PABA (PABA); Octyl dimethoxycinnamate (PARSIL MCX); Octyl salicylate (SUNAROME WMO); p-Amino benzoic acid (PABA); 2-phenylbenzirnidazole-5-sulphonic acid (EUSOLEX 232); Triethanolamine salicylate (SUNAROME W) °. 3- (4-methylbenzylidene) camphor (UNSOLEX 6300); Benzophenone-6 (UVINUL D-49). Benzophenone-12 (UVINUL 408); 4-isopropyldibenzoylmethane (EUSOLEX 8020); Butyl methoxydibenzoylmethane (PAR.SOI.J 789); Etocrylene (UVINUL N-35).

TINOPAL OB (Ciba, 2,5-thiophencdiylbis (5-tert-butyl-1,3-benzoxazole) -TINOPAL ABP-Z (CIBA), TINOPAL NFW-TINOPAL CBS-X (CIBA, 2,2 '- ([ Sodium 1,1'-biphenyl] -4,4'-diyldivinylen (e) bis (benzenesulfonate); TINOPAL DMA-X (Ciba, 4,4'-bis [(4-anilino-6-morpholino)] Disodium 3,5-triazin-2-yl) amino] stilbene-2,2'-disulphonate - TINOPAL MSP (Ciba, 2,2 '- [vinylenebis [(3-sulfonato-4,1-phenylene) imino] hexamethyl-1,3,5-triazine-4,2-diyl) imino]] bis (benzene-1,4-disulfonate), TINOPAL NP Slurry (CIBA), TINOPAL SFP (CIBA, 2,2 [Vinylenebis [(3-sulfonato-4,1-phenylene) imino] (6- diethylamino) -1,3,5-triazine-4,2-diyl) imino] bis (benzene-1) Hexasodium 4-disulphonate) - XYMARA Marker Blue SF2A (CIBA) - UVITEX NFW (CIBA, 4,4'bis (2-sulphostyryl) - biphenyl disodium) - UVITEX OB (CIBA, 2, 5-thiophenediylbis (5-tert-butyl-1,3-benzoxazole);

LEUCOPHOR BSB (CLARIANT); HOSTALUX ETBN (CLARIANT); LEUCOPHOR PC (CLARIANT); LEUCOPHOR N (CLARIANT); LEUCOPHOR UO (CLAMANT); LEUCOPHOR FTS (CLARIANT); LEUCOPHOR SAC (CLARIANT); LEUCOPHOR A. (CLARIANT); ; LEUCOPHOR. VW (CLARIANT); LEUCOPHOR LS (CLARIANT).

More preferably: TINOPAL CBS-X (CIBA, 2,2 '- ([1,1'-biphenyl] -4,4'-diyldivinyiene) bis (benzenesulfonate) sodium; TINOPAL DMA-X (CIRA, 4,4-bis [(4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino] stilbene-2,2'-disodium disulphonate - UVITEX OB (CIBA, 2,5-thiophenediylibis (5-tert-butyl-1,3-benzoxazole) - DC Red No. 33: Disodium 5-amino-4-hydroxy-3 - (phenylazo) naphthalene-2 , 7-disulphonate - FDC Green No. 3: Dihydrogen (ethyl) [4- [4- [ethyl (3-sulphonatobenzyl) amino] [4-hydroxy-2-sulphonatobenzhydrylidene] cyclohexa-2,5-dien-1 -ylidene] (3-sulphonatobenzyl) ammonium, disodium - DC Red # 28: 3,4,5,6-tetrachloro-2- (1,4,5,8-tetrabron) o-6-hydroxy-3-oxoxanthen -9-yl) sodium benzoate 1.0 DC Yellow No. 7 and 8: Disodium 2- (3-oxo-6-oxidoxanthen-9-yl) benzoate - Butyl 4 - ({4 - {[4- (butoxycarbonyl) ) phenyl] amino} -6 - [(3- {1,3,3,3-tetramethyl-1- [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -1,3,5-triazin-2-yl} amino) benzoate 5-Hydroxy-1- (4-sulphophenyl) -4- (4-sulphophenylazo) pyrazole-3-carboxylic acid trisodium-2,7-bis- (2-carboxyethyl) -5-carboxyfluorescein (BDECF ) - Rhod-2, tripotassium - Cascade Blue, trisodium - Cascade Yellow - 7-hydroxy-4-methyl-quinoline 20 - Trisodium-5-hydroxy-1- (4-sulphophenyl) -4- (4-sulphophenylazo) pyrazole-3-carboxylate - 1., e 5-R OX, 1 - [[[2 ', 3', 6 ', 7', 12 ', 13', 16 ', 17'-octahydro-3-oxospiro [isobenzofuran-1 (3H), 9' - [11] 1, 511, 9H, 1111, 15H] xantheno [2,3,4-ij: 5,6,7-i'j '] diqu.inolizin] -5 (or 6) -yl] carboxylic acid - CY- 3 cyanine 25 And even more preferred:

7-hydroxy-4-methyicoumarin Trisodium-5-hydroxy-1- (4-sulphophenyl) -4- (4-sulphophenylazo) pyrazole-3-carboxylate - DC Red No. 33: Disodium 5-amino-4 -hydroxy-3- (phenylazo) naphthalene-2,7-disulphonate TINOPAL CBS-X (Ciba, 2,2 ([1,1 'biphenyl-44' diyldivinylene) bis (benzenesulfonate) sodium); TINOPAL DMA-X (Ciba, 4,4'-bis [(4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino] stilbene-2,2-disulphonate Disodicm Part C comprises or is constituted by at least one organic macromolecular compound or organic compound chosen independently in the G2 group or the G3 group and with a molar mass ranging from 5 × 10 g / mol to 10 g / mol. consists of biocompatible compounds, biodegradable compounds, lipids, polysaccharides, proteins, glycoproteins, glycolipids, neutral or charged lipids selected from group H1 consisting of fatty alcohols containing at least 10 chain carbons. linear or branched, such as polyethylene glycol (PEG), fatty acids containing at least 10 carbons in straight or branched chain, lecithin, sphingolipids, fatty amines containing at least 10 carbons in straight or branched chain, polyesters; polyamides, polyethers polyoxyethylene-9-lauryl-1-ether; polythioethers; polyureas; polycarbonates; polycarbamides; polyaryls; polysilicones selected from the group consisting of polydimethylsiloxanes (PDMS), phenyl polyorganosiloxanes such as plienyltrimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenylmethyldimethyltrisiloxanes, diphenyldiniethicones, phenyldinnethicones and pol.ymethylphenylsiloxanes, which can be fluorinated; polysiloxanes modified with fatty acids, with fatty alcohols or with polyoxyalkylenes, fluorosilicones and perfluorinated silicone oils, and mixtures thereof; silicone volatile oils such as cyclic or linear silicones, preferably with a viscosity at room temperature and at atmospheric pressure of less than 8 mm.sup.2 / s (8 cSt), and in particular having 2 to 7 silicon atoms (Preferably, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexadecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane or heptamethyloctyltrisiloxane). Group G3 consists of metal oxides of valence ranging from 1 to 6, the metal part consisting of metal elements selected from the group consisting of metals of titanium, iron, copper, zinc, zirconium, strontium, indium, silicon , tin, telerium, niobium, bismuth, cerium, ytrium, or their alloy, such as TiO 2, Fe 2 O 3, CuO, ZnO, Y 2 O 3, ZrO 2, In 2 O 3, SiO 2, SnO 2, Ta 2 O 5, Bi 2 O 3, CeO 2, SrO 2, Sixoxy x and y independently comprised between 0.1 and 2. Part C is preferably composed of metal oxide such that, without being limiting, SixOy x and y independently from 0.1 to 2, TiO 2 titanium oxides, SiO 2 silicas, zirconium oxide ZrO2, Fe203 iron oxides; polysilicones such as polydimethylsiloxanes (PDMS), phenyl polyorganosiloxanes; polyethylene glycol (PEG), poly (vinyl) pyrrolidinone PVP; polyacrylates such as for example PMM..A. ; polystyrenes PS, polyureas; Preferably, C is composed of PMMA, PVP, PS, metal oxides selected from Si 3 O x and independently from 0.1 to 2, TiO 2 titanium oxides, SiO 2 silicas; Preferably, C is composed of metal oxides chosen from SixOy silicon oxides, SiO2 silicas, preferably SiO2 silicas. The thickness of the shells C of the structure (I) or (II) is preferably between 2 and 80 nm, preferably between 10 and 50 nm, preferably between 20 and 30 nm. Part D comprises, or even consists of, at least one organic or semi-organic polymeric compound independently selected from groups G2 and G3; whose shape may be spherical and of diameter ranging from 20 to 250 nm, or cylindrical whose minor axis varies from 5 to 50 nm and the major axis from 20 to 250 nm (see N. Halas, ACES Nano, 2009, 3 (3), 744-752). Part D is preferably composed of metal oxide such as, but not limited to, silicon oxides, Si, Oy x and y independently from 0.1 to 2, SiO 2 silicas, Fe 2 O 3 iron oxides; polyacrylates such as, for example, PMMA; polystyrenes PS, polyureas. Preferably, part D consists of PMMA, PS, metal oxides chosen from SixOy x and independently between 0.1 and 2, SiO2 silicas.

Preferably, part D consists of metal oxides chosen from silicon oxides Si3Oy and silicas SiO2; and more preferentially SiO2 silicas. Part E comprises or is constituted by a metal selected from group G1. Part E is preferably selected from the group consisting of silver, gold metals; more preferably gold. Methods of Obtaining An Example of a Process for Obtaining a Particulate Material of Structure (1) Above, may comprise the steps of firstly mixing a precursor of Part C with a dispersion of Part A to obtain hybrid particles A + C, in a second time to disperse these particles A + C in a solution or suspension containing at least one fluorophore compound of part B, then in a third time to isolate the final material if necessary. An exemplary method for obtaining a particulate material of structure (II) above may comprise the steps of first mixing a precursor of Part E with a dispersion of Part D to obtain hybrid particles. D + E after isolation, in a second time to disperse these particles D + E in a solution or suspension containing a precursor of part C to obtain the particles D + E + C after isolation, in a third time to disperse these particles D - ± E + C in a solution or suspension containing at least one luminescent compound of part B, then in a fourth step possibly to isolate the final material.

In a general manner, the fluorophore compound (s) according to the invention may be chosen from the list a) to 1) above, independently of the implementation according to structures (1) or (II) above. above. CALENSE FORMS A composition according to the invention can be solid or fluid. Within the meaning of the invention, the term "solid" means a composition of high consistency, which retains its shape during stating. In contrast to so-called "fluid" compositions, it does not flow under its own weight.

According to a first variant embodiment, a composition according to the invention is presented. in solid form, and more particularly in the form of a compact powder or a cast product. By "compact powder" is meant a mass of product whose cohesion is associated at least in part with compaction during manufacture. By "cast product" is meant a mass of product whose cohesion is ensured by solidification of at least one of its constituents during the implementation. The composition may be hot cast in a mold, and the solidification results from its cooling.

A cast product according to the invention may be in anhydrous form or in the form of a solid emulsion. A solid emulsion does not flow under its own weight at room temperature, as opposed to a conventional emulsion, and is characterized in particular by the presence of wax (es) in the liquid fatty phase. According to another variant embodiment, a composition according to the invention may be in fluid (liquid) form, more or less viscous, of creamy or pasty appearance, such as, for example, in the form of an oily or aqueous solution, an oily gel, an oil-in-water, water-in-oil or multiple emulsion. A composition according to the invention must be cosmetically or dermatologically acceptable, namely to contain a non-toxic medium that can be applied to keratinous substances of human beings, in particular on the skin. By cosmetically acceptable is meant in the sense of the invention a composition of appearance, smell and pleasant touch. The medium is generally adapted to the appearance under which the composition is to be packaged. In particular, the nature and the content of the various compounds are adapted, for example, depending on whether the composition is formulated in solid or fluid form. The composition according to the invention may be in the form of a composition for makeup and / or care of keratin materials, for example a blush, an eyeshadow, a powder for the face, a foundation, in particular to be applied to the face or the cot, a concealer, a concealer, a tinted cream, a lipstick, a lip balm, a composition for the colored care or make-up of the skin, in particular the face or the skin. body.

Those skilled in the art will choose the appropriate dosage form, especially from the fluid or solid forms suitable for topical application on keratinous substances, especially on the skin. In particular, a composition according to the invention may be in the form of a fluid, for example pasty or liquid, a gel, a cream, or in the form of loose or compact powder, or a product sank. For example, it may be an oil-in-water, water-in-oil or multiple emulsion, a solid emulsion, especially of water-in-oil type, an aqueous or oily gel, a compact or free powder or a cast product, in particular under a anhydrous form or in the form of a solid emulsion.

The composition may be packaged in a packaging and applicator device comprising an applicator, the application surface being defined for example by a brush, a sponge, a foam, a flocked membrane, a felt or a nonwoven. The composition may be applied by spraying or transfer, as appropriate. aqueous phase A composition according to the invention may comprise an aqueous phase. The aqueous phase comprises water. 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 and / or thermal water. The aqueous phase may also comprise water-miscible organic solvents (at ambient temperature -25 ° C.), for example monoalcohols having from 2 to 6 carbon atoms, such as ethanol or isopropanol; the polyols having in particular 2 to 20 carbon atoms, preferably having 2 to 10 carbon atoms, and preferably having 2 to 6 carbon atoms, such as glycerol, propylene glycol, butylene glycol, pentylene glycol hexylene glycol, dipropylene glycol, diethylene glycol; glycol ethers (having in particular from 3 to 16 carbon atoms) such as the mono, di or tripropylene glycol (C1-C4) alkyl ethers, the mono, di or triethylene glycol (C1-C4) alkyl ethers; , and their mixtures.

The aqueous phase may further comprise stabilizing agents, for example sodium chloride, magnesium dichloride and magnesium sulfate.

The aqueous phase may also comprise any water-soluble or water-dispersible compound compatible with an aqueous phase such as gelling agents, film-forming polymers, thickeners, surfactants and mixtures thereof. In particular, a composition of the invention may comprise an aqueous phase in a content ranging from 1% to 80% by weight, especially from 5% to 50%, and more particularly from 10% to 45% by weight relative to the weight. total of the composition. According to another embodiment, a composition of the invention may be anhydrous. An anhydrous composition may comprise less than 3% by weight. weight of water, relative to the total weight of the composition, and in particular less than 2%, especially less than 1% by weight of water relative to the total weight of the composition, the water not being added during of the preparation of the composition but corresponding to the residual water provided by the mixed ingredients. More particularly, an anhydrous composition may be completely free of water.

Fatty phase A cosmetic composition according to the present invention may comprise at least one liquid and / or solid fatty phase.

In particular, a composition of the invention may comprise at least one liquid fatty phase, especially comprising at least one oil as mentioned below. The term "oil" means any fatty substance in liquid form at ambient temperature (20-25 ° C.) and at atmospheric pressure.

A composition of the invention may comprise a liquid fatty phase in a content ranging from 1 to 90%, in particular from 5 to 80%, in particular from 1.0 to 70%, and more particularly from 20 to 50% by weight per relative to the total weight of the composition. The oily phase suitable for the preparation of the cosmetic compositions according to the invention may comprise hydrocarbon oils, silicone oils, fluorinated or otherwise, or mixtures thereof. The oils can be volatile or nonvolatile. They can be of animal, vegetable, mineral or synthetic origin.

For the purposes of the present invention, the term "volatile oil" means an oil (or non-aqueous medium) capable of evaporating on contact with the skin in less than one hour, at ambient temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and at atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40,000. Pa (10-3 at 300 mm Hg), and preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01 at 10 mm Hg). For the purposes of the present invention, the term "non-volatile oil" means an oil having a vapor pressure of less than 0.13 Pa. For the purposes of the present invention, 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 term "hydrocarbon oil" means an oil containing mainly hydrogen and carbon atoms. The oils may optionally comprise oxygen, nitrogen, sulfur and / or phosphorus atoms, for example, in the form of hydroxyl or acid radicals.

Volatile oils Volatile oils may be selected from hydrocarbon oils having from 8. 16 carbon atoms, and especially C8-C16 branched alkanes (also called isoparaffins), such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example, the oils sold under the trade names L'oparse or Permethyls®. As volatile oils, it is also possible to use volatile silicones, such as, for example, volatile linear or cyclic silicone oils, especially those having a viscosity S 8 centistokes (eSt) (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 groups. or alkoxy having 1 to 10 carbon atoms. As the volatile silicone oil that can be used in the invention, mention may be made, in particular, of dimethicones of viscosity 5 and 6 cSt, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptarneethylhexyltrisiloxane, heptarneyloctyltrisiloxane, hexamethyl disiloxane, octamethyl tri siloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof. Fluorinated volatile oils, such as nonafluoromethoxybutane or perfluoromethylcyclopentane, and mixtures thereof can also be used. According to one embodiment, a composition of the invention may comprise from 1% to 80% by weight, or even from 5% to 70% by weight, or even from 10% to 60% by weight, and in particular from 15% to 50% by weight. % by weight of volatile oil relative to the total weight of the composition. LO Nonvolatile oils Nonvolatile oils may, in particular, be chosen from hydrocarbon oils, fluorinated oils and / or nonvolatile silicic oils. Non-volatile hydrocarbon oils that may especially be mentioned include: hydrocarbon-based oils of animal origin, such as perhydrosqualene; hydrocarbon-based oils of plant origin, such as phytostearyl esters, such as oleate phytostearyl, isostearate of physostearyl and lauroyl / octyl.dodecylated glutamate / phytostearyl (AJINOMOTO, ELDEW PS203), triglycerides consisting of esters of fatty acids and glycerol, in particular, whose fatty acids may have chain lengths varying from C4 to C36i and, in particular, C1 to C36, these oils being 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, butter shea butter, aloe oil, sweet almond oil, peach almond oil, peanut oil, argan oil, avocado oil, baobab oil, borage oil, broccoli oil, calendula oil, camelina oil, canola oil, carrot oil, safflower oil, coconut oil hemp, rapeseed oil, cottonseed oil, coconut oil, pumpkin seed oil, wheat germ oil, jojoba oil, lily oil, macadamia oil, corn oil, meadowfoam oil, St. John's wort oil, monoi oil, hazelnut oil, apricot kernel oil, walnut oil, olive oil, evening primrose oil, palm oil, blackcurrant seed oil, kiwi seed oil, pepper oil grape nuts, pistachio oil, pumpkin oil, pumpkin oil, quinoa oil, rose hip oil, sesame oil, soybean oil, oil sunflower, castor oil, and watermelon oil, and mixtures thereof, or triglycerides of caprylic / capric acids, such as those sold by the company STEARINERILS DUBOIS or those sold under the names MIGLYOL 810e, 812® and 818e by the company DYNAMI: T 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 squalane; synthetic ethers having from 10 to 40 carbon atoms; synthetic esters, such as the oils of formula RICOOR 2, in which RI represents a residue of a linear or branched fatty acid comprising from 1 to 40 carbon atoms, and R 2 represents a hydrocarbon chain, in particular, branched, containing from 1 to 40 carbon atoms with the proviso that R1 + R2 is? 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 or palmitate. isopropyl, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, isostearyl lactact, octyl hydroxystearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 4-diheptanoate and 2-hexyl ethyl palmitate, allyl benzoate, polyethylene glycol diheptanoate, propylene glycol diethyl-2-hexanoate, and mixtures thereof , C12-C1 alcohol beuzoates, hexyl laurate, esters of the acid neopentanoic acid, such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldocecyl neopentanoate, esters of isononanoic acid, such as isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, hydroxylated esters such as isostearyl lactate, diisostearyl malate; esters of polyols and esters of pentaerythritol, such as dipentaerythritol tetrahydroxystearate / tetraisostearate; esters of diol dimers and diacid dimers, such as Lusplan DD-DA5® and Lusplan DD-DA7®, marketed by NIPPON FINE CHEMICAL company and described in application US 2004-175338, - copolymers of diol dimer and dimer diacid and their esters, such as dimeric copolymers dilinoleyl diol / dimer dilinoleic and their esters, such as for example the Plandool-G copolymers of polyols and diacid dimers, and their esters, such as H.sub.Sususcent ISDA, or copolymer of diisoleic acid / butannediol, fatty alcohols liquid at room temperature with a branched and / or unsaturated carbon chain having from 12 to 26 carbon atoms, such as 2-octyldodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol; C12-C22, 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, - oils of high molar mass having, in particular, a molar mass ranging from approximately 400 to approximately 10,000 g / mol, in particular from approximately 650 to approximately In particular, from about 750 to about 7500 g / mol, and more particularly from about 1000 to about 5000 g / mol. As the high molecular weight oil that may be used in the present invention, there may be mentioned oils chosen from: lipophilic polymers, linear fatty acid esters having a total carbon number ranging from 35 to 70, and hydroxylated esters. aromatic esters, esters of C24-C28 branched fatty alcohols or fatty acids, silicone oils, oils of vegetable origin, and mixtures thereof.

Fluorinated oils which 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 (PDM.S); 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 trimethylsiloxysiticates, and mixtures thereof.

A composition according to the invention may further comprise at least one pasty compound. The presence of a pasty compound may advantageously confer improved comfort during the deposition of a composition of the invention. Such a compound may advantageously be chosen from lanolin and its derivatives; polymeric silicone compounds or not; polymeric or non-polymeric fluorinated compounds; vinyl polymers, especially homopolymers of olefins; olefin copolymers; homopolymers and copolymers of hydrogenated dienes; linear or branched oligomers, homo or copolymers of alkyl (meth) acrylates preferably having a C8-C30 alkyl group; homo and copolymeric oligomers of vinyl esters having C 8 -C 30 alkyl groups; homo- and copolymer oligomers of vinyl ethers having C 8 -C 30 alkyl groups; liposoluble polyethers resulting from the polyetherification between one or more C 2 -C 10 diols, in particular C 2 -C 50; esters of acid or fatty alcohol; and their mixtures. Among the esters, mention may be made especially of esters of an oligomeric glycerol, in particular diglycerol esters, such as polyglyceryl-2-triisostearate, adipic acid and glycerol condensates, for which part of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids, such as stearic acid, capric acid, stearic and isostearic acid and I2-hydroxystearic acid, in the image, in particular, of those marketed under the trademark Softisan 649 by the company Sasol or such as polyacyladipate-2 bis diglyceryl; arachidyl propionate sold under the name Waxenol 801 by Alzo; phytosterol esters; triglycerides of fatty acids and their derivatives, such as hydrogenated coco-glycerides; non-crosslinked polyesters resulting from the polycondensation between a linear or branched C 4 -C 50 dicarboxylic acid or polycarboxylic acid and a C2-050 diol or polyol; aliphatic esters. ester resulting from the esterification of an aliphatic hydroxycarboxylic acid ester with an aliphatic carboxylic acid; polyesters resulting from the esterification, by a polycarboxylic acid, of an aliphatic hydroxycarboxylic acid ester, said ester comprising at least two hydroxyl groups, such as Risocast DA-H® products, and Risocast DA-L®; and their mixtures. or the pasty compounds may be present in a composition of the invention in a content ranging from 0.1 to 30% by weight, more preferably from 0.5 to 20% by weight, relative to the total weight of the composition. .

A composition according to the invention may comprise at least one pulverulent phase, said powdery phase comprising in particular at least one filler, and advantageously also at least one emissive material as defined above and / or at least one pigment.

This is particularly the case for compositions in the form of powders, in particular compact powders.

Charges "Charges" include particles of any form, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured. The fillers may be inorganic or organic, of any form, platelet-shaped, spherical or oblong, irrespective of the crystallographic form (for example, sheet, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®), poly-β-alanine and polyethylene powders, tetrafluoroethylene polymer powders (Teflon e), lauroyl-lysine, starch, boron nitride, bimuth oxychloride, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancela (Nobel industry), copolymers of acrylic acid, silicone resin microbeads (Toshiba Tospearis®, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and magnesium carbonate, hydroxyapatite, barium sulfate, aluminum oxides , polyurethane powders, composite fillers, hollow silica microspheres, glass or ceramic microcrystals, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate. According to a preferred embodiment, use will be made of at least one filler chosen from kaolin, polyamide powders (nylon), acrylic acid copolymers, and mixtures thereof. The filler (s) may be present in a composition according to the invention in a total filler content ranging from 0.1% to 96% by weight, relative to the total weight of the composition, preferably ranging from 1% to 85%. by weight, and preferably ranging from 5% to 80% by weight. In the case of a fluid composition for example, the charge or fillers may be generally present in a content ranging from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight relative to the total weight of said composition, in particular from 1 to 7 by weight relative to the total weight of the composition. In the case of a solid composition in the form of a powder, the charge (s) may be generally present in a content ranging from 50 to 96% by weight, in particular from 70 to 85% by weight, preferably from 75 to 75% by weight. at 80% by weight relative to the total weight of the composition.

Pigments and dyes The composition according to the invention may comprise, in addition to the emissive material or materials according to the invention, one or more pigments or dyes.

By pigments, it is necessary to include particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition.

The pigments may be white or colored, mineral and / or organic. Among the inorganic pigments, titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxides, and oxides of zinc, iron (black, yellow or red) or chromium, the violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metal powders such as aluminum powder, copper powder. Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lacquers, in particular lacquers based on cochineal carmine, barium, strontium, calcium, aluminum. Opaque pigments such as, for example, iron oxides may be present in the composition according to the invention in a content ranging from 0.1% to 15% by weight, relative to the total weight of the composition, preferably ranging from 0.5% to 10% by weight, and preferably ranging from 1% to 10% by weight. The composition according to the invention may comprise an additional pulverulent dyestuff, different from the pigments described above, and which may especially be chosen from pearlescent agents and other interferential pigments, flakes and their mixtures. The nacres may be chosen from white nacres such as mica coated with titanium, or bismuth oxychloride, colored nacres such as titanium mica coated with iron oxides, titanium mica coated with, inter alia, ferric blue or chromium oxide, titanium mica coated with an organic pigment of the aforementioned type and nacres based on bismuth oxychloride. The nacres may be present in a composition according to the invention in a content ranging from 0.1% to 50% by weight, relative to the total weight of the composition, preferably from 0.1% to 40% by weight. weight, and preferably ranging from 0.1% to 30% by weight, The dyes can be chosen from those listed in the European cosmetic annex 4 and those listed by the FDA as authorized in cosmetics. Powder Composition Additives A composition according to the invention may comprise at least one liquid fatty phase structuring agent selected from a wax, a silicone resin, and mixtures thereof.

"Wax" waxes, within the meaning of the present invention, are understood to mean a lipophilic fatty compound, solid at ambient temperature (25 ° C.) and atmospheric pressure (760 mmHg, ie 105 Pa), with solid / liquid state change. reversible, having in particular a melting point greater than or equal to 30 ° C, especially greater than or equal to 55 ° C, and up to 250 ° C, especially up to 230 ° C, and in particular up to 120 ° C. By bringing the wax to its melting temperature, it is possible to render it miscible with oils and to form a microscopically homogeneous mixture, but by restoring the temperature of the mixture to room temperature, a recrystallization of the wax in the oils is obtained. of the mixture. The waxes may be present in the composition according to the invention in a content ranging from 0.1 to 15% by weight, relative to the pulverulent phase, preferably from 1 to 8%. The melting point values correspond, according to the invention, to the melting pIc measured using a differential scanning calorimeter (DSC), for example the calorimeter-sold under the name DSC 30 by the company. METLER, with a rise in temperature of 5 or 10 ° C per minute. The waxes, within the meaning of the invention, may be those generally used in the cosmetic or dermatological fields. They can in particular be hydrocarbon, silicone and / or fluorinated, optionally comprising ester or hydroxyl functions. They can also be of natural or synthetic origin. By way of non-limiting illustration of these waxes, mention may especially be made of: waxes of animal origin, such as beeswax, vegetable waxes such as Carnauba wax, Candellila wax, Ouricury wax, Japan wax - mineral waxes, for example paraffin waxes, or microcrystalline waxes or ozokerites, - synthetic waxes, among which polyethylene waxes, and waxes obtained by Fisher-Tropsch synthesis, - silicone waxes, in particular the linear substituted polysiloxanes; mention may be made, for example, of polyether silicone waxes, alkyl or alkoxy dimethicones having from 16 to 45 carbon atoms, alkyl methicones such as C30-C45 alkylmethicone sold under the trade name "AMS C 30" by DOW CORNING, hydrogenated oils that are solid at 25 ° C., such as hydrogenated castor oil, hydrogenated jojoba oil, hydrogenated palm oil, hydrogenated tallow, hydrogenated coconut oil and concrete fatty esters with 25 ° C such as C20-C40 alkyl stearate sold under the trade name "LESTER WAX K82H .." by KOSTER KEUNEN, and / or mixtures thereof. According to one embodiment, the wax present in the composition according to the invention may be wholly or partly in the form of powder, in particular micronized powder, to facilitate its implementation in the preparation of the. cosmetic composition, especially when the latter is in powder form. Among the waxes that can be used in the form of a powder, mention may especially be made of the Carnauba wax microbeads sold under the name Microcare 350® by the company Micro Powders and the paraffin wax microbeads sold under the name Microease 114Se by the company Micro Powders. Such micronized additional waxes make it possible in particular to improve the properties during the application of the composition to the skin.

Silicone Resins The pulverulent phase of a composition according to the invention may further comprise at least one silicone resin. Silicone resins are products of hydrolysis and polycondensation of siloxane mixtures of formulas (R) 3 SiOCH 3 and Si (OCH 3) 4, R representing an alkyl group having from 1 to 6 carbon atoms. These silicone resins are known or can be prepared according to known methods. Among the commercially available silicone resins that may be mentioned include, for example, those sold under the names KSP 100 (SHIN ETSU). The silicone resin may be present in a content ranging from 0.1 to 35% by weight relative to the total weight of the pulverulent phase.

Other Ingredients A composition according to the invention may furthermore comprise any ingredient (adjuvant) usually used in cosmetics, such as thickening or gelling agents, film-forming polymers, vitamins, trace elements, softeners, sequestering agents, perfumes alkalinizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, cosmetic active agents, moisturizing agents, or mixtures thereof. Of course, those skilled in the art will take care to choose any additional compounds and / or their amount in such a way that the advantageous properties intrinsically attached to the composition according to the invention are not, or not substantially, impaired by the addition envisaged. The invention is illustrated in the examples presented below, given by way of nonlimiting illustration. Unless otherwise indicated, the values in the examples above are expressed in% by weight relative to the total weight of the composition. EXAMPLES Examples 1 to 12 of particulate materials of structure (I). Process for Obtaining These Materials in the Stage: Preparation of AC According to FIG. 4 Synthesis of Ag @ a SiO 2 and Au SiO 2 Nanospheres The synthesis of the nanospheres is carried out according to the protocols described by G. Chemanov, Chem Phys Chem, 2005, 6, 1221-1231, J. Phys Chem B, 2004, 108, 1522-1524, Nano Lett 2001, 647-649, J. Am.Chem.Soc. 1999, 121, 10642-10643; HCGerritssen, Adv., Matter., 2006, 18, 91-95, A. van Blaaderen, Langmuir, 2003, 19, 6693-6700, Langmuir, 2003, 19, 1384-1389;

The gold nanospheres of spherical shape and diameter of 5, 50, 100, 200 nm are provided by the company Ted Pella Inc. The silver nanospheres of spherical shape and diameter of 20, 40, 60, 80 nm are 30 supplied by Ted Pella Inc.

Spherical silver nanospheres with a diameter of 100, 110 nm are provided by Nanocomposix Inc. Spherical gold nanospheres with a diameter of 80 nm are supplied by Nanocomposix Inc.

Protocol 1 Synthesis of Ag @ SiO2 and A..0 @ SiO2 Nanospheres An aqueous solution of poly (vinylpyrrolidone) PVP with a molar mass of 360 Kg / mol and an aqueous suspension of spherical noble metal (gold or silver) colloids of diameter d ( nm) are mixed with vigorous stirring at room temperature for 24 hours. The amount of PVP is calculated so that the number of PVP molecules is about 60 per μN1N. After centrifugation of the colloids obtained, the supernatant liquid is removed. The colloids are then dispersed in an ethanolic solution of ammonia (4.2% v / v) and an ethanolic solution of tetraethoxysilane (TEOS) at 10% v / v is introduced with vigorous stirring at room temperature. The hydrolysis reaction of the TEOS is prolonged for 1.2 h at room temperature, then the dispersed colloids obtained are centrifuged and washed with water three times and then redispersed in 20 ml of water. The relative concentration of TEOS makes it possible to govern the thickness of the silica shell.

The following silica-coated silver and gold colloids were thus obtained (r 1 and r 2 refer to FIG. 1A): [Ag @ SiO 2] 4 io: Ri 40 ± 5 nm; R 2 = 60 13 min [Ag @ SiO 2) 40.7a: 40 ± 5 nm; r 2 = 70 i 3 min. [Ag @ SiO,]; 60 nm; r 801 3 11m [Ag @ SiO2] 00y0: r1 60 ± 5 nm; R 2 = 901 nm [@] SiO 2] s, too: ri 80 ± 5 nm. ; where 100 nm 3 nm [Ag @ SiO 2] ≤ 0, ir o: ri 80 5 nm; r 2 = 1001 nrn [Ag r], SiO 2] 110 x 30, and 110 ± 5 nm; r2 = 1301-3 nm [AgCr], SiO2] 1 L0.140 rr 110 5 nm; R 2 = 140 + 3 nm [A 1 SiO 2 0 1 0 7 0 7 (3: r 1 501 3 nrn; 701 2 nm [Au 2 SiO 2] 50 nm, 501 nm; r 2 = 75 + 2 min [Au a SiOo], too: ri 80 ± 3 nm; R 2 100 ± 2 nm [A] SiO 2] en.tia: 801 3 nm; r 2 = 1101 2 nm [Au @ SiO 2] lao, El 1: 100 nm 3 nm; R 2 -120 .t 2 nm [A.tu.SiO 2] 10.130: RI 100 + 3 nrn; R 2 = 1301 2 mn Protocol 2: Synthesis of the nanospheres Ag a SiO 2 and leu @ SiO 2 An iso-propanol solution is mixed with deionized water and with a colloidal aqueous suspension of silver. To this suspension is added a 30% v / v ammonium hydroxide solution at ambient temperature, and then tetraethoxysilane (TEOS) with vigorous stirring. After stirring for 15 minutes at room temperature, the suspension is left standing for 24 hours at 4 ° C. before being centrifuged and washed with deionized water three times and then redispersed in 20 ml of water. The relative concentration of TEOS makes it possible to govern the thickness of the silica shell.

The following silica-coated silver colloids were thus obtained (r 1 and r 2 refer to Figure 1A): [AgSiO 2] 85.95: ri 85: 12 5 nm; [?], SiO 2, 85.106: 85 ± 5 nm; r 2 = 106 ÷ 3 nmr [λ SiO 2] 85.125: r 1, 85 ± 5 nm; r2 = 125 + 3 minutes

Protocol 3: Ag @ PMMA and Au, PMMA nanosphere synthesis. The protocol described in J. Am. Chem. Sac. 1999, 121, 10642-1.0643. Protocol 4: Synthesis of Ag @ PVP and Au @ PVP Nanospheres The procedure described in Nano Lett 2001, 1, 647-649 2nd step: Method for Obtaining Composite Emissive Materials 20. fluorophores is carried out according to the protocols described in the following publications: W. L, Vos, J. Phys. Chem. B 1999, 103 (9), pp 14081415; I. Sokolov, Smal 2007, 3, 3, 41.9-4123; Small 2008, 4, 7, 934-939; N. Halas, Small 2008, 4, 10, 1716-1722; A. E. Ostafin, J.Non-Crystal. Ground. 2007, 353, 354-365; W. H. Tan, Adv.Mater. 2004, 16, 173- 176; Anal. k3ioannal. Chem. 2006, 385, 518-524; Nano Lett. 2006, 6, 1, 84-88; Langmuir 2004, 20, 8336-8342; Langmuir 2001, 17, 4812-4817; J. Nanosci. NanoTechnol. 2002, 2, 405-409; J. Z. Zhou, Anal.Chem. 2004, 76, 5302-5312; D. Levy, Langmuir 2000, 16, 7377-7382;

General Protocol 7a: To a suspension of Ag @ SiO2 or Au @ SiO2 nanospheres, in deionized water is added (3-aminopropyl) triethoxysilane APTES with vigorous stirring at room temperature. After 30 minutes of reaction, the suspension of colloids thus functionalized is centrifuged and washed three times with deionized water and then resuspended in deionized water. To this aqueous suspension is then added dropwise and at room temperature 5 equivalents of fluorophore solubilized in ethanol with stirring for 30 min. After 24 hours at rest and at a temperature of 4 ° C., the suspension is centrifuged and washed several times with a mixture of deionized water and ethanol until the residual fluorophore washing water is used up.

General Protocol 7b: To a suspension of the Ag @ SiO2 or Au @ SiO2 nanospheres in deionized water is added a mixture of phenyltriethoxysilane (PTES) and tetraethoxysilane (TEOS) with vigorous stirring at room temperature. After 30 minutes of reaction, the colloid suspension is centrifuged and washed three times with deionized water and then resuspended in deionized water, to this aqueous suspension is then added dropwise and at room temperature. equivalents of fluorophore solubilized in ethanol with stirring for 30 minutes. After 24 hours at rest and at a temperature of 4 ° C., the suspension is centrifuged and washed several times with a mixture of deionized water and ethanol until the residual fluorophore washing water is exhausted.

General Protocol 7c: A. A suspension of the Ag @ SiO2 or Au @ SiO2 nanospheres in deionized water is added dropwise and at room temperature 5 equivalents of fluorophore solubilized in ethanol with stirring for 30 min. After 24 hours at rest and at a temperature of 4 ° C., the suspension is centrifuged and washed several times with a mixture of deionized water and ethanol until it is used up in the residual fluorophore wash water.

The following fluorescent emissive composite materials can be obtained: Ex1: [Ag @ SiO2 Cascade Blue Cascade: Bluej40.60 7'-Hydroxy-4-methylcoumari ne: Ex2: [Ag @ SiO2 -7-hydroxy-4-Ho Methylcoumarin ] 40.60 Yellow Ex3 Cascade: [Ag @ SiO2-Ycllow Cascade] 80,100 Alexa 488: E; x4: [Ag cUSi02 Alexa 488] 80,100 Ex5: [Ag @ SiO2 Rhod-2], Do, 30 Cy3: 1. 3 ## STR5 ## ## STR3 ## [Ag-SiO 2 -Fluorescein] 100, dihydroxy-5-amino-Cy3 SFiro (isobenzofuran-1 (3H), 9 '- (9H) xanthen) -3. -one, 5-ROX: 8: [Ag-SiO 5-ROX] 100,130 5-ROX: 5-carboxy-X-Rhodamine GON Ex9: [Au + SiO2 7-hydroxy-4-methylcoumarin] 80, ~ c Exl l .: [Au @ SiO2 - cascade yello @ so, 3 ta Ex1.O: [Au @ SiO2 - 5-R.0 le ,! Ex. 12: [Au @ SiO 2 -T inopal AMS-GX] 50, 75 Examples 13 and 14 of structural particulate materials (1. :)

Step: Preparation of C-D-E according to Figure 5, namely a silica core covered with metal and a silica bark.

A triplet of values, for example 250, 270, 290, denotes a structure where r1, r7 and r1 are respectively 250 nm, 270 nm and 290 nm. The production of particles of the SiO 2 @ M @ SiO 2 type (M represents Au or Ag) is carried out according to the protocols described in the publications N. T. Halas, Small 2008, 10, 1716-1722; W. St6ber, J. Colloid Interface Science, 26, 62-69, 1968; D.G. Duff described in Langmuir, 1993, 9, 2301.

Protocol 5: Obtaining Nanospheres [SiO2 @ Au @ S 102] 250,270,290 and [S1O2 @ Au @ SiO2] 250,290,310

In a first step, the silica nanospheres with a diameter ranging from 50 nm to 300 nm are produced according to the protocol described by W. Stöber, J. Colloid Interface Science, 26, 62-69, 1968 by hydrolyzing tetraethoxysilane (TEOS) by a basic solution of saturated ammonium hydroxide in a lower alcohol such as ethanol or a 3: 1 mixture of propanol: methanol at room temperature and with mechanical stirring.

In a 500 ml flask, 70 mmol of TEOS are added to an ethanolic solution of 105 mmol of ammonium hydroxide with mechanical stirring. After introduction of 25 ml of deionized water, the reaction medium is left to stand for 24 hours. The reaction medium is then brought back to room temperature, then the ethanol and the ammonia are evaporated under reduced pressure. After repeated washing with ethanol, 1 g of powder corresponding to silica nanospheres 250 mm in diameter are isolated. After introducing 100 ml of ethanol into these nanospheres, 1.5 × 10 4 eq of (3-aminopropyl) tri-methoxysilane (APTES) are introduced with vigorous stirring, and the reaction is continued for 24 h, then refluxed for 1 h. After cooling to room temperature, the reaction medium is centrifuged and washed with ethanol three times and nanospheres of silica functionalized with amine terminations are recovered in suspension in 50 ml of ethanol. To 10 ml of ethanolic suspension of functionalized silica nanospheres are added with stirring. 40 ml of a normal solution of sodium chloride at ambient temperature and then 200 ml of a solution of gold nanospheres of 2 to 3 nm in diameter prepared according to the method of DG Duff described in Langnuir, 1993, 9, 2301. After stirring for 12 h, the colloidal solution of SiO 2 @ Au nanospheres. It is centrifuged and washed with water three times and then redispersed in 100 ml of deionized water. The dispersion obtained (5 mL) of SiO2 @ Au nanospheres thus decorated is then mixed with stirring and at ambient temperature with 300 mL of a 0.1% aqueous solution of HAuO14 gold tetrachloride acid containing 1.3 g of potassium carbonate. After 15 minutes, 1.5 mL of formaldehyde at 38% in water are introduced and the reaction is stirred for 1h30. After centrifugation and washing with water three times, nanospheres of silica SiO 2 .Au are obtained, enveloped in a continuous gold shell with a thickness of 40 ± 5 nm, which are redispersed in 10 ml of water. By choosing a dispersion of 10 mL of SiO2 @ Au nanospheres thus decorated with gold, an aqueous suspension of SiO2 @ Au silica nanospheres is obtained, enveloped in a continuous gold shell with a thickness of 20 ± 5 nm.

The nanospheres SiO 2 a, Au in aqueous dispersion are introduced into pure ethanol at room temperature and vigorous stirring. To this dispersion are added simultaneously and with vigorous stirring for 1 h 30% ammonium hydroxide solution and a solution of tetraethylsiloxane (TEOS). The amount of TEOS added is adjusted to control the thickness of the silica shell obtained around the SiO2 @ Au nanospheres. After one night at 4 ° C., the SiO 2 @ Au @ SiO 2 nanospheres are centrifuged and washed several times with water and redispersed in 20 ml of water.

The SiO 2 @ Arp r, SiO 2 silicate colloids were thus obtained: [SiO 2 @ Au @ SiO 2] 25o, 270,290: ri 250 + IO no. ; r 2 = 270 ± 3 nm; r3 = 290 ± 3 nm [SiO2 @ 4u @ SiO2] 2so, 29o, 300: 250 ± 10 nm; r 2 = 290 ± 3 nm; r3 = 310 + 3 nm. Protocol 6: Obtaining Nanospheres [SiO2 @ Ag @ SiO2] 25o, 28o, 300 and [SiO2 @ Ag] SiO2] 250,290,310:

In a first step, the silica nanospheres with a diameter ranging from 50 nm to 300 nm are produced according to the protocol described by W. St®ber, 7. Colloid Interface Science, 26, 62-69, 1968 and Y. Zhang, Chinese Chem. Lett., 15, 8, 1005-1008, 2004 by introducing an ethanolic solution of tetraethoxysilane (TEOS) in a basic solution of 25% w / w ammonium hydroxide in a lower alcohol such as ethanol or a mixture 3: 1 propanol: methanol at room temperature and with mechanical stirring. The mixture is stirred for 1 hour at room temperature and the silica colloids thus obtained are left at room temperature. rest 24h at rest. After evaporation of the ethanol, the ammonia under reduced pressure and then washing with ethanol three times, nanospheres of SiO2 silica with a diameter of 250 ± 10 nm are obtained.

In a second step, the previously obtained silica nanospheres are mixed with a water: ethanol 1: 9 solution containing silver nitrate AgNO 3 at 0.1 ° / a with vigorous stirring. Then, an ethanolic solution of ammonium citrate in excess is introduced slowly. The dispersion is allowed to stand for 24 hours, then centrifuged and washed with water three times to remove residual reagents and to lead to the SiO2 @ Ag nanospheres redispersed in water LML.

The SiO2 @ Ag nanospheres thus obtained placed in aqueous solution are dispersed in pure ethanol at room temperature and with vigorous stirring. To this dispersion are added simultaneously and with vigorous stirring for 1 h 30% ammonium hydroxide solution and a tetraethylsiloxane solution (TEOS). The amount of TEOS added is adjusted to control the thickness of the silica shell obtained around the SiO 2 @ Ag nanospheres.

After one night at 4 ° C., the SiO 2 @ Ag @ SiO 2 nanospheres are centrifuged and washed several times with water and redispersed in 20 ml of water.

The following SiO2 @ Ag @ SiO2silice colloids were thus obtained: SiO2 @ Ag @ SiO2] 2so, 2 o, 300: ri 250 ± 10 nm; r 2 = 280 ± 3 nm; r3 = 300 ± 3 nm [SiO2 @ Ag @ SiO2] 250,290,310 ri 250 i 10 nm; r 2 = 290 ± 3 nm; r3 = 310 d: 3 nm

2nd step: Process for obtaining composite emissive materials of formula (II) The obtaining of the materials doped with fluorophores is carried out according to the protocols described in the following publications: W. L. Vos, J. Phys. Chem. B 1999, 103 (9), pp 14081415; I. Sokolov, Smal 2007, 3, 3, 419-4123; Small 2008, 4, 7, 934-939; N. Halas, Small 2008, 4, 10, 1716-1722; A. E. Ostafin, J.Non-Crystal. Ground. 2007, 353, 354-365; W. H. Tan, Adv.Mater. 2004, 16, 173-176; Anal. Bioannal. Chem. 2006, 385, 518-524; Nano Lett. 2006, 6, 1, 84-88; Langmuir 2004, 20, 8336-8342; Langmuir 2001, 17, 481.2-4817; J. Nanosci. NanoTechnol. 2002, 2, 25, 405-409; J. Z. Zhou, Anal.Chein. 2004, 76, 5302-5312; D. Levy, Langmuir 2000, 16, 7377-7382;

General Protocol 7a: To a suspension of the SiO 2 @ Au @ SiO 2 or SiO 2 (çAg · SiO 2) nanospheres in deionized water is added (3-aminopropyl) triethoxysilane APTES with vigorous stirring at room temperature. The suspension of colloids thus functionalized is centrifuged and washed three times with deionized water and then resuspended in deionized water to this aqueous suspension is then added dropwise and at room temperature 5 equivalents of fluorophore solubilized in water. Ethanol with stirring for 30 minutes After 24h at rest and at a temperature of 4 ° C., the suspension is centrifuged and washed several times with a mixture of deionized water and ethanol until the residual fluorophore washing water is used up.

General Protocol 7b: To a suspension of the SiO 2 @ Au @ SiO 2 or SiO 2 rJAg @ SiO 2 d.a.ns deionized water nanoparticles is added a phenyltriethoxysilane (.PTES) 1tetraethoxysilane (TEOS) mixture 10 with vigorous stirring at room temperature. After 30 minutes of reaction, the colloid suspension is centrifuged and washed three times with deionized water and then resuspended in deionized water. To this aqueous suspension is then added dropwise and at room temperature 5 equivalents of fluorophore solubilized in ethanol with stirring for 30 minutes. After 24 hours at rest and at a temperature of 4 ° C., the suspension is centrifuged and washed several times with a mixture of deionized water and ethanol until the residual fluorophore washing water is used up. The following fluorescent composite emissive materials were obtained: Ex 13: [SiO 2 @ Ag @ SiO 2 -7-hydroxy-Ex 14: [SiO 2 Al 2 O 4 SiO 2-methylcoumarin] 250,280,300 yellow] 250,270,290 Exixels of compositions The following were prepared according to standard methods for those skilled in the art with the particulate materials as described above. After application to the skin, according to the protocol described above, a lightening is observed with, for example E1, a slightly yellow hue for example E2, a slightly yellow hue for example E3, a slightly red hue for Example E4, a slightly red hue for Example E5, a slightly beige hue

Ingredients (% by mass) El E2 E3 E4 ES 2-OLEAMIDO-1,3-OCTADECANEDIOL 0.03 0.03 0.03 0.03 0.03 68 MAGNESIUM SULPHATE 0.7 CHLORPHENESIN 0.25 METHYLPARABEN 0.25 BUTYLPARABEN 0.15 PHENOXYETHANOL 0.6 CYCLOPENTASILOXANE (and) DISTEARDIMONIUM HECTORITE (and) ALCOHOL DENAT. 5.82 DIMETHICONE 2.91 CYCLOPENTASILOXANE 10.35 ACETYLATED GLYCOL STEARATE 0.51 PROPYLENE GLYCOL [Ag @ SiO2. Cascade Blue] 40.60 1.5 [Ag] SiO 2 7-hydroxy-4-methylcoum.arine] 40.60 [Au @ SiO 2 7 1 ~ @ roxy 4 methylcoumari]] [Ag @ SiO 2 - Cascade Yellow] 80,100 1. [Ag @ SiO 2 Alexa 488] 80,100 [Ag c SiO 2 Rhod-2100,130 [Ag @ SiO 2 -cy 3] 100,130

ISODODECANE 1.88 WATER 62.5 POLYGLYCERYL-4 ISOSTE.ARATE (and) CETYL PEGIPPG-I0 / 1 DIMETHICONE (and) HEXYL LAUR.ATE 6.55 100 2956028 0.7 0.7 0.7 0.7 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.15 0.15 0.15 0.15 0.6 0.6 0.6 0.6 5.82 5.82 5.82 5.82 2.91 2.91 2.91 2.91 10.35 10.35 10.35 10.35 0.51 0.51 0.51 0.51 5 5 5 5 1.5 1.5 1 1.5 1.5 1.5 1 1 1.88 1.88 1.88 1.88 62.5 615 62.5 61 6.55 6.55 6.55 6.55 100 100 100 100 The expression "comprising a (e) "is synonymous with" having at least one (c) ". 5

Claims (5)

REVENDICATIONS1. Composition. cosmetic composition comprising: a first fluorophore compound having an absorption spectrum; a second fluorophore compound having an emission spectrum overlapping the absorption spectrum of the first fluorophore compound, at least one of the two fluorophore compounds having an increased luminescence by a proximity interaction effect with at least one metal, the metal and the fluorophore compound belonging to the same particle. 2. Composition according to claim 1, the first fluorophore compound having an increased luminescence within a particle comprising the first fluorophore and a metal. 3. The composition of claim 1 or 2 wherein the second fluorophore compound has increased luminescence within a particle having the second fluorophore and a metal. 4. Composition according to any one of the preceding claims, comprising a third fluorophore compound. 5. Composition according to the preceding claim, the third fluorophore compound having an increased luminescence within a particle comprising the third fluorophore and a metal. '6. Composition according to any one of the preceding claims, the emission spectrum of the first fluorophore compound ranging in the range from 580 to 700 nm, preferably with a width at half height of the emission curve of the first compound. fluorophore between 580 and 700 nm. 7. A composition according to any one of the preceding claims, the emission spectrum of the second fluorophore compound extending in the range of 480 to 620 nm, preferably with a width at half height of the emission curve. the second fluorophore compound between 480 and 620 nm. 8. Composition according to any one of claims 1 to 7, the first fluorophore compound having an emission curve comprised at mid-height between 580 and 700 nm and a visible absorption curve at mid-height between 480 and 620 nm, 2956028. The second fluorophore compound having an emission curve at mid-height between 480 and 620 nm. 9. Composition according to any one of claims 1 to 5, the first fluorophore compound having a standard emission curve covering the relative luminous efficiency curve in the range 600-700 nm. 10. Composition according to any one of claims 1 to 5, the first fluorophore compound having a standard emission curve covering the relative luminous efficiency curve in the range 500-600 min. He. A composition according to any one of claims 1 to 5, the second fluorophore compound having a standard emission curve covering the relative luminous efficiency curve in the 400-500 nm range. 12. Composition according to any one of claims 1 to 5, the first fluorophore compound having a standard emission curve covering the relative luminous efficiency curve in the range 600-700 nm and the second fluorophore compound having a normalized curve of emission covering the relative luminous efficiency curve in the range 500-600 nm. 13. Composition according to any one of the preceding claims, wherein the overlap of the absorption spectra of the first fluorophore compound and emission of the second fluorophore compound defines an area whose double is at least 50% of the sum of the areas of said spectra. 14. Composition according to claim 4 or 5, the third fluorophore compound emitting a fluorescent light in the visible range such that the normalized emission curve of the second fluorophore compound and the curve of relative luminous efficiency defined by the CIE overlap the each other in the wavelength range between 400 and 500 nm; in that the second fluorophore compound emits a fluorescent light in the visible range such that the normalized emission curve of the second fluorophore compound and the relative luminous efficiency curve defined by the CIE overlap each other on the domain. wavelengths between 500 and 600 nm; in that the first fluorophore emits a fluorescent light in the visible range such that the normalized emission curve of the first fluorophore and the relative luminous efficiency curve defined by the CIE overlap each other over the range of lengths. 600 to 700 nm, in that the absorption curve of the second fluorophore and the emission curve of the third fluorophore overlap each other and that the absorption curve of the first fluorophore and the emission curve of the second fluorophore overlap each other under irradiation with natural light. 15. Composition according to any one of the preceding claims, the coverage of the composition being less than or equal to 70%, better 65%, even better 60%. 16. A composition according to any one of the preceding claims, wherein the emission spectrum of the red composition has a peak which substantially coincides with the maximum peak of sensitivity in human red according to the CIE. 17. Composition according to any one of the preceding claims, all the fluorophore compounds being free of rare earths. 18. Composition according to any one of claims 1 to 17, the particle comprising a. metal core covered with a bark of a semi-organic or organic matrix containing the corresponding fluorophore compound, in particular a matrix of SiO2, PMMA, PVP or PS. 19. Composition according to any one of claims 1 to 17, the particle comprising a core having a non-metallic core covered with a layer of at least one metal, in particular gold or silver, and a bark of a matrix containing the corresponding fluorophore compound, in particular a silica matrix. 20. The composition of claim 19, the eteur and the matrix being formed from the same material, in particular silica. 21. A process for lightening the complexion, in which a composition as defined in any one of the preceding claims is applied to the skin, the covering capacity of the composition preferably being less than or equal to 70%, better 65% , even better 60%. 22. A method of modifying the hue of the skin, in which a composition as defined in any one of Claims 1 to 20 is applied to the skin, the covering capacity of the composition being less than or equal to 70%, better 65%, even better 60%. 23. A method for lightening the complexion or modulating the hue of the skin, wherein a cosmetic composition is applied to the skin comprising at least one fluorophore compound having an increased fluorescence, in particular a compound comprising particles having a nanometric metal core, and a coating coating the core, this coating comprising at least one fluorescent molecule disposed on the surface of the coating or impregnating it and located at a distance from the metal core sufficiently small to increase the fluorescence of the molecule. 24. A method for increasing skin reflectance in the wavelength range of 600 to 700 nm, comprising the step of applying to the skin a cosmetic composition according to any one of claims 1 to 20 comprising at least one at least two fluorophore compounds F1 and F2 characterized in that the fluorophore compound Fi. emits a fluorescent light in the visible range such that the normalized emission curve of said fluorophore compound F1 and the relative luminous efficiency curve defined by the CIE overlap each other over the range of wavelengths between 600 and 700 nm; and in that the absorption curve of the fluorophore F1 and the emission curve of the fluorophore F2 overlap each other under irradiation with natural light. 25. A method for increasing skin reflectance in the wavelength range of 500 to 600 nm, comprising the step of applying to the skin a cosmetic composition according to any one of claims 1 to 20 comprising at least one minus two fluorophore compounds F3 and F4, characterized in that the fluorophore compound F4 emits fluorescent light in the visible range such that the normalized emission curve of the fluorophore compound F4 and the relative luminous efficiency curve defined by the CIE overlap with each other. each other over the wavelength range between 500 and 600 nm and in that the absorption curve of the fluorophore compound F4 and the emission curve of the fluorophore F3 overlap each other under irradiation with natural light. A method for increasing the skin reflectance in the wavelength range of 500 to 700 nm, comprising the step of applying to the skin a cosmetic composition according to any one of claims 1 to 20 comprising at least one at least three fluorophore compounds F5, F6 and F7 characterized in that the fluorophore compound F5 emits fluorescent light in the visible range such as the normalized emission curve of the fluorophore compound F5 and the relative luminous efficiency curve defined by the CIE overlap each other over the range of wavelengths between 400 and 500 nm; in that the fluorophore F6 emits a fluorescent light in the visible range such that the normalized emission curve of said fluorophore compound F6 and the relative luminous efficiency curve defined by the CIE overlap each other on the domain wavelengths between 500 and 600 nm; in that the fluorophore F7 emits a fluorescent light in the visible range such that the normalized emission curve of the fluorophore F7 and the relative luminous efficiency curve defined by the CIE overlap each other over the range of lengths. wavelength between 600 and 700 nm; in that the absorption curve of the fluorophore F6 and the emission curve of the fluorophore F5 overlap each other and in that the absorption curve of the fluorophore F7 and the emission curve of the fluorophore F6 are cover each other under irradiation with natural light. 27. Method according to any one of claims 24 to 26, the overlap between the curves being such that twice the common area of the two overlapping curves represents at least 20%, better 30%, even better 40%, 50%, 60%, 70% or 80% of the sum of the areas of each of these curves.