FR2845897A1 - Cosmetic composition containing photochromic and goniochromic dyes, useful e.g. in make up, provides rapid and reversible change in color and brightness on exposure to light - Google Patents

Abstract

Cosmetic composition (A) comprises at least one first component (A1) containing a photochromic dye (PC) or a naphthopyran dye (NPD) and a second component (A2) containing at least one goniochromic dye (GD), with both components in physiologically acceptable medium. An Independent claim is also included for a make up kit containing (A).

Description

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 The present invention relates to a new cosmetic product including makeup of the skin, lips and / or integuments associating at least one goniochromatic coloring agent and at least one photochromic coloring material.

 By makeup product is meant a product containing a coloring material for depositing a color on a keratinous material (the skin, lips or superficial body growths) of a human being such as a lipstick, a make-up, an eye -liner, a foundation, a self-tanner or a makeup product with care properties or a semi-permanent makeup product (tattoo).

 More particularly, the product considered according to the invention comprises at least two cosmetic compositions that can be applied successively to the skin of both the face and the human body, on the lower and upper eyelids of human beings, on the lips and on the dander like nails, eyebrows, eyelashes or hair, as well as a process of bilayer makeup of the face and the human body.

 Cosmetic composition means a composition as defined in Council Directive 93/35 / EEC of 14 June 1993.

 One of the main functions of makeup is to bring color effects and / or optical areas to make up on the skin, lips, eyelashes and nails.

 In general, these effects are static, that is to say do not change over time, nor according to the ambient brightness. The most frequent evolution generally consists of a progressive alteration in time of the original color and / or optical effects. This alteration is generally due either to a transfer and / or a migration of the composition, phenomena particularly pronounced for lipsticks, or to poor performance of the pigments present in the makeup composition vis-à-vis sebum, a phenomenon more particularly met with foundations.

 So far there is no makeup product that could be described as dynamic in terms of hue, that is to say, likely to change significantly in terms of color and / or brightness, response for example to a change in ambient brightness.

 However, it is clear that this type of makeup product would respond precisely to a desire of consumers who are looking for original colorful makeup contrasting with conventional makeup compositions.

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 The main purpose of the invention is to meet this need. More particularly, it aims to provide a cosmetic product with a color effect and / or optical said dynamic.

 In this case, the present invention makes particular use of the ability of certain photochromic dyestuffs to change color as soon as they are subjected to radiation containing ultraviolet rays and this in a reversible manner.

 The use of photochromic pigments in cosmetic compositions is known. EP 970 689 discloses a bi-layer makeup product for superimposing on a base layer containing a photochromic pigment, a surface layer containing an ultraviolet light filter. The corresponding make-up makes it possible to form patterns that appear or disappear depending on the nature of the light, but it is not associated with any dynamics in terms of color. The application WO 02/078665 proposes for its part cosmetic compositions comprising photochromic agents of the naphthopyran type. However, these are incorporated in the cosmetic composition in a liquid form encapsulated in a microcapsule. This dispersible form is described as having antioxidant activity.

 Unexpectedly, the inventors have found that it is particularly advantageous to associate at least one goniochromatic coloring material with at least one specific photochromic coloring material to obtain an original dynamic effect in terms of color and brightness.

 In the present case, the present invention relates, according to a first aspect, to a cosmetic product, in particular a makeup product for the skin, lips and / or integuments comprising at least a first and a second composition, the first composition comprising, in a first a physiologically acceptable medium, at least a first dyestuff and the second composition comprising in a second physiologically acceptable medium, at least a second dyestuff, one of the dyestuffs being at least one goniochromatic dye and the other dyestuff being photochromic.

 Advantageously, the combination of a photochromic coloring material in accordance with the invention with at least one goniochromatic coloring agent in a cosmetic composition more particularly intended for make-up makes it possible to confer on

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 said composition a fast dynamic and reversible in terms of hue and / or brightness effect. Thus, the hue difference is significant enough to be noticed with the naked eye.

On the other hand, it is immediate, that is to say, manifests itself in a very short time, after either the exposure of the makeup to UV radiation, or stop this exposure.

 In addition to this aspect effect of hue and / or dynamic brightness, the products according to the invention are particularly advantageous to supplement the phenomenon of color alteration which has been discussed previously and which is generally related to poor performance of conventional pigments with sebum. The combination with these pigments of a photochromic coloring material in accordance with the invention advantageously makes it possible to compensate for this type of deterioration insofar as said photochromic dye is capable on its own, in response to a UV-type light excitation. to restore a colored effect equivalent to that initially obtained by said pigments.

 As stated above, the product according to the invention comprises two (or more) physiologically acceptable compositions.

 The compositions may be packaged separately or together in the same packaging article or in two (or more) separate or separate packaging articles. Each composition can be a free or compacted powder, a foundation, a blush, an anti-ring product, a blush, a lipstick, a lip balm, a lip gloss, a pencil. lips or eyes, a mascara, an eyeliner, a nail polish or a product of body make-up or skin coloring. In this case, the first composition of the product according to the invention may constitute a base layer applied to the support to be made up, in particular the lips and the second composition, a top layer (or top coat). However, it is possible to apply, under the first layer, an under layer having the constitution or not of the second composition. It is also possible to deposit an overlayer on the second layer having a constitution identical or not to that of the first layer.

 According to another of its aspects, the invention relates to a makeup kit containing a cosmetic makeup product as defined above, in which the various compositions may in particular be packaged separately and are accompanied by appropriate application means. These means may be brushes, brushes, pens, pencils, felts, feathers, sponges and / or foams.

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 The invention also relates, according to another of its aspects, to a process for making up the skin, the lips and / or the integuments of applying to the skin, the lips and / or the integuments a cosmetic makeup product such as previously defined.

 More particularly, in a first layer, a first composition comprising, in a first physiologically acceptable medium, at least one photochromic coloring material is applied, then a layer of the second composition comprising at least some of said first layer is applied to all or part of said first layer. in a second physiologically acceptable medium, at least one goniochromatic coloring agent.

 Preferably, the makeup obtained is a bilayer makeup. In particular, the basecoat is a foundation, a makeup, a lipstick, a lip gloss, an eyeliner, a body makeup product, and the top layer or top coat a care product or protection.

 Preferably, the first layer of the first so-called base layer composition is allowed to dry before applying the second layer of the second composition.

 The order of superposition, and / or the superposition mode of the two compositions, namely total or partial, may moreover be interesting for imparting additional visual effects. The second layer may for example be arranged to form patterns on the surface of the base layer. Thus, when the top coat contains the photochromic coloring material, it is possible to apply the second layer to only a portion of the first layer containing the goniochromatic agent. Only the part on which are superimposed the two layers will be likely to have a color effect in the absence of UV radiation.

 This bilayer makeup can be adapted for all skin makeup products as well as the face and the scalp and body of human beings, mucous membranes such as the lips, the interior of the lower eyelids, and integuments such as nails , eyelashes, hair, eyebrows, even hair.

COLORING MATERIAL PHOTOCHROME
In general, a photochromic dyestuff is a coloring material having the property of changing color when illuminated by ultraviolet light and restoring its original color when it is no longer illuminated by this light

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 or to go from an uncolored state to a colored state and vice versa. In other words, such a material has different hues depending on whether it is illuminated by light containing a certain amount of UV radiation such as sunlight or artificial light.

 For the purposes of the present invention, photochromic coloring material denotes a coloring material characterized by a difference in color AE at least equal to 5.

 For the purposes of the present invention, AE denotes the color difference observed at the level of the photochromic material between its excited state, that is to say in the presence of UV irradiation and its non-excited state, that is to say say in the absence of UV irradiation.

 The AE can be determined from the chromatic space and more particularly from the specific chromaticity coordinates of the photochromic coloring material considered, evaluated on the one hand after 2 minutes of exposure to a UV radiation, generally on the using an artificial light containing UV radiation, and secondly at rest, that is to say 5 seconds after stopping the radiation.

 More specifically, the measurement protocol is as follows: 1% by weight of the photochromic coloring matter in question is formulated in 100% by weight of a white lipstick base of the following composition: 2-octyl dodecanol 0, 5% - modified hectorite with di-stearyl di-methyl ammonium chloride 0.6% - liquid lanolin 27.2% - microcrystalline wax 10.5% - polyglycerolated beeswax (3 moles) 4.2% - acetylated lanolin 6.7% - arara oil (oleic acid esters) 13.5% - oxypropylenated lanolin wax (5 op) 6.7% - oleyl erucate 13.5% - oleic-linoleic acid triglycerides - linolenic acid 1.7% - palmitic-oleic-linoleic acid triglycerides 13.5% - sodium hyaluronate 0.1%

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- preservatives 0.1% - vitamin 0.5% - UV filter 0.7%
On a LENETA brand contrast card and FORM 1A PENOPAC reference card, a layer of 50 m thickness of the composition is spread with the aid of an automatic spreader. The layer covers at least the white background of the card.

 The reflection measurements are performed using a MINOLTA 3700D spectrocolorimeter. The initial trichromatic coordinates of the composition before irradiation (Lo, ao and bo) are thus determined. The composition is then subjected to a flow of 2 mW / cm 2 of UVA radiation for two minutes and then immediately after stopping the irradiation, the new trichromatic coordinates (L, a and b) are determined. There is less than 5 seconds between stopping irradiation and determining the new coordinates.

The AE is calculated as follows: AE = [(L - Lo) 2 + (a - ao) 2 + (b - bo) 2]
Advantageously, the photochromic dyestuffs according to the invention have an AE of at least 5, in particular greater than or equal to 10, in particular greater than or equal to 25, more particularly greater than or equal to 35 or even greater than or equal to 45.

 A measure of AE greater than about 30 means that the photochromic dye gives a bright color.

 In the context of the present invention, the photochromic dyes also have the advantage of responding in a short time either to excitation by UV light or to stopping such excitation. It follows a rapid change in terms of color. This change in hue can thus result in a period of time advantageously less than or equal to 2 minutes, in particular less than or equal to 1 minute and in particular less than or equal to 50 seconds.

 According to a variant of the invention, the product according to the invention contains at least two photochromic dyes as defined above, especially within the same composition, in association or not with a non-photochromic dyestuff.

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 The photochromic coloring material considered according to the invention may be present in an amount ranging from 0.001 to 20% by weight, especially from 0.005 to 10% by weight, in particular from 0.01 to 5% by weight, and more particularly from 0 to 5% by weight. 0.5 to 2% by weight, or even 0.1 to 1% by weight, relative to the total weight of the composition containing it.

 The photochromic dyestuffs according to the invention may be present in a solubilized or dispersed form within the first or second composition.

According to a particular variant, they are present in a solubilized form.

 More particularly, the photochromic coloring substances considered according to the invention are of organic nature.

dans lesquelles : - RI représente : - (i) un atome d'hydrogène; - (ii) un groupement hydrocarboné ayant 1 à 30, notamment 1 à 18, et en particulier 1 à 12, voire 1 à 6 atomes de carbone, linéaires ramifiés ou cycliques, saturés ou insaturés, éventuellement comportant 1 à 5 hétéroatomes choisis parmi N, 0, S, Si et P, et/ou éventuellement halogéné ou perhalogéné, notamment par FI, Br et/ou Cl; - (iii) un cycle hydrocarboné formé avec l'une des liaisons "f' ou "gh" et le radical R7; ou More specifically, the photochromic organic dyestuffs according to the invention are naphthopyrans, and more particularly are chosen from 3Hnaphtho- [2,1-b] -pyrans which can be represented by the formula (I) of 2H-naphtho- [ 1,2-b] -pyrans which can be represented by the formula (II):

in which: - RI represents: - (i) a hydrogen atom; (ii) a hydrocarbon group having 1 to 30, especially 1 to 18, and in particular 1 to 12, or even 1 to 6 carbon atoms, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N , 0, S, Si and P, and / or optionally halogenated or perhalogenated, especially by FI, Br and / or Cl; (iii) a hydrocarbon ring formed with one of the bonds "f" or "gh" and the radical R7;

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(iv) a group chosen from -COOR4, -C (O) NR2R3, -NR2R3, -OR4 and -SR4, in which: R2 and R3 represent, independently of one another, a hydrocarbon group having 1 to 20, especially 1 to 12, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally comprising 1 to 5 heteroatoms selected from N, O, S, Si and P, taken together with the nitrogen atom to which they are attached, form a hydrocarbon heterocycle, saturated or unsaturated, having 3 to 10, especially 4 to 6 carbon atoms and optionally 1 to 5 other heteroatoms selected from N, O, S, Si and P, said ring being optionally substituted by at least one hydrocarbon radical having 1 to 20, especially 1 to 15, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 selected heteroatoms; from N, 0, S, Si and P; - R4 represents a hydrocarbon group having 1 to 20, especially 1 to 12, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally halogenated or perhalogenated, especially by FI, Br and / or Cl; and / or optionally comprising 1 to 5 heteroatoms selected from N, O, S, Si and P; - R5 and R6 represent, independently of one another, a group chosen from: - (i) saturated cyclic aminoaryl groups of formula (IIa) or (IIb):

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dans laquelle R10 et Ru représentent, indépendamment l'un de l'autre, un groupement choisi parmi (i) les groupements hydrocarbonés ayant 1 à 30, notamment 1 à 18, et en particulier 1 à 12, voire 1 à 6 atomes de carbone, linéaires ramifiés ou cycliques, saturés ou insaturés, éventuellement comportant 1 à 5 hétéroatomes choisis parmi N, 0, S, Si et P, et/ou éventuellement halogéné ou perhalogéné, notamment par FI, Br et/ou Cl; (ii) les atomes d'halogène, et notamment FI, Br et/ou Cl; (iii) les groupements-CN (nitrile), - COOH (carboxylate), -N02 (nitro) ; (iv) un atome d'hydrogène ; un groupement choisi parmi -C(O)NR2R3, -NR2R3, -OR4 ou -SR4 avec R2, R3 et R4 ayant les significations données ci-dessus ; les radicaux R10 et Ru pouvant former ensemble un cycle hydrocarboné saturé ou insaturé ayant au total 5 à 8 atomes (incluant les atomes du cycle indoline), lesdits atomes étant choisis parmi C, 0, S et/ou NR avec R représentant H ou un radical hydrocarboné ayant 1 à 20, voire 1 à 12 atomes de carbone, linéaire, ramifié ou cyclique, saturé ou insaturé, éventuellement comportant 1 à 5 hétéroatomes choisis parmi N, 0, S, Si et P, - (iii) les groupements de formule (IV) : in which the ring containing N and X is a saturated ring which comprises in total 3 to 30 atoms, in particular 4 to 10 and in particular 5 to 8 or even 5,6 or 7 atoms, including nitrogen, the remainder being atoms of carbon and / or heteroatoms selected from O, S, Si, P and / or groups selected from -NH and -NR with R representing a hydrocarbon radical having 1 to 20, especially 1 to 15, and in particular 1 to 6 linear, branched or cyclic, saturated or unsaturated carbon atoms, optionally containing 1 to 5 heteroatoms selected from N, O, S, Si and P; - (ii) the indolinoaryl groups of formula (III):

in which R10 and Ru represent, independently of one another, a group chosen from (i) hydrocarbon groups having 1 to 30, especially 1 to 18, and in particular 1 to 12, or even 1 to 6 carbon atoms linear, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, in particular by FI, Br and / or Cl; (ii) halogen atoms, and especially FI, Br and / or Cl; (iii) CN (nitrile), -COOH (carboxylate), -NO2 (nitro) groups; (iv) a hydrogen atom; a group selected from -C (O) NR 2 R 3, -NR 2 R 3, -OR 4 or -SR 4 with R 2, R 3 and R 4 having the meanings given above; the radicals R10 and Ru may together form a saturated or unsaturated hydrocarbon ring having a total of 5 to 8 atoms (including the atoms of the indoline ring), said atoms being selected from C, O, S and / or NR with R representing H or a hydrocarbon radical having 1 to 20 or even 1 to 12 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P; - (iii) the groups of formula (IV):

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dans laquelle m et p sont, indépendamment l'un de l'autre, des entiers allant de 2 à 5; - (iv) les groupements aminoaryles cycliques insaturés de formules (Va), (Vb) ou (Vc) :

dans lesquelles Rg et R9, représentent, indépendamment l'un de l'autre, un groupement choisi parmi (i) les groupements hydrocarbonés ayant 1 à 30, notamment 1 à 18, et en particulier 1 à 12, voire 1-6 atomes de carbone, linéaires ramifiés ou cycliques,

wherein m and p are, independently of one another, integers ranging from 2 to 5; (iv) unsaturated cyclic aminoaryl groups of formulas (Va), (Vb) or (Vc):

in which Rg and R9 represent, independently of one another, a group chosen from (i) hydrocarbon groups having 1 to 30, especially 1 to 18, and in particular 1 to 12, or even 1-6 carbon atoms. carbon, linear branched or cyclic,

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 saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, in particular by FI, Br and / or Cl; (ii) halogen atoms, and especially FI, Br and / or Cl; (iii) CN (nitrile), -COOH (carboxylate), -NO2 (nitro) groups; (iv) a hydrogen atom; a group selected from -C (O) NR 2 R 3, -NR 2 R 3, -OR 4 or -SR 4 with R 2, R 3 and R 4 having the meanings given above; (v) a hydrocarbon group having 1 to 30, especially 2 to 18, and in particular 3 to 12 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally comprising 1 to 5 heteroatoms chosen from N, O, S; , Si and P; in particular a group chosen from -C6H4-CONR2R3, -C6H4-NR2R3 and -C6H4-OR4 with R2, R3 and R4 having the meanings given above; - R7 represents a group chosen from: - (i) hydrocarbon groups having 1 to 30, especially 1 to 18, and in particular 1 to 12 carbon atoms, linear branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, in particular by FI, Br and / or Cl; - (ii) halogen atoms, and especially FI, Br and / or Cl; (iii) CN-groups (nitrile), -COOH (carboxylate), -NO2 (nitro); N = N- (azo); = NH (imino); -CONH2 (amide); - (iv) a hydrogen atom; (v) a group selected from -C (O) NR 2 R 3, -NR 2 R 3, -OR 4 or -SR 4 with R 2, R 3 and R 4 having the meanings given above; (vi) the radical R7 may additionally form, with one of the bonds "i", "j", "k", or "g, h" taken with the radical R1, or "f 'taken with the radical R 1, a saturated hydrocarbon ring having in total 3 to 8, in particular 4 to 7, and in particular 5 or 6, carbon atoms, optionally comprising 1 to 5 heteroatoms chosen from N, O, S, Si and P; 1 represents a group chosen from: - a hydrogen atom, - (ii) a hydrocarbon group having 1 to 30, especially 1 to 18, and in particular 1 to 12 carbon atoms, branched or cyclic, saturated or unsaturated, optionally comprising 1 to 5 heteroatoms chosen from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, in particular by FI, Br and / or Cl;

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 (iii) a group chosen from -C (O) NR 2 R 3, -NR 2 R 3, -OR 4 and -SR 4, with R 2, R 3 and R 4 having the meanings given above; - R'2 represents a group chosen from: - (i) hydrocarbon groups having 1 to 30, especially 1 to 18, and in particular 1 to 12 carbon atoms, linear branched or cyclic, saturated or unsaturated, optionally comprising 1 to Heteroatoms selected from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, especially by FI, Br and / or Cl; - (ii) halogen atoms, and especially FI, Br and / or Cl; (iii) CN-groups (nitrile), -COOH (carboxylate), -NO2 (nitro); N = N- (azo); = NH (imino); -CONH2 (amide); - (iv) a hydrogen atom; (v) a group chosen from -C (O) NR 2 R 3, -NR 2 R 3, -OR 4 or -SR 4 with R 2, R 3 and R 4 having the meanings given above.

dans lesquelles RI, R5, R6, R7, R'1 et R'2 sont définis tels que précédemment. In particular, the photochromic organic dyestuffs according to the invention may correspond to one of the following formulas (Ia) and (IIa):

in which R1, R5, R6, R7, R'1 and R'2 are defined as above.

 In particular, R 1 may represent a hydrogen atom; hydrocarbon ring with one of the "f 'or" gh "bonds and the radical R7 or a group selected from -COOR4, -NR2R3, -OR4 and -SR4, wherein: R2 and R3 are independently one of the other, a hydrocarbon group having 1 to 20, especially 1 to 12, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally comprising 1 to 5 heteroatoms chosen from N, 0, S, Si and P,

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 taken together with the nitrogen atom to which they are attached, can form a hydrocarbon heterocycle, saturated or unsaturated, having 3 to 10, especially 4 to 6 carbon atoms and optionally 1 to 5 other heteroatoms selected from N, 0, S, Si and P, said ring being optionally substituted with at least one hydrocarbon radical having 1 to 20, especially 1 to 15, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally containing 1 with 5 heteroatoms selected from N, O, S, Si and P; - R4 may represent a hydrocarbon group having 1 to 20, especially 1 to 15, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally halogenated or perhalogenated, especially by FI, Br and / or C1, and / or optionally comprising 1 to 5 heteroatoms chosen from N, O, S, Si and P.

dans lesquelles le cycle comportant N et X est un cycle saturé qui comprend au total 3 à 30 atomes, notamment 4 à 10 et encore en particulier 5,6 ou 7 atomes, inclus l'azote, le reste étant des atomes de carbone et/ou des hétéroatomes choisis parmi 0, S, Si, P et/ou des groupements choisis parmi-NH et-NR avec R représentant un radical hydrocarboné ayant 1 à 20, notamment 1 à 15, et en particulier 1 à 6 atomes de carbone, linéaire, ramifié ou cyclique, saturé ou insaturé, éventuellement comportant 1 à 5 hétéroatomes choisis parmi N, 0, S, Si et P; In this case R5 and R6 may represent, independently of one another, a group chosen from: - saturated cyclic aminoaryl groups of formula (IIa) or (IIb)

in which the ring comprising N and X is a saturated ring which comprises in total 3 to 30 atoms, in particular 4 to 10 and in particular 5, 6 or 7 atoms, including nitrogen, the remainder being carbon atoms and / or heteroatoms selected from O, S, Si, P and / or groups selected from -NH and -NR with R representing a hydrocarbon radical having 1 to 20, especially 1 to 15, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms selected from N, O, S, Si and P;

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a hydrocarbon group having 1 to 30, in particular 2 to 18, and in particular 3 to 12 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P; in particular a group chosen from -C6H4-CONR2R3, -C6H4-NR2R3 and -C6H4-OR4 with R2, R3 and R4 having the meanings given above;
In particular, R7 may represent a group chosen from: - (i) hydrocarbon groups having 1 to 30, in particular 1 to 18, and in particular 1 to 12 carbon atoms, branched or cyclic, saturated or unsaturated, optionally comprising 1 to Heteroatoms selected from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, especially by FI, Br and / or Cl; - (ii) halogen atoms, and especially FI, Br and / or Cl; (iii) CN-groups (nitrile), -COOH (carboxylate), -NO2 (nitro); N = N- (azo); = NH (imino); -CONH2 (amide); - (iv) a hydrogen atom; - (v) a group selected from -NR2R3, -OR4 or -SR4 with R2, R3 and R4 having the meanings given above; (vi) the radical R7 may additionally form, with one of the bonds "i", "j", "k", or "g, h" taken with the radical Ri, or "f taken with the radical Ri a saturated hydrocarbon ring having in total 3 to 8, in particular 4 to 7, and in particular 5 or 6 carbon atoms, optionally comprising 1 to 5 heteroatoms chosen from N, O, S, Si and P.

 In particular, R'1 can represent hydrogen or a hydrocarbon group having 1 to 30, especially 1-18, and in particular 1 to 12 carbon atoms, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, in particular by FI, Br and / or Cl.

In particular, R '2 represents hydrogen or a group chosen from -NO2, NR2R3 and -C (O) NR2R3, in which R2 and R3 represent, independently of one another, a hydrocarbon group having 1 to 20, especially 1 to 12, and in particular 1 to
6, carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally comprising 1 to 5 heteroatoms chosen from N, O, S, Si and P; taken together with the nitrogen atom to which they are attached, form a hydrocarbon heterocycle, saturated or unsaturated, having 3 to 10, especially 4 to 6 carbon atoms and optionally 1 to 5

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 other heteroatoms chosen from N, O, S, Si and P, said ring being optionally substituted with at least one hydrocarbon radical having 1 to 20, especially 1 to 15, and in particular 1 to 6, linear, branched or cyclic carbon atoms saturated or unsaturated, optionally containing 1 to 5 heteroatoms selected from N, O, S, Si and P.

et/ou - R5 et R6 représentent, indépendamment l'un de l'autre, soit (i) un groupement de formule (IIa) :

dans laquelle le cycle comportant N et X est un cycle saturé qui comprend au total 4 à 7 atomes, notamment 5 ou 6 atomes, inclus l'azote, et notamment 3 à 5 atomes de carbone et 0 ou 1 atome d'oxygène ; en particulier un groupement de formule:

It is more particularly possible to mention photochromic dyestuffs of formula (I) or (la) for which: R 1 represents hydrogen; or a -COOR group with R being a saturated hydrocarbon radical having 1 to 12, especially 1 to 6 carbon atoms, and in particular a methyl or ethyl radical; a group

and / or - R5 and R6 represent, independently of one another, either (i) a group of formula (IIa):

wherein the ring having N and X is a saturated ring which comprises in total 4 to 7 atoms, especially 5 or 6 atoms, including nitrogen, and especially 3 to 5 carbon atoms and 0 or 1 oxygen atom; in particular a group of formula:

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dans lesquelles R est un radical hydrocarboné saturé ayant 1 à 12, notamment 1 à 6 atomes de carbone, et notamment un radical méthyle ou éthyle ; R2 et R3 sont, indépendamment l'un de l'autre, un groupement hydrocarboné ayant 1 à 20, notamment 1 à 15, et en particulier 1 à 6 atomes de carbone, linéaire, ramifié ou cyclique, saturé ou insaturé, éventuellement comportant 1 à 5 hétéroatomes choisis parmi N, 0, S, Si et P; et/ou - R7 représente un atome d'hydrogène ou un groupement -NR2R3, avec R2 et R3 représentant, indépendamment l'un de l'autre, un groupement hydrocarboné saturé, linéaire ou ramifié, ayant 1 à 12, notamment 1 à 6 atomes de carbone, et notamment un groupement méthyle et/ou éthyle. or (ii) a hydrocarbon group having 5 to 14, especially 6 to 10 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally comprising 1 to 2 heteroatoms chosen from N, O or S; especially a group

in which R is a saturated hydrocarbon radical having 1 to 12, especially 1 to 6 carbon atoms, and especially a methyl or ethyl radical; R2 and R3 are, independently of one another, a hydrocarbon group having 1 to 20, especially 1 to 15, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally containing 1 with 5 heteroatoms selected from N, O, S, Si and P; and / or - R7 represents a hydrogen atom or a group -NR2R3, with R2 and R3 representing, independently of one another, a linear or branched, saturated hydrocarbon group having 1 to 12, especially 1 to 6 carbon atoms, and in particular a methyl and / or ethyl group.

Mention may also be made of organic dyes of formula (II) or (IIa) for which: R'1 represents hydrogen or a group-COOR with R being a saturated hydrocarbon radical having 1 to 12, in particular 1 to 6 carbon atoms, carbon, and especially a methyl or ethyl radical; and / or - R5 and R6 represent, independently of one another, either (i) a group of formula (IIa):

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soit (ii) un groupement hydrocarboné ayant 5 à 14, notamment 6 à 10 atomes de carbone, linéaire, ramifié ou cyclique, saturé ou insaturé, éventuellement comportant 1 à 2 hétéroatomes choisis parmi N, 0 ou S; en particulier un groupement :

dans lesquelles R est un radical hydrocarboné saturé ayant 1 à 12, notamment 1-6 atomes de carbone, et notamment un radical méthyle ou éthyle ; etR2 et R3 sont, indépendamment l'un de l'autre, un groupement hydrocarboné ayant 1 à 20, notamment 1 à 15, et en particulier 1 à 6 atomes de carbone, linéaire, ramifié ou cyclique, saturé ou insaturé, éventuellement comportant 1 à 5 hétéroatomes choisis parmi N, 0, S, Si et P; et/ou - R'2 représente l'hydrogène, ou un groupement-NR'R" avec R' et R", identiques ou différents, représentant un groupement hydrocarboné saturé, linéaire ou ramifié, ayant 1 à 12, notamment 1 à 6 atomes de carbone, et notamment un groupement méthyle et/ou éthyle ; ou un groupement

wherein the ring having N and X is a saturated ring which comprises in total 4 to 7 atoms, especially 5 to 6 atoms, including nitrogen, and especially 4 to 5 carbon atoms and 0 or 1 oxygen atom; in particular a group of formula:

or (ii) a hydrocarbon group having 5 to 14, especially 6 to 10 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally comprising 1 to 2 heteroatoms chosen from N, O or S; in particular a grouping:

in which R is a saturated hydrocarbon radical having 1 to 12, especially 1-6 carbon atoms, and in particular a methyl or ethyl radical; andR2 and R3 are, independently of one another, a hydrocarbon group having 1 to 20, especially 1 to 15, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally comprising 1 with 5 heteroatoms selected from N, O, S, Si and P; and / or R'2 represents hydrogen, or a group-NR'R "with R 'and R", which are identical or different, representing a linear or branched saturated hydrocarbon group having 1 to 12, especially 1 to 6 carbon atoms, and in particular a methyl and / or ethyl group; or a group

Representative and non-limiting examples of naphthopyrane-type dyes that may be mentioned are those described in WO94 / 22850, WO98 / 45281 and WO00 / 18755.

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The following compounds are particularly suitable for the invention:
3,3-di (4-methoxyphenyl) -6-morpholino-3H-naphtho [2,1-b] pyran having the formula:

3-phenyl-3- (4-morpholinophenyl) -6-morpholino-3H-naphtho [2,1-b] pyran of formula:

3-phenyl-3- (4-piperidinophenyl) -6-morpholino-3H-naphtho [2,1-b] pyran of formula:

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3-phenyl-3- (4-piperidinophenyl) -6-carboxymethyl-9-N-dimethyl-3H-naphtho [2,1b] pyran of formula:

et leurs mélanges. 2-phenyl-2- (4-piperidinophenyl) -5-carboxymethyl-9-N-dimethyl-2H-naphtho [1,2-b] pyran of formula:

and their mixtures.

GONIOCHROMATIC COLORING AGENTS
For the purpose of the present invention, the term "gionochromatic coloring agent" denotes a coloring agent which makes it possible to obtain, when the composition containing it is spread on a support, a color path in the plane a * b * of the colorimetric space. CIE 1976 which corresponds to a variation Dh of the angle of the hue h of at least 20 when the angle of observation is varied with respect to the normal between 0 and 80, for an angle of incidence of the light of 45.

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 The color path can be measured for example by means of an INSTRUMENT SYSTEMS spectrogoniorflectometer and GON 360 GONIOMETER reference, after the cosmetic composition has been spread in the fluid state with a thickness of 300 m by means of a automatic spreader on an ERICHSEN brand contrast card and Typ 24/5, the measurement being made on the black background of the card.

 The gioniochromatic coloring agent may be present for example in an amount that may vary, by weight relative to the total weight of the composition containing it, from 0.1 to 60%, even from 1 to 20% or from 2 to 15%, and better from 2 to 10%, especially for a composition intended to be applied to the lips. A nail polish composition may contain, for example, between 0.1% and 5% of goniochromatic coloring agent; a foundation may contain from 10 to 15% and a lipstick may contain from 2 to 8% by weight.

 The gionochromatic coloring agent may be selected to have a relatively large color change with the viewing angle.

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

 In the case of a multilayer structure, this may comprise for example at least two layers, each layer, independently or not of the other layer (s) being made for example from at least one material selected from the group consisting of the following materials: MgF 2, CeF 3, ZnS, ZnSe, Si, SiO 2, Ge, Te, Fe 2 O 3, Pt, Va, Al 2 O 3, MgO, Y 2 O 3, S 2 O 3, SiO, HfO 2, ZrO 2, CeO 2, Nb 2 O 5, Ta 2 O 5, TiO 2, Ag, Al, Au, Cu, Rb, Ti, Ta, W, Zn, MoS 2, cryolite, alloys, polymers and their combinations.

 As for the goniochromatic liquid crystal particles that may be used in the composition according to the invention, they may in particular be based on a polymer that can be obtained by polymerization of a monomer mixture comprising: a) at least one first monomer A of formula (I) Y1-A1-M1-A2-Y2 in which -i) Y1 and Y2, which may be identical or different, represent a polymerizable group chosen from acrylate or methacrylate groups, an epoxy group, a group isocyanate, hydroxy, vinylether (-O-CH = CH2) or vinylester (-CO-O-CH = CH2), and

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 ii) Al and A2, which may be identical or different, represent a group of formula -CnH2n-, in which n is an integer ranging from 0 to 20 and one or more methylene groups of said -CnH2n- group may be replaced by one or more oxygen atoms, and iii) M1 denotes a group of general formula (I ') -R1-X1-R2-X2-R3-X3-R4-, in which R1, R2, R3 and R4, which are identical or different, denote a divalent group selected from -O-, -COO-, -CONH-, -CO-, -S-, -C # C-, -CH = CH-, -N = N-, -N = N (O) ) -, and -R2-X2-R3- or -R2-X2- or -R2-X2-R3-X3- may also be a single covalent bond, and X1, X2, X3 are groups, identical or different, chosen among the 1,4-phenylene and 1,4-cyclohexylene groups, the arylene or heteroarylene groups having an aryl ring comprising from 6 to 10 atoms optionally substituted with B1 and / or B2 and / or B3, said heteroarylene containing from 1 to 3 heteroatoms selected from 0, N and S atoms, the cycloalkylene groups having 3 to 10 carbon atoms optionally substituted with -BI and / or-B2 and / or -B3, -BI, -B2, and -B3, which may be identical or different, are chosen from C1-C4 alkyl groups; C 20, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylcarbonyl, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthiocarbonyl, -OH, -F, -Cl, -Br, -I, -CN, -NO2, formyl, acetyl, and alkyl, alkoxy or alkylthio groups having from 1 to 20 carbon atoms, interrupted by one or more oxygen atom (s) or one or more atom (s) sulfur or one or more ester groups, and - b) at least one second chiral monomer B of formula (II) V1-A'1-W1-Z-W2-A'2-V2, wherein - i) VI and V2, which may be identical or different, denote a group chosen from an acrylate or methacrylate group, an epoxy group, a vinylether or vinylester group, an isocyanate group, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group or an alkylthio group. C1-C20, a (C1-C20) alkoxycarbonyl l, a (C 1 -C 20) alkyl thiocarbonyl, -OH, -F, -Cl, -Br, -I, -CN, -NO 2, formyl, acetyl and alkyl, alkoxy or alkylthio groups having from 1 to 20 atoms of carbon, and interrupted by one or more atom (s) or one or more sulfur atom (s) or one or more ester group (s) (-CO-O-),

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 and at least VI or V2 denotes a polymerizable group chosen from acrylate or methacrylate groups, an epoxy group, an isocyanate group, hydroxy, vinylether (-O-CH = CH 2) or vinylester (-CO-O-CH = CH 2), ii) A'1 and A'2, identical or different, represent a group of formula -CnH2n-, in which n is an integer ranging from 0 to 20 and one or more methylene groups of said group CnH2n can be replaced by one or more oxygen atoms, and - iii) Wlet W2 denote a divalent group of general formula R'1-X'1-R'2-X'2-R'3- in which R'1, R'2 and R ' 3, which are identical or different, denote a divalent group chosen from -O-, -COO-, -COH-, -CO-, -S-, -C # C-, -CH = CH-, -N = N-, -N = N (O) -, and R'1, R'2, R'3 or R'2-X'2 can also be a simple covalent bond, and X'1 and X'2 are identical groups or different, selected from 1,4-phenylene, 1,4-cyclohexylene, arylene or hetero groups oarylenes having an aryl ring comprising from 6 to 10 atoms optionally substituted with B'1 and / or B'2 and / or B'3, said heteroarylene containing from 1 to 3 heteroatoms selected from 0, N and S atoms, cycloalkylene groups having from 3 to 10 carbon atoms optionally substituted with -B'1 and / or -B'2 and / or -B'3, -B'1, -B'2, and -B'3, which may be identical or different, being chosen from C1-C20alkyl, C1-C20alkoxy, C1-C20alkylthio, (C1-C20) alkylcarbonyl, (C1-C20) alkoxycarbonyl, (C1-C20) alkylthiocarbonyl, -OH, -F, -Cl, -Br, -I, -CN, -NO2, formyl, acetyl, and alkyl, alkoxy or alkylthio groups having from 1 to 20 carbon atoms, interrupted by one or more atom (s) or a or more than one sulfur atom (s) or one or more group (s) and Z denotes a divalent chiral group comprising at least 4 carbon atoms, in particular from 4 to 20 carbon atoms, and more preferably from 4 to 10 carbon atoms, ( the chiral group divalent comprenan at least one asymmetric carbon, in particular one or two asymmetric carbons, and in particular two asymmetric carbons) and in particular a divalent chiral group derived from the group of dianhydrohexites, hexoses, pentoses, binaphthyl derivatives (binaphthyl groups), biphenyl derivatives ( biphenyl groups), tartaric acid derivatives or optically active glycols.

 Preferably, the liquid crystal polymer is obtained by polymerization of a monomer mixture comprising:

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- a) at least one first monomer A of formula (I) Y 1 -A 1 -M 1 -A 2 -Y 2 in which -i) Y 1 and Y 2, which may be identical or different, represent an acrylate or methacrylate group, preferably a group acrylate; ii) Al and A2, which may be identical or different, represent a group of formula -CnH2n-, in which n is an integer ranging from 1 to 20, preferably ranging from 2 to 6, and more preferably equal to 4; iii) MI denotes a group of general formula (I ') -Ri-Xi-R2-X2-R3-X3-R4-, in which R1 and R4 denote -O-, R2 and R3 denote -COO-, and X1 X2, X3 are a 1,4 phenylene group, the carbonyl group -CO respectively of R2 and R3 being respectively linked to the group XI, X3, and - b) at least one second chiral monomer B of formula (II) V1-W1 -Z-W2-V2, wherein - i) VIdisigne an acrylate or methacrylate group, and preferably an acrylate group, and V2 denotes a C1-C20 alkyl group, a C1-C20 alkoxy, a C1-C20 alkoxy ) carbonyl, -OH, and preferably denotes a C1-C20 alkoxy group, especially C1-C4, and in particular a methoxy group; ii) Wrepresents a divalent group of formula -X '1 -CO-O-,
W2 represents a divalent group of formula -O-CO-X'1-, in which X'1 denotes a 1,4-phenylene group, and Z denotes a chiral group with two bonds, derived from the dianhydrohexite group, in particular a divalent radical of formula:

Preferably, the monomer mixture comprises from 70 to 99% by weight of monomer A and from 1 to 30% by weight of monomer B, based on the total weight of monomer A and monomer B, and better comprises from 90 to 95% by weight. % by weight of monomer A and 5 to 10% by weight of monomer B.

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 Preferably, the concentration of the polymerizable groups present in the mixture of monomer A and monomer B (polymerizable groups Y1, Y2 of monomer A and polymerizable groups VI, V2 of monomer B) ranges from 3.2 to 15 mmol / g.

 According to a particular embodiment of the invention, the liquid crystal polymer is such that the mixture of monomer A and monomer B comprises polymerizable groups, at least 90% of which are present in monomers having at least two polymerizable groups, in a concentration ranging from 3.2 to 15 mmol / g.

 In particular, the liquid crystal polymer essentially comprises or consists of a mixture of the monomers A and B defined above.

 The liquid crystal polymer has in particular a helical pitch greater than 450 nm, especially ranging from 455 nm to 5000 nm, in particular ranging from 455 nm to 1000 nm, or even ranging from 455 nm to 650 nm.

 The monomer A may have a weight average molecular weight ranging from 150 to 800, and especially ranging from 460 to 625. The monomer A may in particular be an unsubstituted hydroquinone dibenzoate derivative.

 The monomer B may have a weight average molecular weight ranging from 500 to 1000, and especially ranging from 500 to 700.

 The liquid crystal polymer may have a weight average molecular weight of less than 625.

 The liquid crystal polymer defined above can be prepared according to the methods known in the state of the art, such as those described in documents US Pat. No. 5,356,215 and US Pat. No. 5,807,497, from the monomer mixture described above.

 The polymerization of the oriented monomer mixture may, in an already known manner, be carried out, for example, in a radical manner with the use of commercial thermal initiators, using electron rays or UV light in combination with commercial photoinitiators. or by addition or condensation reactions.

 The crosslinking of the monomer mixtures, in the chiral structural state, is preferably carried out by means of a polycreaction which, depending on the type of the polymerizable groups, polycondensable or polyadditionable, takes place in the form of a radical polymerization, ionic or catalyzed to the metal, or a polycondensation reaction or a polyaddition reaction.

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 The initiation of the radical polymerization can be carried out by means of corresponding initiators or by UV radiation, using commercial photoinitiators or by high energy radiation, such as electron radiation. An advantage of the radical polymerization of the radicals or of the polymerization via electron beam hardening is that the polymerizable mixture can also be added a light-protecting agent, such as a UV absorber ( UVA) or radical scavengers (HALS), for stabilizing the resulting pigments or films against UV light, for example for outdoor applications, without causing losses in the polymerization conversion, as is the case during UV curing, because of the screening effect of the photoinitiator by a UVA. There is thus no reduction in the crosslinking density.

 If the curing of the films is peroxidic or by electron radiation, the monomer mixture preferably contains commercially available light-shielding agents, such as UV absorbers or radical scavengers, in one form. overall concentration of 0.5 to 5% by weight.

 In addition to light stabilizers, the monomer mixtures may also contain other conventional additives for inhibiting oxidation, inhibiting polymerization, or additives to improve rheological properties. In addition, absorbent fillers, such as pigments or soot, as well as fluorescent dyes or pigments may be contained.

 The film obtained after the polymerization is then ground into particles, especially in the form of platelets.

 Preferably, the liquid crystal polymer particles have a larger size ranging from 1 m to 3 mm, and preferably from 30 m to 500 m. These particles are advantageously in the form of platelets.

 The particles can be separated (sorted) by a grain size selective process.

 Such polymers and their particles are described in application EP-A-1046692.

 Examples of liquid crystal polymer particles that may be used are those known under the name CTFA Polyacrylate-4 and sold under the names HELICONE # HC Sapphire, HELICONE # HC Scarabeus, HELICONE #

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 HC Jade, HELICONE # HC Maple, HELICONE # HC XL Sapphire, HELICONE # HC XL Scarabeus, HELICONE # HC XL Jade, HELICONE # HC XL Maple by WACKER.

 The particles of the liquid crystal polymer may be present in the product according to the invention at a content ranging from 0.01% to 99% by weight, relative to the total weight of the composition containing them, in particular ranging from 0.1% 60% by weight, in particular ranging from 1% to 30% by weight, and even ranging from 5% to 15% by weight.

OTHER COLORFUL MATERIALS
Within the meaning of the present invention, it is intended to cover, under this term, the so-called non-photochromic dyestuffs in the sense of the present invention and non-goniochromatic and more particularly any compound chosen from fat-soluble and water-soluble monochromatic dyes, nacres and reflective particles.

Monochrome fat-soluble and water-soluble dyes
The first and / or second composition (s) may further comprise at least one monochromatic dye, in particular a natural organic dye such as cochineal carmine, and / or a synthetic dye such as halo-acid, azo dyes, anthraquinone. Mention may also be made of mineral dyes such as copper or iron sulphate. Other examples include Sudan Brown, Sudan Red and Annatto, as well as beet juice, carotene and methylene blue.

 The dye may be present in the composition in question, alone or as a mixture, in an amount of from 0.001 to 15% by weight, and especially from 0.01 to 5% by weight and in particular from 0.1 to 2% by weight, relative to total weight of ladites composition.

Pigments
By pigments, it is necessary to include white or colored particles, mineral or organic, intended to color and / or opacify the composition.

 Pigments may be present in the first and / or second composition (s) in particular in a proportion of from 0.01 to 25% by weight of the composition in question, and preferably in a proportion of 3 to 10% by weight.

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 They can be white or colored, mineral or organic, of usual size or nanometer. They can be in the form of powder or pigment paste. There may be mentioned oxides of titanium, zirconium or cerium, as well as oxides of zinc, iron or chromium, ferric blue, chromium hydrate, carbon black, ultramarines (polysulfides of aluminosilicates) , manganese pyrophosphate and some metal powders such as silver or aluminum. Mention may also be made of D & C pigments and lacquers commonly used to give the lips and the skin a make-up effect, which are salts of calcium, barium, aluminum, strontium or zirconium.

Mother-of-pearl
By nacres, it is necessary to understand iridescent particles which reflect the light, in particular produced by some shellfish in their shell or else synthesized.

 Nacres may be present in the first and / or second composition (s) in particular at a rate of from 0.01 to 20% by weight, preferably at a rate of about 3 to 10% by weight relative to the weight total of the composition under consideration. Among the nacres that can be envisaged, mention may be made of natural mother-of-pearl, mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride, and with colored titanium mica.

Reflective particles
For the purposes of the present invention, the term "reflective particles" denotes particles whose size, structure, in particular the thickness of the layer or layers constituting it and their physical and chemical nature, and the surface state, enable them to to reflect the incident light with sufficient intensity to be able to create on the surface of the claimed composition, when the latter is applied to the support to be made up, highlight points visible to the naked eye, that is to say brighter points that contrast with their surroundings while appearing to shine.

 Reflective particles may be present in the first and / or second composition (s) by being dispersed in a homogeneous manner for example at a content ranging from 0.1% to 20% relative to the total weight of the composition, in particular from 1 % at

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 15% by weight, and in particular from 1% to 10% by weight, for example about 2%, especially for a composition intended to be applied to the lips.

 Reflective particles which allow a metallic reflection of the incident light are particularly suitable. This is particularly the case when the reflective particles allow whatever their shape, a reflection on a layer of a metal, for example money. Such particles are relatively neutral with respect to the color of the composition.

 Reflective particles that can be used in the invention, with a metallic or white sheen, can for example reflect light in all visible components without significantly absorbing one or more wavelengths. The spectral reflectance of these reflective particles may, for example, be greater than 70% in the range 400-700 nm, and in particular at least 80%, even 90% or even 95%.

 The light reflected by the reflective particles may be non-iridescent, especially in the case of a metallic reflection.

 Reflective particles of any shape may have a multilayer structure or not and, in the case of a multilayer structure, for example at least one layer of uniform thickness, including a reflective material.

 The reflective material may include a layer of metal or a metal compound.

 Particles of glass coated with a metal layer are described in particular in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460, JP-A-05017710.

 The first and / or second composition (s) further comprise at least one photochromic compound but distinct from those considered according to the invention, that is to say generally characterized by a #E <5 and, where appropriate, a insolubility in the composition under consideration. Mention may in particular be made of mineral photochromic compounds, and more particularly doped aluminosilicates such as halogen doped sodalite, or metal oxides or hydrates such as titanium oxides rendered photochromic with the aid of a metal chosen from iron , chromium, copper, nickel, manganese, cobalt, molybdenum, as such or in salt form such as sulfate, chlorate, nitrate, acetate. Such a photochromic compound can be incorporated into the

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 first composition and / or the second composition (s) an amount of 0.001 to 20% by weight relative to the total weight of the composition in question, especially in an amount of 0.1 to 10% by weight.

PHYSIOLOGICALLY ACCEPTABLE ENVIRONMENT
The physiologically acceptable media of each of the compositions composing the product according to the invention will be adapted to the nature of the makeup to be applied, the nature of the surface to be made up or treated on which the product is to be applied and to the form in which the product is intended to be conditioned, especially solid or fluid at ambient temperature and atmospheric pressure.

 The first and / or second composition (s) produced according to the invention may comprise at least one aqueous phase and / or at least one fatty phase.

 The first and / or second composition (s) of the product according to the invention may be anhydrous, or may also comprise an aqueous phase, which may comprise water, floral water such as cornflower water and / or mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water.

 Said aqueous phase may comprise from 0.1 to 14% by weight, relative to the total weight of the aqueous phase, of a C2-C6 monoalcohol, such as ethanol, propanol, butanol, isopropanol and isobutanol.

 Oils Generally, the first and / or second composition (s) produced according to the invention comprise at least one oily phase which may comprise one or more cosmetically acceptable oils.

 By cosmetically acceptable oil according to the invention is meant any liquid fat at 25 C, 1 atm, and having a molecular weight greater than or equal to 160, especially between 170 and 106, or even between 200 and 5. 105, compatible with an application on the skin, mucous membranes (lips) and / or integuments (nails, eyelashes, eyebrows, hair).

 Preferably, the oily phase is macroscopically homogeneous, that is to say homogeneous with the naked eye.

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 The oily phase may comprise one or more oils, which may be polar or apolar, volatile or non-volatile, and preferably hydrocarbon-based.

 By polar oil is meant an oil composed of chemical compounds comprising at least one polar group. The polar groups are well known to those skilled in the art: they may in particular be groups of the alcohol, ester or carboxylic acid type.

 In particular, the polar oils according to the invention can be defined as having an average solubility parameter 8a according to the Hansen solubility space, at 25 ° C, of: #a> 5.0 (J / cm3) '/ 2 .

 Polar oils include the rather polar oils which have an average solubility parameter at 25 C of: 5.0 # 7.0 (J / cm 3), and the frankly polar oils which have an average solubility parameter of 25.0. C of: 8a> 7.0 (J / cm 3).

 In the same way, apolar oils within the meaning of the invention have a mean solubility parameter δa according to the Hansen solubility space, at 25 ° C., of: 0 δ 8a <5.0 (J / cm 3).

 Non-polar oils within the meaning of the invention include the substantially apolar oils (6a = 0) and the low polar oils which have an average solubility parameter at 25C of: 0 <8a <5.0 (J / cm3).

 Thus, the higher the value of 8a, the higher the polarity of the oil.

 The definition and calculation of the solubility parameters in the HANSEN three-dimensional solubility space are described in the article by C. M. Hansen: "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967).

According to this Hansen space: #D characterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular shocks; - #p characterizes the DEBYE interaction forces between permanent dipoles as well as the KEESOM interaction forces between induced dipoles and permanent dipoles; - 8h characterizes the specific interaction forces (hydrogen bond, acid / base, donor / acceptor type, etc.); - δa is determined by the equation: 8a = (# p2 + ôh2)
The parameters 8p, 8h, 8D and 8a are expressed in (J / cm3).

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 When the oily phase is a mixture of different oils, the solubility parameters of the mixture are determined from those of the compounds taken separately, according to the following relations: #Dmel = # xi #Di = xi 8pi = # xi 8hi #Dmel = Z xi #Di; # = Z if #pi and # = Z if #hi #amel = (# 2pmel + 8 hmel) l / 2 where xi represents the volume fraction of compound i in the mixture.

 It is within the abilities of those skilled in the art to determine the amounts of each oil to obtain an oily phase satisfying the desired criteria.

 According to a first embodiment of the invention, the oily phase is polar and may comprise mainly, or even exclusively, one or more polar oils (rather or substantially polar) in a mixture, which can therefore represent 5 to 100% by weight, in particular from 10 to 90%, even from 15 to 60% and in particular from 20 to 50% by weight of the total weight of said oily phase.

 According to this first embodiment, the polar oily phase has an average solubility parameter 8a according to the Hansen solubility space, at 25 ° C., greater than or equal to 5.0 (J / cm 3), in particular greater than or equal to 5.3 , or even greater than or equal to 5.5 and even better than or equal to 6.0 (J / cm3), or even greater than or equal to 7.0 (J / cm3).

 According to a second embodiment of the invention, the oily phase is apolar and can comprise from 5 to 100% by weight, especially from 10 to 90%, or even from 15 to 60% and in particular from 20 to 50% by weight. one or more apolar oils (apolar or slightly polar); it has an average solubility parameter 8a according to the solubility space of Hansen, at 25 ° C., less than 5.0, especially less than or equal to 4.9, more preferably less than or equal to 4.5, and even more preferably less or equal to 4.0 (J / cm3).

 The oils that may be used in the oily phase may be chosen from, alone or as a mixture, oils of animal, vegetable, mineral or synthetic origin; volatile or not.

 The term "volatile oil" means the oils having, at 25 ° C., a vapor pressure of between 0.02 and 300 mmHg (evening 2.66 at 40000 Pa). Preferably, volatile oils are used whose flash point is of the order of 30-100 C.

 These include:

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 animal or vegetable oils, in particular formed by esters of fatty acids and polyols, in particular liquid triglycerides, for example sunflower, corn, soya, squash, grape seed, sesame, hazelnut, apricot, almond or avocado; fish oils, tricaprocaprylate of glycerol, or vegetable or animal oils of formula R1COOR2 in which R1 represents the residue of a higher fatty acid having 7 to 19 carbon atoms and R2 represents a branched hydrocarbon chain containing from 3 to 20 carbon atoms, for example, Purcellin oil; paraffin oil, petroleum jelly, calophyllum, macadamia, rapeseed, copra, peanut, palm, castor oil, jojoba, olive or cereal sprouts; shea butter; perhydrosqualene; esters and synthetic ethers, in particular of fatty acids, for example oils of formula R1COOR2 in which R1 represents the residue of a higher fatty acid containing from 7 to 29 carbon atoms and R2 represents a hydrocarbon-based chain containing from 3 to at 30 carbon atoms such as isopropyl myristate, 2-ethylhexyl palmitate, octyl-2-dodecyl stearate, octyl-2-dodecyl erucate, isononanoate isononyl, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate; pentaerythritol esters such as pentaerythritol tetraisostearate; esters of the tridecyl trimellitate type; fatty alcohols in particular having from 12 to 26 carbon atoms, such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol and oleyl alcohol; linear or branched hydrocarbons of mineral or synthetic origin, such as paraffin oils and their derivatives, petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam; isoparaffins such as isohexadecane and isodecane; glycerides and in particular acetylglycerides or triglycerides of fatty acids having 4 to 10 carbon atoms, such as the triglycerides of heptanoic acid, octanoic acid and capric / caprylic acid,

<Desc / Clms Page number 33>

 - and their mixtures.

 Particularly preferred polar oils include octyldodecanol, hexyldecanol, octyldecanol, oleic alcohol, castor oil, diisostearyl malate, glyceryl triheptanoate, glyceryl trioctanoate, triglyceride, and the like. capric / caprylic acids, triisononanoïn, tridecyl trimellitate, and mixtures thereof.

 Among the particularly preferred apolar oils include aliphatic hydrocarbons including C6-C40 such as paraffin oils, volatile, such as isohexadecane or isododecane, or non-volatile, and derivatives thereof; petroleum jelly, hydrogenated or non-hydrogenated polydecenes, hydrogenated polyisobutene such as Parleam oil, squalane, polybutylenes, isononyl isononanoate; fluorinated oils, especially perfluorinated oils, and mixtures thereof.

The following oils may especially be mentioned:

<Tb>
<tb> Sa <SEP> (J / cm3)
<tb> oil <SEP> of <SEP> ricinus <SEP> 9.09
<tb> 2-hexyldecanol <SEP> 8.55
<tb> alcohol <SEP> oleic <SEP> 8,17
<tb> octyldodecanol <SEP> 7.69
<tb> triglyceride <SEP> of <SEP><SEP> heptanoic acid <SEP> 7.29
<tb> diisostearyl malate <SEP> 7.19
<tb> triglyceride <SEP> of <SEP><SEP> octanoic acid <SEP> 6.87
<tb> triglyceride <SEP><SEP> acids <SEP> capric / caprylic <SEP> 6.69
<tb> Triisononanoïne <SEP> 6.54
<tb> Trimellilate <SEP> of <SEP> tridecylate <SEP> 5.35
<tb> isononyl isononanoate <SEP><SEP> 4.87
<tb> Polyisobutene <SEP> hydrogenated <SEP> 0
<tb> Isododecane <SEP> 0
<Tb>

The oily phase is preferably chosen so that the photochromic dye (s) are in the absence of soluble, dispersible as such, that is to say without surface treatment annex.

<Desc / Clms Page number 34>

 The oily phase is preferably in an amount of 1 to 99% by weight, especially 10 to 90% by weight, preferably 15 to 80% by weight, relative to the total weight of the composition in question.

 The first and / or second composition (s) produced according to the invention may furthermore comprise other fatty substances than the above oils, which may be chosen by those skilled in the art on the basis of their general knowledge, in order to give the final product the desired properties, for example in consistency and / or texture.

 These additional fatty substances may be waxes, gums and / or pasty fatty substances of animal, vegetable, mineral or synthetic origin, and mixtures thereof.

 A wax, within the meaning of the present invention, is a lipophilic fat compound, solid at room temperature (25 C), with reversible solid / liquid state change, having a melting point greater than 40 C and up to 200 C, generally a hardness greater than 0.5 MPa, and having in the solid state an anisotropic crystalline organization.

 Mention may be made in particular of waxes of animal, vegetable, mineral or synthetic origin, such as microcrystalline waxes, paraffin wax, petrolatum, petroleum jelly, ozokerite, montan wax; beeswax, lanolin wax and its derivatives; Candelilla wax, Ouricury wax, Carnauba wax, Japan wax, cocoa butter, cork fiber or sugar cane wax, lignite wax, rice bran wax, fir wax, cotton wax; hydrogenated oils having a melting temperature above about 40 C (about), such as hydrogenated jojoba oil; fat esters and glycerides concretes at 25 C; polyethylene waxes and waxes obtained by Fischer-Tropsch synthesis; hydrogenated oils that are solid at 25 ° C .; lanolines.

 The pasty fatty substances generally have a melting point of between 25 and 60 [deg.] C., preferably between 30 and 45 [deg.] C., and / or a hardness of between 0.001 and 0.5 MPa, preferably between 0.005 and 0.4 MPa. There may be mentioned lanolines and their derivatives, or cholesterol esters.

 These additional fatty substances may be present in an amount of 0.1 to 50% by weight, especially 3 to 40% by weight, more preferably 5 to 30% by weight, relative to the total weight of the composition in question.

<Desc / Clms Page number 35>

surfactants
The first and / or second composition (s) of the product according to the invention may optionally comprise a surfactant, especially when they are in the form of an emulsion, in particular in an amount of 0.01 to 30% by weight per relative to the total weight of the composition containing them.

 The alkali salts, ammonium salts, amine salts or aminoalcohol salts of the following compounds may be mentioned, alone or as a mixture, of the following compounds: alkyl sulphates, alkyl ether sulphates, alkyl sulphates and ether sulphates, alkylaryl polyethersulphates, monoglyceride sulphates , alkylsulphonates, alkylamides sulphonates, alkylaryl sulphonates, a-olefin sulphonates, paraffin sulphonates, alkyl sulphosuccinates, alcoyléthersulfosuccinates, alkylamides sulfosuccinates, alcoylsulfosuccinamates, alcoylsulfoacétates, alcoylpolyglycérol carboxylates, alkyl phosphates / alcoylétherphosphates, acyl sarcosinates, alcoylpolypeptidates, alcoylamidopolypeptidates, acyl isethionates, alcoyllaurates. The alkyl or acyl radical in all these compounds generally refers to a chain of 12 to 18 carbon atoms.

 Mention may also be made of soaps and salts of fatty acids such as oleic, ricinoleic, palmitic or stearic acids, coconut oil acids or hydrogenated coconut oil acids and especially amine salts such as stearates. amine; acyl lactylates, the acyl radical of which comprises 8-20 carbon atoms; carboxylic acids of polyglycol ethers.

 Mention may also be made of fatty-chain polyethoxylated, polypropoxylated or polyglycerolated alcohols, alkyl phenols and fatty acids containing 8 to 18 carbon atoms; copolymers of ethylene oxide and propylene oxide, condensates of ethylene oxide and propylene oxide on fatty alcohols, polyethoxylated fatty amides, polyethoxylated fatty amines, ethanolamides, glycol fatty acid esters, fatty acid esters (stearate, oleate) of sorbitan, oxyethylenated or otherwise, sucrose fatty acid esters, polyethylene glycol fatty acid esters (monostearate or polyethylene glycol monolaurate); phosphoric triesters, fatty acid esters of glucose derivatives; alkylpolyglycosides and alkylamides of amino sugars; condensation products of an α-diol, a monoalcohol, an alkylphenol, an amide or diglycolamide with glycidol or a glycidol precursor.

<Desc / Clms Page number 36>

 Trioleyl phosphate may also be mentioned; fatty acid ester of polyols such as mono-, di-, tri- or sesquiolates or stearates of sorbitol or glycerol, laurates of glycerol or polyethylene glycol; alkyl or alkoxy dimethicone copolyols having an alkyl or pendant alkoxy chain or a silicone backbone having, for example, from 6 to 22 carbon atoms; polyoxyethylenated (lauryl, cetyl, stearyl, octyl) ethers and dimethicone copolyols.

 Thickening agent The first and / or second composition (s) produced according to the invention may also comprise one or more thickening agents, for example in concentrations of 0.01 to 6% by weight relative to the total weight of the composition. or containing them.

 The thickening agent may be chosen from, alone or as a mixture: polysaccharide biopolymers such as xanthan gum, locust bean gum, guar gum, alginates, modified celluloses such as hydroxyethylcellulose, methylcellulose, hydroxypropylcellulose and carboxymethylcellulose, starch derivatives, cellulose ether derivatives having quaternary ammonium groups, cationic polysaccharides; synthetic polymers such as polyacrylic acids such as poly (meth) acrylate glyceryl polymers such as HISPAGEL or LUBRAGEL from the companies HISPANO QUIMICA or GARDIAN, polyvinylpyrrolidone, polyvinyl alcohol, crosslinked polymers of acrylamide and ammonium acrylate such as PAS 5161 or BOZEPOL C from HOECHST; acrylate / octyl-acrylamide copolymers such as National Starch's Dermacryl; polyacrylamide-based polymers such as SEPIGEL 305 from SEPPIC, crosslinked polymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride such as SALCARE SC 92 from ALLIED COLLOIDS, magnesium aluminum silicate; optionally modified clays, such as hectorites modified with a C10-C22 fatty acid ammonium chloride, such as hectorite modified with di-stearyl-dimethyl ammonium chloride; - optionally modified silica;

<Desc / Clms Page number 37>

 galactomannans containing from one to six and better still from two to four hydroxyl groups per sac, substituted by a saturated or unsaturated alkyl chain, such as guar gum alkylated by C1-C6 alkyl chains and better still C1-C3 and more particularly ethyl guar having a degree of substitution of 2 to 3 such as that sold by Aqualon under the name N-HANCE-AG; cellulose derivatives such as ethylcellulose.

 block copolymers, in particular of the "diblock" or "triblock" type, of the polystyrene / polyisoprene, polystyrene / polybutadiene, polystyrene / copoly (ethylene-butylene) or polystyrene / copoly (ethylene-propylene) type, sold under the name of 'Kraton' by Shell Chemical; polymers of the polyamide type, for example comprising a polymer backbone having amide repeating units, and optionally at least one pendant fatty chain and / or at least one optionally functionalized terminal chain, having from 8 to 120 carbon atoms and being linked to these amide units, among which mention may be made of the commercial products sold by Arizona Chemical under the names Uniclear 80 and Uniclear 100 which are a mixture of copolymers of a C36 diacid condensed on ethylene diamine, having a mean molecular mass of approximately 6000 weight, the terminal ester groups resulting from the esterification of the remaining acid termini by cetyl alcohol, stearyl alcohol or mixtures thereof (also known as cetylstearyl alcohol).

Film-forming polymer
Depending on the intended application, the first and / or second composition (s) produced according to the invention may further comprise at least one film-forming polymer.

 This is generally the case when it is desired to prepare a product such as nail polish or lip lacquer.

 Among the film-forming polymers that may be used in the product of the present invention, mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin, and mixtures thereof.

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

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

<Desc / Clms Page number 38>

 of these acid monomers and / or amides of these acidic monomers such as α, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid.

 The vinyl film-forming polymers can also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters such as vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and t-butyl benzoate. vinyl and styrene monomers such as styrene and alpha-methyl styrene. In particular, these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above.

 Among the film-forming polycondensates, mention may be made of polyurethanes, polyesters, polyester amides, polyamides, and epoxy ester resins, polyureas.

 The polymers of natural origin, which may be modified, may be chosen from shellac resin, sandarac gum, dammars, elemis, copals, water-insoluble cellulosic polymers, such as nitrocellulose or cellulose acetate. cellulose acetate butyrate, cellulose acetate propionate, ethyl cellulose, and mixtures thereof.

 The polymers may be dissolved or dispersed in the cosmetically acceptable medium of the first and / or second composition. The polymers may be present at a content ranging from 0.01% to 40% by weight relative to the total weight of the composition containing them.

 The first and / or second composition (s) produced according to the invention may also comprise a plasticizer chosen from the usual plasticizers and which may be present at a content ranging from 0.1 to 40% by weight relative to the total weight of the composition containing it.

 Charging The first and / or second composition (s) produced according to the invention may further comprise fillers usually used in cosmetic compositions.

<Desc / Clms Page number 39>

 By fillers, it is necessary to include colorless or white particles, mineral or synthetic, lamellar or non-lamellar, intended to give the body or rigidity to the composition, and / or softness, dullness and uniformity make-up.

 The fillers, which may be present in a proportion of 0.01 to 60% by weight, preferably 3 to 10%, in the first and / or second composition of the product according to the invention may be mineral or synthetic, lamellar or not lamellar. Mention may be made of talc, mica, silica, kaolin, nylon and polyethylene powders, Teflon, starch, boron nitride, polymer microspheres such as Expancel (Nobel Industrie), polytrap (Dow Corning) and silicone resin microbeads (eg Toshiba Tospearls), precipitated calcium carbonate, magnesium carbonate or hydrocarbonate, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms.

additives
The first and second composition (s) of the makeup product according to the invention may also contain one or more cosmetic, dermatological, hygienic or pharmaceutical active ingredients.

 As cosmetic, dermatological, hygienic or pharmaceutical active agents that may be used in the compositions of the invention, mention may be made of moisturizers (polyol as glycerol), vitamins (C, A, E, F, B or PP), essential fatty acids, oils essential, ceramides, sphingolipids, liposoluble sunscreens or in the form of nano-particles, the specific active agents for the treatment of the skin (protective agents, anti-bacterial agents, anti-wrinkles, etc.).

 The product according to the invention can also be free of UV filter.

 These active agents are used in an amount customary for those skilled in the art and especially at concentrations of 0 to 20% and especially 0.001 to 15% of the total weight of the first or second composition.

 Each composition of the product according to the invention may, in addition, comprise, depending on the type of application envisaged, the constituents conventionally used in the fields considered, which are present in an amount appropriate to the desired dosage form.

<Desc / Clms Page number 40>

 Each composition of the product according to the invention may be in any galenical form normally used for topical application and especially in the form of an oily or aqueous solution, an oily or aqueous gel, an oil-in-water emulsion. or water-in-oil, a multiple emulsion, an oil dispersion in water through vesicles, the vesicles being located at the oil / water interface, or a powder. Each composition can be fluid or solid.

 The compositions of the product according to the invention can be prepared in the usual manner by those skilled in the art.

 They may be in the form of a cast product and for example in the form of a stick or stick, in the form of a flexible paste in a hot-water bottle, or in the form of a cup that can be used by direct contact or with a sponge. In particular, they constitute, together or separately, a cast foundation, blush or eyelid cast especially colored, lipstick, gloss for the lips, concealer or eye contour product.

 They can also be each in the form of a soft paste of an ointment, an ointment, a lotion or gel, more or less fluid cream.

It can then constitute foundations or fluid or pasty lipsticks, lip glosses, sunscreens or skin coloring, eyeliners, body make-up products or even present care properties. and then present yourself in the basic form or balm of care of the lips.

 Advantageously, the first or second composition, or both, are continuous-phase and preferably in anhydrous form and may contain less than 5% water, and even more preferably less than 1% water relative to the total weight. of each of the compositions. In particular, the entire bilayer makeup product is in anhydrous form.

 Preferably, each composition is in the form of a more or less rigid stick.

 Each composition can be packaged separately in one and the same packaging article, for example in a bi-compartmented pen.

 Preferably, the composition which is applied in the first layer is in solid form, which allows a more practical application, a better stability in the

<Desc / Clms Page number 41>

 time and temperature of the composition and allows a precise pattern of makeup, which is highly desirable in the case of a lipstick or an eyeliner.

 The product according to the invention can be advantageously used for the makeup of the skin, lips and / or integuments according to the nature of the ingredients used.

 Preferably, the product according to the invention is a makeup product for the skin or the lips. More particularly, it is in the form of a two-layer lipstick.

Examples
The percentages below are all expressed by weight relative to the total weight of the composition.

The three photochromic dyes used in the examples below are naphthopyran derivatives of the company James ROBINSON marketed under the names:

<Tb>
<tb> Reversacol <SEP> 195 <SEP> Ref. <SEP> 1
<tb> Reversacol <SEP> 208 <SEP> Ref. <SEP> 2
<tb> Reversacol <SEP> 306 <SEP> Ref. <SEP> 3
<Tb>

Their respective lE were evaluated according to the protocol described in the description. Table I reports the differences in hue (DE) obtained after 2 minutes of exposure.

<Tb>
<Tb>

Photochromic <SEP> AE
<tb> Ref. <SEP> 1 <SEP> 39 <SEP>
<tb> Re <SEP> 2 <SEP> 6 <SEP>
<tb> D <SEP> 3 <SEP> 34 <SEP>
<Tb>

Each of these three photochromic dyes is formulated in a composition lipstick base as follows and intended to be one of the two components of a bilayer lipstick product.

<Desc / Clms Page number 42>

Basic lipstick formulation: - octyl-2 dodecanol 0.5% - hectorite modified with di-stearyl di-methyl ammonium chloride 0.6% - liquid lanolin 27.2% - microcrystalline wax 10.5% - wax polyglycerolated bee (3 moles) 4.2% - 6.7% acetylated lanolin - arara oil (oleic acid esters) 13.5% - oxypropylenated lanolin wax (5 op) 6.7% - erucate of oleyl 13.5% - oleic-linoleic-linolenic acid triglycerides 1.7% - palmitic-oleic-linoleic acid triglycerides 13.5% - 0.1% sodium hyaluronate - 0.1% preservatives - vitamin 0.5% - UV filter 0.7% - pigments 7% - photochromic dye considered 2%
For each of the three formulations thus obtained, a layer of gloss formulation comprising 95% of polybutylene and 5% of helicone marketed by WACKER is superimposed on a layer thereof.

 Upon exposure to the sun, the product applied significantly changes color for each of the 3 products tested. Sun exposure reveals the helicones. This color change is particularly marked with the formulations comprising respectively the dyestuffs Ref. 1 and 3.

Claims (44)

A cosmetic product comprising at least a first and a second composition, the first composition comprising, in a first physiologically acceptable medium, at least one first dyestuff and the second composition comprising, in a second physiologically acceptable medium, at least one second dyestuff, one of the coloring materials being at least one goniochromatic coloring agent and the other coloring material being photochromic.  2. Product according to claim 1, characterized in that the photochromic coloring material is organic and in particular of the naphthopyran type.  3. Product according to claim 1 or 2, characterized in that the photochromic dyestuff is at least one 2H-naphtho- [2,1-b] -pyran of formula (I) or a 3H-naphtho- [2.1 -b] -pyran of formula (II):

 in which: - R1 represents: - (i) a hydrogen atom; (ii) a hydrocarbon group having 1 to 30, especially 1 to 18, and in particular 1 to 12, or even 1 to 6 carbon atoms, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N , 0, S, Si and P, and / or optionally halogenated or perhalogenated, in particular by F, Br and / or Cl; (iii) a hydrocarbon ring formed with one of the bonds "f" or "gh" and the radical R7; <Desc / Clms Page number 44>  in which the ring containing N and X is a saturated ring which comprises in total 3 to 30 atoms, in particular 4 to 10 and even more preferably 5 to 8, in particular 5.6 or 7

 (iv) a group chosen from -COOR4, -C (O) NR2R3, -NR2R3, -OR4 and SR4, in which: R2 and R3 represent, independently of one another, a hydrocarbon group having 1 at 20, in particular 1 to 12, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally comprising 1 to 5 heteroatoms chosen from N, O, S, Si and P, taken together with the nitrogen atom to which they are attached form a hydrocarbon heterocycle, saturated or unsaturated, containing 3 to 10, especially 4 to 6 carbon atoms and optionally 1 to 5 other heteroatoms chosen from N, O, S, Si and P said cycle being optionally substituted by at least one hydrocarbon radical having 1 to 20, especially 1 to 15, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P; - R4 represents a hydrocarbon group having 1 to 20, especially 1 to 12, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally halogenated or perhalogenated, in particular by F, Br and / or Cl; and / or optionally comprising 1 to 5 heteroatoms selected from N, O, S, Si and P; - R5 and R6 represent, independently of one another, a group chosen from: - (i) saturated cyclic aminoaryl groups of formula (IIa) or (IIb): <Desc / Clms Page number 45>  in which R10 and R11 represent, independently of one another, a group chosen from (i) hydrocarbon groups having 1 to 30, especially 1 to 18, and in particular 1 to 12, or even 1 to 6 carbon atoms linear, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, in particular by F, Br and / or Cl; (ii) halogen atoms, and especially F, Br and / or Cl; (iii) CN (nitrile), -COOH (carboxylate), -NO2 (nitro) groups; (iv) a hydrogen atom; a group selected from -C (O) NR 2 R 3, -NR 2 R 3, -OR 4 or -SR 4 with R 2, R 3 and R 4 having the meanings given above; the radicals R10 and R11 may together form a saturated or unsaturated hydrocarbon ring having a total of 5 to 8 atoms (including the atoms of the indoline ring), said atoms being chosen from C, O, S and / or NR with R representing H or a hydrocarbon radical having 1 to 20 or even 1 to 12 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P; - (iii) the groups of formula (IV):

 atoms, including nitrogen, the remainder being carbon atoms and / or heteroatoms selected from O, S, Si, P and / or groups selected from -NH and -NR with R representing a hydrocarbon radical having 1 to 20 , especially 1 to 15, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally comprising 1 to 5 heteroatoms chosen from N, O, S, Si and P; - (ii) the indolinoaryl groups of formula (III): <Desc / Clms Page number 46>  in which R8 and R9 represent, independently of one another, a group chosen from (i) hydrocarbon groups having 1 to 30, in particular 1 to 18, and in particular 1 to 12, or even 1 to 6 carbon atoms. carbon, linear branched or cyclic,

 wherein m and p are, independently of one another, integers ranging from 2 to 5; (iv) unsaturated cyclic aminoaryl groups of formulas (Va), (Vb) or (Vc):

<Desc / Clms Page number 47>  saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, in particular by F, Br and / or Cl; (ii) halogen atoms, and especially F, Br and / or Cl; (iii) CN (nitrile), -COOH (carboxylate), -NO2 (nitro) groups; (iv) a hydrogen atom; a group selected from -C (O) NR 2 R 3, -NR 2 R 3, -OR 4 or -SR 4 with R 2, R 3 and R 4 having the meanings given above; (v) a hydrocarbon group having 1 to 30, especially 2 to 18, and in particular 3 to 12 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally comprising 1 to 5 heteroatoms chosen from N, O, S; , Si and P; in particular a group chosen from -C6H4-CONR2R3, -C6H4-NR2R3 and -C6H4-OR4 with R2, R3 and R4 having the meanings given above; - R7 represents a group chosen from: - (i) hydrocarbon groups having 1 to 30, especially 1 to 18, and in particular 1 to 12 carbon atoms, linear branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, in particular by F, Br and / or Cl; - (ii) the halogen atoms, and especially F, Br and / or Cl; (iii) CN (nitrile), -COOH (carboxylate), -NO2 (nitro) groups; N = N- (azo); = NH (imino); -CONH2 (amide); - (iv) a hydrogen atom; (v) a group selected from -C (O) NR 2 R 3, -NR 2 R 3, -OR 4 or -SR 4 with R 2, R 3 and R 4 having the meanings given above; (vi) the radical R7 may additionally form, with one of the bonds "i", "j", "k", or "g, h" taken with the radical R1, or "f 'taken with the radical R 1, a saturated hydrocarbon ring having in total 3 to 8, in particular 4 to 7, and in particular 5 or 6 carbon atoms, optionally comprising 1 to 5 heteroatoms chosen from N, O, S, Si and P; - R'1 represents a group chosen from: - (i) a hydrogen atom, - (ii) a hydrocarbon group having 1 to 30, in particular 1 to 18, and in particular 1 to 12 carbon atoms, linear branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, in particular by F, Br and / or Cl; <Desc / Clms Page number 48>  (iii) a group chosen from -C (O) NR 2 R 3, -NR 2 R 3, -OR 4 and -SR 4, with R 2, R 3 and R 4 having the meanings given above; - R'2 represents a group chosen from: - (i) hydrocarbon groups having 1 to 30, especially 1 to 18, and in particular 1 to 12 carbon atoms, linear branched or cyclic, saturated or unsaturated, optionally comprising 1 to Heteroatoms chosen from N, O, S, Si and P, and / or optionally halogenated or perhalogenated, in particular by F, Br and / or Cl; - (ii) the halogen atoms, and especially F, Br and / or Cl; (iii) the groups-CN (nitrile), -COOH (carboxylate), -NO2 (nitro); N = N- (azo); = NH (imino); -CONH2 (amide); - (iv) a hydrogen atom; (v) a group chosen from -C (O) NR 2 R 3, -NR 2 R 3, -OR 4 or -SR 4 with R 2, R 3 and R 4 having the meanings given above.  4. Product according to any one of the preceding claims, characterized in that it comprises at least one photochromic coloring material corresponding to the following formula (Ia) or (IIa):

 in which R1, R5, R6, R7, R'1 and R'2 are as defined in claim 3.  5. Product according to claim 3 or 4, characterized in that R1 represents a hydrogen atom; a hydrocarbon ring with one of the "f 'or" gh "bonds and the radical R7 or a group selected from -COOR4, -NR2R3, -OR4 and -SR4, wherein: R2 and R3 are independently from each other, a hydrocarbon group having 1 to 20, in particular 1 to 12 and in particular 1 to 6 carbon atoms, <Desc / Clms Page number 49>  in which the ring comprising N and X is a saturated ring which comprises in total 3 to 30 atoms, in particular 4 to 10 and in particular 5, 6 or 7 atoms, including nitrogen, the remainder being carbon atoms and / or heteroatoms selected from O, S, Si,

 carbon, linear, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms selected from N, O, S, Si and P, taken together with the nitrogen atom to which they are attached, can form a hydrocarbon heterocycle saturated or unsaturated, having 3 to 10, in particular 4 to 6 carbon atoms and optionally 1 to 5 other heteroatoms selected from N, O, S, Si and P, said ring being optionally substituted by at least one hydrocarbon radical having 1 to 20, especially 1 to 15, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms selected from N, O, S, Si and P; and / or - R4 represents a hydrocarbon group having 1 to 20, especially 1 to 15, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally halogenated or perhalogenated, in particular by F, Br and or C1, and / or optionally comprising 1 to 5 heteroatoms chosen from N, O, S, Si and P and / or - R5 and R6 may represent, independently of one another, a group chosen from: saturated cyclic aminoaryl groups of formula (IIa) or (IIb): <Desc / Clms Page number 50>  P and / or groups chosen from -NH and -NR with R representing a hydrocarbon radical having 1 to 20, especially 1 to 15, and in particular 1 to 6 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally having 1 to 5 heteroatoms selected from N, O, S, Si and P; a hydrocarbon group having 1 to 30, in particular 2 to 18, and in particular 3 to 12 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally containing 1 to 5 heteroatoms chosen from N, O, S, Si and P; in particular a group chosen from -C6H4-CONR2R3, -C6H4-NR2R3 and -C6H4-OR4 with R2, R3 and R4 having the meanings given above; 6. Product according to any one of claims 3,4 or 5, characterized in that it comprises at least one photochromic coloring material corresponding to formula (I) or (la) for which: - R 1 represents hydrogen ; a COOR group with R being a saturated hydrocarbon radical having 1 to 12, in particular 1 to 6 carbon atoms, and in particular a methyl or ethyl radical; a group

 and / or - R5 and R6 represent, independently of one another, either (i) a group of formula (IIa):

 wherein the ring having N and X is a saturated ring which comprises a total of 4 to 7 atoms, especially 5 or 6 atoms, including nitrogen, and especially 3 to 5 carbon atoms and zero or 1 oxygen atom; in particular a group of formula: <Desc / Clms Page number 51>  or (ii) a hydrocarbon group having 5 to 14, especially 6 to 10 carbon atoms, linear, branched or cyclic, saturated or unsaturated, optionally comprising 1 to 2 heteroatoms chosen from N, O or S; and / or - R7 represents a hydrogen atom or a group -NR2R3, with R2 and R3 representing, independently of one another, a linear or branched, saturated hydrocarbon group having 1 to 12, especially 1 to 6 carbon atoms, and in particular a methyl and / or ethyl group.

 7. Product according to any one of claims 3 to 6, characterized in that it comprises at least one photochromic coloring material corresponding to formula (II) or (IIa) for which: - R'1 represents hydrogen or a COOR group with R being a saturated hydrocarbon radical having 1 to 12, in particular 1 to 6 carbon atoms, and in particular a methyl or ethyl radical; and / or - R5 and R6 represent, independently of one another, either (i) a group of formula (IIa):

<Desc / Clms Page number 52>  in which the ring containing N and X is a saturated ring which comprises in total 4 to 7 atoms, in particular 5 to 6 atoms, including nitrogen, or (ii) a hydrocarbon group having 5 to 14, especially 6 to 10 carbon atoms. linear, branched or cyclic carbon, saturated or unsaturated, optionally having 1 to 2 heteroatoms selected from N, O or S; and / or R'2 represents hydrogen, or a group -NR'R "with R 'and R", which are identical or different, representing a linear or branched saturated hydrocarbon group having 1 to 12, especially 1 to 6 carbon atoms.  8. Product according to any one of the preceding claims, characterized in that it comprises at least one photochromic dye chosen from - 3,3-di (4-methoxyphenyl) -6-morpholino-3H-naphtho [2, 1-b] pyran - 3-phenyl-3- (4-morpholinophenyl) -6-morpholino-3H-naphtho [2,1-b] pyran - 3-phenyl-3- (4-piperidinophenyl) -6- morpholino-3H-naphtho [2,1-b] pyran - 3-phenyl-3- (4-piperidinophenyl) -6-carboxymethyl-9-N-dimethyl-3H-naphtho [2,1-b] pyran 2-phenyl-2- (4-piperidinophenyl) -5-carboxymethyl-9-N-dimethyl-2H-naphtho [1,2-b] pyran and - mixtures thereof.  9. Product according to any one of the preceding claims, characterized in that the material (s) photochromic (s) (are) present (s) at a rate of 0.001 to 20% by weight, especially from 0.005 to 10% by weight, in particular from 0.01 to 5% by weight, more particularly from 0.05 to 2% by weight, or even from 0.1 to 1% by weight, relative to the total weight of the composition containing them .  10. Product according to any one of the preceding claims, characterized in that it comprises at least two separate photochromic dyes in the same composition.  11. Product according to any one of the preceding claims, characterized in that the goniochromatic coloring agent is present in a proportion of 0.1 to 60%, in particular from 1 to 20%, in particular from 2 to 15%, or even 2 to 10% by weight relative to the total weight of the composition containing it. <Desc / Clms Page number 53>  12. Product according to any one of the preceding claims, characterized in that the goniochromatic coloring agent is chosen from interferential multilayer structures and liquid crystal coloring agents.  13. Product according to claim 12, characterized in that the goniochromatic coloring agent with multilayer interference structure comprises at least two layers, each layer, independently or not of the other layer (s), being made from at least one material selected from the group consisting of the following materials: MgF 2, CeF 3, ZnS, ZnSe, Si, SiO 2, Ge, Te, Fe 2 O 3, Pt, Va, Al 2 O 3, MgO, Y 2 O 3, S 2 O 3, SiO , HfO 2, ZrO 2, CeO 2, Nb 2 O 5, Ta 2 O 5, TiO 2, Ag, Al, Au, Cu, Rb, Ti, Ta, W, Zn, MoS 2, cryolite, alloys, polymers and their combinations.  14. Product according to claim 12, characterized in that the liquid crystal coloring agent is obtained by polymerization of a monomer mixture comprising: a) at least one first monomer A of formula (I) Y1-A1- M1-A2-Y2 wherein -i) Y1 and Y2, identical or different, represent an acrylate or methacrylate group, preferably an acrylate group; ii) Al and A2, which are identical or different, represent a group of formula -CnH2n-, in which n is an integer ranging from 1 to 20, in particular ranging from 2 to 6, and in particular equal to 4; iii) MI denotes a group of general formula (I ') -Ri-Xi-R2-X2-R3-X3-R4-, in which R1 and R4 denote -O-, R2 and R3 denote -COO-, and Xi , X2, X3 are a 1,4-phenylene group, the carbonyl group -CO respectively of R2 and R3 being respectively linked to the group X1, X3, and -b) at least one second chiral monomer B of formula (II) V1-W1 -Z-W2-V2, in which - i) VIdisigne an acrylate or methacrylate group, and especially an acrylate group, and V2 denotes a C1-C20 alkyl group, a C1-C20 alkoxy, a (C1-C20) alkoxy group; carbonyl, -OH, and preferably denotes a C 1 -C 20 alkoxy group, especially a C 1 -C 4 alkoxy group, and in particular a methoxy group; ii) W1 represents a divalent group of formula-X '1 -CO-O-, <Desc / Clms Page number 54>

W2 represents a divalent group of formula -O-CO-X'1-, in which X'1 denotes a 1,4-phenylene group, and Z denotes a chiral group with two bonds, derived from the dianhydrohexite group, in particular a divalent radical of formula: 15. Product according to claim 14, characterized in that the liquid crystal coloring agent is obtained from a monomer mixture comprising from 70 to 99% by weight of monomer A and from 1 to 30% by weight of monomer B, relative to the total weight of monomer A and monomer B, and in particular comprising from 90 to 95% by weight of monomer A and from 5 to 10% by weight of monomer B.  16. Product according to claim 12, 14 or 15, characterized in that the liquid crystal coloring agent is present in a proportion of from 0.01% to 99% by weight, in particular from 0.1% to 60% by weight. , in particular from 1% to 30% by weight, and even from 5% to 15% by weight relative to the total weight of the composition containing it.  17. Product according to any one of the preceding claims, characterized in that the first and / or second composition (s) further comprise at least one non-photochromic and non-goniochromatic dyestuff.  18. The product of claim 17, characterized in that said coloring material is selected from water-soluble or fat-soluble monochromatic dyes, pigments, reflective particles, pearlescent agents and mixtures thereof.  19. Product according to any one of the preceding claims, characterized in that the first and / or second composition (s) further comprise at least one liposoluble or water-soluble monochromic dye, in particular in a proportion of 0.001 to 15% by weight relative to to the total weight of the composition containing it.  20. Product according to any one of the preceding claims, characterized in that the first and / or second composition (s) furthermore at least one pigment, especially present in a proportion of 0.01 to 25% by weight relative to the total weight. of the composition containing it.  21. Product according to any one of the preceding claims, characterized in that the first and / or second composition (s) in addition to <Desc / Clms Page number 55>  less a mother-of-pearl, especially present in a proportion of 0.01 to 20% by weight relative to the total weight of the composition containing it.  22. Product according to any one of the preceding claims, characterized in that the first and / or second composition (s) further comprise at least reflective particles, in particular present in a proportion of 0.1% to 20% by weight per relative to the total weight of the composition containing them.  23. Product according to any one of the preceding claims, characterized in that the first and / or second composition (s) comprise at least one oily phase.  24. The product as claimed in claim 23, characterized in that the oily phase comprises one or more oils, polar or apolar, volatile or nonvolatile, and preferably hydrocarbon-based.  25. Product according to claim 23 or 24, characterized in that the oily phase comprises from 5 to 100% by weight, in particular from 10 to 90%, even from 15 to 60% and in particular from 20 to 50% by weight of oil (s) relative to the total weight of said oily phase.  26. Product according to claim 23, 24 or 25, characterized in that the oily phase comprises from 5 to 100% by weight, in particular from 10 to 90%, or even from 15 to 60% and in particular from 20 to 50% by weight. weight of oil (s) relative to the total weight of said oily phase.  27. Product according to any one of claims 23 to 26, characterized in that the oils can be chosen from, oils of animal, vegetable, mineral or synthetic, volatile or non-volatile and mixtures thereof.  28. The product as claimed in claim 27, characterized in that they are chosen from animal or vegetable oils, esters and synthetic ethers, in particular of fatty acids, fatty alcohols, linear or branched hydrocarbons, of mineral origin. or synthetic glycerides and their mixtures.  29. Product according to any one of claims 23 to 28, characterized in that the oily phase is such that the coloring material (s) photochromic (s) are soluble therein.  30. Product according to any one of claims 23 to 29, characterized in that the oily phase is present in a proportion of 1 to 99% by weight, in particular from 10 to <Desc / Clms Page number 56>  90% by weight, in particular from 15 to 80% by weight relative to the total weight of the composition containing it.  31. The product as claimed in any one of the preceding claims, characterized in that the first and / or second composition (s) furthermore contain from 0.1 to 50% by weight, in particular from 3 to 40% by weight, and particularly from 5 to 30% by weight of a fatty substance other than an oil relative to the total weight of the composition containing it.  32. Product according to any one of the preceding claims, characterized in that the first and / or second composition (s) anhydrous.  33. Product according to any one of claims 1 to 32, characterized in that the first and / or second composition (s) at least one aqueous phase.  34. Product according to claim 33, characterized in that the said aqueous phase comprises from 0.1 to 14% by weight of a C2-C6 monoalcohol, such as ethanol, propanol, butanol, isopropanol and isobutanol, based on the total weight of said aqueous phase.  35. Product according to any one of the preceding claims, characterized in that the first and / or second composition (s) furthermore at least one surfactant, and in particular in an amount ranging from 0.01 to 30% by weight. relative to the total weight of the composition containing it.  36. Product according to any one of the preceding claims, characterized in that the first and / or second composition (s) further comprises at least one thickening agent, especially in the proportion of 0.01 to 6% by weight relative to to the total weight of the composition containing it.  37. Product according to any one of the preceding claims, characterized in that the first and / or second composition (s) further comprise at least one film-forming polymer, in particular at a proportion of 0.01 to 40% by weight relative to total weight of the composition containing it.  38. Product according to any one of the preceding claims, characterized in that the first and / or second composition (s) furthermore at least one filler, in particular at the rate of 0.01 to 60%, in particular from 3 to 10%. % by weight relative to the total weight of the composition containing it. <Desc / Clms Page number 57>  39. A method of making up the skin, lips and / or integuments comprising applying at least one product according to any one of the preceding claims to the skin, the lips and / or the superficial body growths.  40. The method of claim 42, characterized in that is applied in a first layer a first composition comprising in a first physiologically acceptable medium at least one photochromic coloring material, then it is applied on all or part of said first layer, a layer of the second composition comprising, in a second physiologically acceptable medium, at least one goniochromatic coloring agent.  41. Makeup kit comprising a product according to any one of claims 1 to 38.  42. Kit according to claim 41, characterized in that it contains means for applying the first and the second composition to the skin, the lips and / or the integuments.  43. Kit according to claim 41 or 42, characterized in that it contains application means selected from brushes, brushes, pens, pencils, felts, feathers, sponges, foams.  44. Kit according to any one of claims 41 to 43, characterized in that the first and second compositions are packaged in separate packaging articles.