FR2921559A1 - COMPOSITION TO BE APPLIED ON KERATINIC MATERIALS, COMPRISING A HOLOGRAPHIC PIGMENT - Google Patents

Abstract

The present invention relates to a composition to be applied to keratin materials, comprising in a medium acceptable for keratin materials at least one holographic pigment sensitive to a stimulus.

Description

The present invention relates to the compositions to be applied to keratin materials and to the makeup or treatment processes comprising the application of such compositions to keratin materials. US 4,898,192 discloses an artificial nail having a hologram.

Cosmetic or dermatological compositions are frequently applied to the skin of persons with colored or pigmented skin, rosacea or dark circles, in order to lighten and / or to homogenize the complexion. These compositions may include skin whitening agents. It may be necessary to use these bleaching agents for a long time and in high amounts to observe an effect. Moreover, the effect resulting from the application of such compositions may not be immediate. These compositions may also comprise fluorescent compounds, in particular optical brighteners. Such compositions provide an immediate brightening effect only in accordance with predefined lighting conditions, for example a high intensity natural light. Compositions comprising covering products for concealing skin imperfections are also known. Nevertheless, such compositions can mask the natural appearance of the skin and give the user the sensation of wearing a mask.

Compositions comprising interferential pigments arranged to conceal cutaneous imperfections exist. However, such interferential pigments can give a shiny and unnatural appearance to the skin. There is a need to benefit from a composition having a lightening effect and / or homogenization of the complexion while preserving as much as possible the natural appearance of the skin. Finally, interferential pigments having a surface diffraction grating are known. These pigments are for example used to extend the color path of a make-up composition. There is a need to benefit from new compositions to be applied to keratin materials, capable for example of producing new optical effects, after application and / or during use. The invention aims to meet all or part of the needs mentioned above. The subject of the invention is, according to a first of its aspects, a composition to be applied to keratin materials, comprising in a medium that is acceptable for keratin materials at least one holographic pigment sensitive to a stimulus, for example a holographic pigment comprising a matrix polymeric matrix, for example a polymeric matrix in which a volume hologram is recorded. The invention offers new possibilities in terms of optical effects by the use of such a holographic pigment, which can be sensitive to its environment and thus allow a variation of the appearance of the composition, including an observable variation in the naked eye under the conditions of use of the composition. The stimulus may be a content of at least one compound in the pigment environment. The compound may be at least one of the constituents of the composition, for example a solvent of the composition or an analyte present in and / or on keratin materials. The invention may make it possible, for example, to produce a composition that changes its appearance on application, which may make it possible, for example, to encourage the use of the composition and / or to create an entertaining and / or aesthetic, attractive effect. for the user.

The polymeric matrix may for example be hydratable and the optical properties of the hologram may depend on the state of hydration of the matrix. This may allow a change of appearance of the composition on drying. For example, the pigment may be colorless in the composition prior to application and develop at least one color upon application.

In the case of a care composition, the fact that the pigment is colorless before application may encourage the user to use the composition which will be colorless, preferentially to a composition which would appear before the colored application. The invention further relates, in another of its aspects, a cosmetic or dermatological treatment process comprising the step of applying to the keratin materials a composition as defined above. The composition relating to the holographic pigment according to the invention may also be used, if appropriate, in combination with another composition intended to be applied to keratin materials as a base coat or a topcoat ).

Holographic Pigment The holographic pigment according to the invention may comprise a polymeric matrix in which a volume hologram is recorded. A volume hologram differs from a surface hologram resulting from embossing or etching. The matrix may have, for example, within it a periodic variation of the refractive index and / or the concentration of an absorbent material. For example, a holographic pigment particle comprises a polymeric matrix in which is recorded a volume hologram in the form of a series of fringes, for example grains from the development of the hologram, for example silver grains, leading to to a periodic variation of the index of refraction of the matrix. The volume hologram converts the incident light into one or more beams having spatial and spectral dependencies depending on the parameters of the hologram. An example of a volume hologram is the Denisyuk type hologram which is a reflection hologram that can be obtained in a holographic film using a single laser beam, serving both as an object beam and as a reference beam. as disclosed in EP 1 754 968 A2 and at http://www.smartholograms.com/site/sections/technology/creating-sensors. htm, and in the application EP 1 369 681 A1 (see Figures la and lb in particular), these publications being incorporated by reference. For the manufacture of the holographic film, a polymer soluble in a solvent compatible with silver and silver halogenated salts may be selected, usually water, the polymer also being selected to stabilize the growth of the colloidal particles. silver halide, and to be able to form a stable film and becomes insoluble under the conditions required to work the film. A known holographic film is, as recalled in WO 99/63408, a film of a polymer such as gelatin, for example, containing silver halides, obtained from the formation of a colloidal liquid phase and the deposit. on a suitable support. Publication WO 99/63408 discloses examples of methods for making a holographic film with polymers other than gelatin. A modification of the polymeric matrix in the composition according to the invention can lead to an alteration of the optical properties of the hologram, in particular to a modification of the reflected wavelength, which can cause a color change of the pigment. Thus, the optical response of the pigment to the stimulus may be a variation in color or color intensity.

The polymeric matrix may be configured to react to one or more stimuli that result in a change in the volume hologram. As mentioned above, an example of a stimulus is a change in the content of a compound in the pigment environment, resulting in a change in the polymeric matrix, e.g., swelling or shrinking thereof. The pigment may for example pass from a moist environment, for example hydrated, where the matrix is swollen, to a dry environment, for example anhydrous, where the matrix is refracted, during the drying of the composition. The polymeric matrix may be so that the pigment is colorless in the composition, before its application, and takes a color during the drying thereof, for example due to the evaporation of a volatile solvent, for example water, or the opposite, from colored to colorless, or changing color. The polymeric matrix may also be chosen so as to react chemically with certain analytes, such as, for example, sebum, metal ion, heavy metal, sulphide, carbonate / bicarbonate, alcohol, and enzyme contents. glucose, lactose / glutamate, 13-lactose, urea, amylase, protease, oxidase, certain gases (eg O2, CO2, NO, NH3). The polymeric matrix may undergo a modification that may be reversible or non-reversible, such that the appearance or color change is reversible or not. For example, the color holographic pigment may disappear in case of rewetting, including rehydration, the polymeric matrix. The appearance of color due to the holographic pigment may also be transient, which may for example allow the appearance of different colors successively, depending for example on the degree of drying of the composition or the amount of a predefined analyte to the surface of keratin materials. A transient appearance is for example obtained when the pigment environment evolves between extreme states and the pigment changes twice in appearance between these extreme states. The pigment is, for example, colorless for one of the extreme states, becomes colored and then again colorless in the other extreme state. The holographic pigment may for example reflect a range of wavelengths in the visible range in the intermediate state and wavelength ranges respectively located in the infrared and in the ultraviolet for the extreme states above. The holographic pigment can be produced in a variety of ways. The pigment may be produced by grinding a macroscopic volume holographic film obtained, for example, as indicated above. The pigment has, for example, an average volume size of between 5 and 500 m. Grinding of the holographic film can be performed with conventional grinding means such as for example a ball mill, an air jet knife, or by cryocrushing. Fragmentation of the holographic film can also be done by spraying. WO 2004/103345 incorporated by reference discloses examples of grinding means. The polymeric matrix may comprise, for example, at least one natural or synthetic polymer, which may be a homopolymer or a copolymer. The polymeric matrix may comprise a polymer having a regular structure with, for example, at least 50 to 100 repeating units in the primary chain. The polymeric matrix may comprise at least one polymer chosen from: polyvinyl alcohol, polyvinylpyrrolidone, polyhydroxyethylacrylate, polyhydroxyethylmethacrylate, polyacrylamide, polymethacrylamide and polymers with LCST grafts as disclosed in US Pat. No. 7,115,255, US 6 689,856, WO 02/055589, WO 02/055607 and those of natural origin such as gelatin, agarose and cellulose derivatives, this list not being limiting. The polymeric matrix may comprise a gel, in particular a hydratable gel. An example of a holographic film reacting to the hydration state is described in [0095] of EP 1 754 968 A2, incorporated by reference. In this example, the hologram is recorded in a polymeric gelatin matrix formed by a technique as disclosed by H. Thiry in Journal of Photographic Science, Vol. 35, 1987. The mass content of the holographic pigment in the composition may be between 0.01 and 10%, preferably between 0.5 and 5%, more preferably between 0.5 and 3%, relative to the total weight of the composition. the composition. The composition may comprise two different holographic pigments according to the invention, so as to produce different colors in response to the same stimulus and / or react respectively to different stimuli.

Of course, the invention is not limited to a particular material to achieve the volume hologram. Acceptable Medium The composition comprises a medium compatible with the application thereof to external keratin materials. The composition may thus comprise a cosmetically or dermatologically acceptable medium, that is to say a non-toxic medium that can be applied to the skin, superficial body growths, in particular the hair, the nails and the eyelashes, or the lips of the skin. 'Human being.

The acceptable medium is generally adapted to the nature of the support on which the composition is to be applied and to the form in which the composition is packaged. The composition may comprise at least one coloring agent other than the holographic pigment, in a content that does not detract from the desired effect.

Other coloring agents The coloring agent may be a particulate compound or not. The composition may comprise at least one coloring agent producing light by absorption of at least a portion of the visible spectrum. Such a coloring agent producing a color by an absorption phenomenon may consist of an organic or inorganic or hybrid pigment comprising both organic material and inorganic material. The composition may comprise a composite pigment having a core at least partially coated with a bark. The composition may comprise at least one coloring agent producing substantially the same color as the holographic pigment in a predefined state thereof. This allows for example to obtain a color enhancement in response to the stimulus, for example during the drying of the composition. When the coloring agent comprises a dye, it may be chosen from liposoluble and water-soluble dyes.

Liposoluble dyes are, for example, Sudan Red, DC Red 17, DC Green 6, (3-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, Orange DC 5 quinoline yellow The water-soluble dyes are, for example, beet juice and methylene blue.

The coloring agent may also be a lacquer or an organic pigment chosen from the materials below and their mixtures: cochineal carmine, organic pigments of azo, anthraquinone, indigo, xanthene, pyrenic, quinoline dyes fluoran triphenylmethane, - organic lakes or insoluble salts of sodium, potassium, calcium, barium, aluminum, zirconium, strontium, titanium, acid dyes such as azo, anthraquinone, indigo, xanthene, pyrenic, quinoline, triphenylmethane, fluorane, these dyes may comprise at least one carboxylic or sulfonic acid group. Among the organic pigments, mention may be made of those known under the following names: D & C Blue No. 4, D & C Brown No. 1, D & C Green No. 5, D & C Green No. 6, D & C Orange No. 4, D & C Orange No. 5, D & C Orange No. 10, D & C Orange No. 11, D & C Red No. 6, D & C Red No. 7, D & C Red No. 17, D & C Red No. 21, D & C Red No. 22, D & C Red No. 27, D & C Red No. 28, D & C Red No. 30, D & C Red No. 31, D & C Red No. 33, D & C Red No. 34, D & C Red No. 36, D & C Violet No. 2, D & C Yellow No. 7, D & C Yellow # 8, D & C Yellow # 10, D & C Yellow # 11, FD & C Blue # 1, FD & C Green # 3, FD & C Red # 40, FD & C Yellow # 5, FD & C Yellow # 6. The color may be an organic lacquer supported by an organic carrier such as rosin or aluminum benzoate, for example. Among the organic lakes, mention may be made in particular of the following denominations: D & C Red No. 2 Aluminum Lake, D & C Red No. 3 Aluminum Lake, D & C Red No. 4 Aluminum Lake, D & C Red No. 6 Aluminum Lake, D & C Red # 6 Barium Lake, D & C Red # 6 Barium / Strontium Lake, D & C Red # 6 Strontium Lake, D & C 25 Red # 6 Potassium Lake, D & C Red # 7 Aluminum Lake, D & C Red # 7 Barium Lake, D & C Red # 7 Calcium Lake, D & C Red # 7 Calcium / Strontium Lake, D & C Red # 7 Zirconium Lake, D & C Red # 8 Sodium Lake, D & C Red # 9 Aluminum Lake, D & C Red # 9 Barium Lake, D & C Red # 9 Barium / Strontium Lake, D & C Red # 9 Zirconium Lake, D & C Red # 10 Sodium Lake, D & C Red # 19 Aluminum Lake, D & C Red # 19 Barium 30 Lake, D & C Red # 19 Zirconium Lake , D & C Red # 21 Aluminum Lake, D & C Red No. 21 Zirconium Lake, D & C Red No. 22 Aluminum Lake, D & C Red No. 27 Aluminum Lake, D & C Red No. 27 Aluminum / Titanium / Zirconium Lake, D & C Red No. 27 Barium lake, D & C Red # 27 Ca lcium lake, D & C Red # 27 Zirconium lake, D & C Red # 28 Aluminum lake, D & C Red # 30 lake, D & C Red # 31 Calcium lake, D & C Red # 33 Aluminum lake, D & C Red # 34 Calcium lake, D & C Red No. 36 Lake, D & C Red No. 40 Aluminum Lake, D & C Blue No. 1 Aluminum Lake, D & C Green No. 3 Aluminum Lake, D & C Orange No. 4 Aluminum Lake, D & C Orange No. 5 Aluminum Lake, D & C Orange No. ° 5 Zirconium lake, D & C Orange # 10 Aluminum lake, D & C Orange # 17 Barium lake, D & C Yellow # 5 Aluminum lake, D & C Yellow # 5 Zirconium lake, D & C Yellow # 6 Aluminum lake, D & C Yellow # 7 Zirconium lake, D & C Yellow # 10 Aluminum Lake, FD & C Blue # 1 Aluminum Lake, FD & C Red # 4 Aluminum Lake, FD & C Red # 40 Aluminum Lake, FD & C Yellow # 5 Aluminum Lake, FD & C Yellow # 6 Aluminum Lake . The chemical materials corresponding to each of the organic dyestuffs mentioned above are mentioned in the International Cosmetic Ingredient Dictionary and Handbook, Edition 1997, pages 371 to 386 and 524 to 528, published by The Cosmetic, Toiletry, and Fragrance Association, whose Content is incorporated herein by reference. The composition may contain at least one goniochromatic coloring agent other than the holographic pigment. The goniochromatic coloring agent may be chosen, for example, from interferential multilayer structures and liquid crystal coloring agents. As the goniochromatic coloring agent, it is possible to use nacres, pigments with effects on a synthetic substrate, in particular an alumina-type substrate, silica, borosilicate, iron oxide, aluminum, or interferential holographic flakes resulting from a polyterephthalate film. By nacre, it is necessary to understand colored particles of any shape, iridescent or not, in particular produced by certain shellfish in their shell or else synthesized and which exhibit a color effect by optical interference. The nacres may be chosen from pearlescent pigments such as iron oxide-coated titanium mica, bismuth oxychloride-coated mica, titanium mica coated with chromium oxide, titanium mica coated with a dye. organic especially of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. It may also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic dyestuffs. The nacres may more particularly have a color or a yellow, pink, red, bronze, orange, brown, gold and / or coppery reflection.

As an illustration of the nacres that can be introduced into the first composition, mention may especially be made of gold-colored mother-of-pearls marketed by Engelhard under the name Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica) , Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); bronze nacres sold especially by the company Merck under the name Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by Engelhard under the name Super Bronze (Cloisonne); orange nacres sold especially by the company Engelhard under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion Orange (Colorona) and Matte Orange (17449) (Microna); brown-colored pearlescent agents marketed by Engelhard under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); nacres with a copper sheen sold especially by Engelhard under the name Copper 340A (Timica); the nacres with a red glint sold especially by MERCK under the name Sienna fine (17386) (Colorona); yellow-colored pearlescent agents marketed by ENGELHARD under the name Yellow (4502) (Chromalite); the red-colored pearlescent agents with a gold glint sold especially by ENGELHARD under the name Sunstone G012 (Gemtone); pink nacres sold especially by Engelhard under the name Tan opal G005 (Gemtone); the black nacres with gold reflection sold by the company Engelhard under the name Nu antique bronze 240 AB (Timica), the blue nacres sold especially by the company Merck under the name Matte Blue (17433) (Microna), the white nacres with reflection silver sold in particular by the company Merck under the name Xirona Silver and the golden-green orange-colored mother-of-pearl marketed by Merck under the name Indian summer (Xirona) and their mixtures. The nacres may also be those described in EP 1 656 927, the average volume size of which is less than 40 m, more preferably 15 m, especially nacres of the mica / tin oxide / titanium oxide type such as, for example, those marketed under the names TIMIRON SILK BLUE, SILK RED TIMIRON, TIMIRON SILK GREEN, TIMIRON SILK GOLD and TIMIRON SUPER SILK offered by the company MERCK and mica / iron oxide / titanium oxide pearls such as for example FLAMENCO SATIN BLUE, FLAMENCO SATIN RED and FLAMENCO SATIN VIOLET, proposed by the company ENGELHARD and their mixtures. The composition may also comprise reflective particles chosen from particles with a synthetic substrate at least partially coated with at least one layer of at least one metal oxide, chosen, for example, from titanium oxides, in particular TiO 2, in particular Fe 2 O 3, tin, chromium, barium sulfate and the following materials: MgF 2, CrF 3, ZnS, ZnSe, SiO 2, Al 2 O 3, MgO, Y 2 O 3, SeO 3, SiO, HfO 2, ZrO 2, CeO 2, Nb 2 O 5, Ta 2 O 5, MoS 2 and mixtures thereof . By way of example of such particles, mention may be made, for example, of particles comprising a synthetic mica substrate coated with titanium dioxide, or particles of coated glass of brown iron oxide, of titanium oxide, of tin oxide or a mixture thereof such as those sold under the trade name REFLECKS by ENGELHARD. The composition may further comprise a thermochromic, mechanochromic or photochromic coloring agent. The composition may comprise a solvatochromic coloring agent, for example DC Red 7 Solvents The composition may comprise at least one solvent, chosen in particular as a function of the dosage form. The nature of the solvent may also be chosen so as to interact with the polymeric matrix of the holographic pigment or not. The choice of a possibility of interaction between the solvent and the matrix may allow, for example, a change in the otic properties of the hologram as a function of the solvent content in the environment of the pigment, which can lead, for example, to appearance of color and / or color change during drying. Choosing a lack of interaction between the solvent and the matrix can make the holographic pigment sensitive to a stimulus other than the solvent content in the surrounding medium of the pigment, which can facilitate the observation of a pigment. modification of the hologram in response to the presence of an analyte, for example, lactic acid, urea, pH, etc. The composition may comprise water, an aqueous solvent or a mixture of water and hydrophilic organic solvents commonly used in cosmetics, such as alcohols and in particular lower linear or branched monoalcohols having from 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol, polyols such as glycerine, diglycerine, propylene glycol, sorbitol, penthylene glycol, polyethylene glycols. The first composition may further contain C 2 ethers and C 2 -C 4 hydrophilic aldehydes.

The water or the mixture of water and hydrophilic organic solvents may be present in the composition in a content ranging for example from 0% to 90%, especially 0.1% to 90% by weight and preferably from 0% to 60% by weight, especially 0.1% to 60% by weight, relative to the total weight of the composition. The composition may comprise a volatile solvent, aqueous or organic.

For the purposes of the present invention, the term "volatile solvent" is intended to mean a solvent which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular having a vapor pressure of 0.13 Pa. at 40,000 Pa (10-3 at 300 mm Hg), and preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0. , 01 to 10 mmHg). When the composition comprises one or more organic solvents, these solvents may be present in a content ranging from 0.1% to 99%, relative to the total weight of the composition concerned. In general, the amount of solvent (s), in particular organic (s), will depend on the nature of the support on which the composition is intended to be applied. The composition may comprise at least one volatile solvent consisting of a volatile oil. The oil can be a silicone oil or a hydrocarbon oil, or comprise a mixture of such oils.

For the purposes of the present invention, the term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group. The term "hydrocarbon-based oil" means an oil containing mainly hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur and / or phosphorus atoms.

The volatile hydrocarbon oils may be chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially branched C8-C16 alkanes (also known as isoparaffins), such as isododecane (also called 2,2,4,4,6 -pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names ISOPARS or PERMETHYLS.

As volatile oils, it is also possible to use volatile silicones, for example volatile linear or cyclic silicone oils, in particular those having a viscosity of 8 centistokes (8 × 10 -6 m 2 / s), and especially having from 2 to 10 silicon atoms, and in particular from 2 to 7 silicon atoms, these silicones optionally containing alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil that may be used in the invention, mention may be made in particular of dimethicones of viscosity 5 and 6 cSt, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane and hexamethyl. disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof. It is also possible to mention volatile alkyltrisiloxane linear oils of general formula (I): CH 3 (CH 3) SiO Si SiCH 3 R 3 R 3 R 3 where R represents an alkyl group comprising from 2 to 4 carbon atoms and one or more hydrogen atoms may be substituted by a fluorine or chlorine atom Among the oils of general formula (I), mention may be made of: 3-butyl 1,1,1,3,5,5, 5-heptamethyl trisiloxane, 3-propyl 1,1,1,3,5,5,5-heptamethyltrisiloxane, and 3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, corresponding with the oils of formula (I) for which R is a butyl group, a propyl group or an ethyl group respectively, or volatile fluoro oils such as nonafluoromethoxybutane or perfluoromethylcyclopentane, and mixtures thereof. invention may comprise, for example, between 0.01% and 95% by weight of volatile oil, relative to the total weight of the composition, or even be 1% and 75% by weight.

The composition may comprise at least one organic solvent chosen from the following list: ketones that are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone; alcohols which are liquid at room temperature, such as ethanol, isopropanol, diacetone alcohol, 2-butoxyethanol or cyclohexanol; glycols that are liquid at room temperature, such as ethylene glycol, propylene glycol, pentylene glycol or glycerol; propylene glycol ethers which are liquid at ambient temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-butyl ether; short-chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, acetate isopentyl; alkanes which are liquid at ambient temperature, such as decane, heptane, dodecane and cyclohexane.

Fatty phase The composition, for example when it is intended to be applied to the lips or the eyelashes, may comprise a fatty phase and in particular at least one fatty substance that is liquid at room temperature (25 ° C.) and at atmospheric pressure (760 mm). of Hg) and / or a fat solid solid at room temperature such as waxes, pasty fatty substances, gums and mixtures thereof. The fatty phase may further contain lipophilic organic solvents. The composition may for example have a continuous fat phase, which may contain less than 5% water, especially less than 1% water relative to its total weight and in particular be in anhydrous form.

As liquid fatty substances at room temperature, often called oils, mention may be made of: vegetable hydrocarbon-based oils such as liquid triglycerides of fatty acids with 4 to 10 carbon atoms, for example triglycerides of heptanoic or octanoic acids, or oils of sunflower, corn, soybean, grape seed, sesame, apricot, macadamia, castor oil, avocado, caprylic / capric acid triglycerides, jojoba oil, shea butter, lanolin, acetylated lanolin; linear or branched hydrocarbons of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam; esters and synthetic ethers, in particular of fatty acids, for example purcellin oil, isopropyl myristate, 2-ethylhexyl palmitate, octyl-2-dodecyl stearate, erucate octyl-2-dodecyl, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; isononyl isonanoate, isopropyl lanolate, tridecyl trimellilate, diisostearyl malate; polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate; and pentaerythritol esters; fatty alcohols having 12 to 26 carbon atoms such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol; partially hydrocarbon and / or silicone fluorinated oils; silicone oils, such as volatile or nonvolatile polymethylsiloxanes (PDMS), linear or cyclic, liquid or pasty at room temperature, such as cyclomethicones, dimethicones, optionally comprising a phenyl group, such as phenyl trimethicones, phenyltrimethylsiloxydiphenylsiloxanes or diphenylmethyldimethyltrisiloxanes, diphenyl dimethicones, phenyl dimethicones, polymethylphenyl siloxanes; their mixtures. The oils may be present in a content ranging from 0.01 to 90%, and more preferably from 0.1 to 85% by weight, relative to the total weight of the composition. The presence of an oily phase may impart gloss, and this oily phase may have, for example, a refractive index of between 1.47 and 1.51, better still between 1.48 and 1.50. The refractive index is measured at room temperature (25 ° C), using a refractometer. The composition may comprise at least one structuring agent of the liquid fatty phase (formed by the volatile and non-volatile oils and / or organic solvents described above) chosen from waxes, semi-crystalline polymers, lipophilic gelling agents and mixtures thereof. The pasty fatty substances are generally hydrocarbon compounds with a melting point between 25 and 60 ° C., preferably between 30 and 45 ° C., and / or a hardness of between 0.001 and 0.5 MPa, preferably between 0.005 and 0.4 MPa, such as lanolins and their derivatives.

The waxes may be solid at room temperature (25 ° C), reversible solid / liquid state change, having a melting temperature greater than 30 ° C up to 200 ° C, hardness greater than 0.5 MPa, and having in the solid state an anisotropic crystalline organization. In particular, the waxes may have a melting point greater than 25 ° C. and better still greater than 45 ° C. The waxes may be hydrocarbon-based, fluorinated and / or silicone-based and may be of vegetable, mineral, animal and / or synthetic origin. As useful waxes, mention may be made of beeswax, carnauba or candelilla wax, paraffin wax, microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene or Fischer Tropsch waxes, silicone waxes such as alkyl or alkoxy dimethicone having from 16 to 45 carbon atoms. The composition may contain from 0 to 50% by weight of waxes, relative to the total weight of the composition, or even from 1 to 30% by weight. The gums that can be used are generally high molecular weight polydimethylsiloxanes (PDMS) or cellulose gums or polysaccharides. Film-forming polymers The composition may also comprise, for example, a film-forming polymer, in particular in the case of a mascara, a nail polish or a foundation. "Film-forming polymer" means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials. The composition may also comprise an auxiliary film-forming agent promoting the formation of a film with the film-forming polymer. Among the film-forming polymers that can be used in the composition according to the invention, mention may be made, inter alia, of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin, such as nitrocellulose or cellulose esters, and their mixtures. 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 acidic group and / or esters of these acidic 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, vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers selected from vinyl esters. such as vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate and styrene monomers such as styrene and alpha-methyl styrene.

Among the film-forming polycondensates, there may be mentioned polyurethanes, polyesters, polyesters amides, polyamides, and polyureas, this list not being limiting. The polymers of natural origin, optionally modified, may be selected from shellac resin, sandarac gum, dammars, elemis, copal, cellulosic polymers, such as nitrocellulose, ethylcellulose or selected nitrocellulose esters. for example, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and mixtures thereof. The film-forming polymer may be present in the form of solid particles in aqueous or oily dispersion, generally known as latex or pseudolatex. The film-forming polymer may comprise one or more stable dispersions of generally spherical polymer particles of one or more polymers in a physiologically acceptable liquid fatty phase. These dispersions are generally referred to as NAD (Non-Aqueous Dispersion) polymer as opposed to latexes which are aqueous polymer dispersions. These dispersions can in particular be in the form of polymer nanoparticles in stable dispersion in said fatty phase. The nanoparticles are preferably of a size between 5 and 600 nm. The techniques for preparing these dispersions are well known to those skilled in the art. As the aqueous dispersion of film-forming polymer, it is possible to use the acrylic dispersions sold under the names NEOCRYL XK-90, NEOCRYL A-1070, NEOCRYL A-1090, NEOCRYL BT-62 'NEOCRYL A-1079, NEOCRYL A-523 by the company AVECIA -NEORESINS, DOW LATEX 432 by the company DOW CHEMICAL, DAITOSOL 5000 AD by the company DAITO KASEI KOGYO; or the aqueous polyurethane dispersions sold under the trade names NEOREZ R-981, NEOREZ R-974 by the company AVECIA-NEORESINS, the AVALURE UR-405, AVALURE UR-410, AVALURE UR-425, AVALURE UR-450, SANCURE 875 , SANCURE 861, SANCURE 878, SANCURE 2060 by the company GOODRICH, IMPRANIL 85 by the company BAYER, AQUAMERE H-1511 by the company HYDROMER; sulfopolyesters sold under the trade name Eastman AQ by Eastman Chemical Products. The composition may comprise at least one film-forming polymer which is a film-forming linear ethylenic block polymer. This polymer preferably comprises at least a first block and at least a second block having different glass transition temperatures (Tg), said first and second blocks being interconnected by an intermediate block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second sequence. Advantageously, the first and second sequences and the block polymer are incompatible with each other. Such polymers are described for example in EP 1411069 or WO 04/028488, which are incorporated by reference. The composition may comprise at least one filler, in a quantity that does not adversely affect the desired effect. Loads are defined as particles of any form, insoluble in the medium of the composition, regardless of the temperature at which the composition is made. A filler can serve in particular to modify the rheology or the texture of the composition. The nature and quantity of the particles may depend on the desired mechanical properties and textures. By way of an example of fillers, mention may be made, inter alia, of talc, mica, silica, kaolin, sericite, powders of polyamide, polyolefin, for example polyethylene, polytetrafluoroethylene, polymethacrylate or methyl, polyurethane, starch powders and silicone resin beads, the hollow sphere portions, consisting of an organosilicon material, having a mean diameter of between 0.05 and 10 m, as described in EP 1,530,961, for example those commercially available from TAKEMOTO OIL & FAT under the trade names NLK-500, NLK-501 and NLK-506.

The fillers may be intended to create, inter alia, a blur effect, particularly in the case of a foundation, in order to conceal imperfections of the skin. Active ingredients The composition may comprise at least one cosmetic or dermatological active agent. As cosmetic, dermatological, hygienic or pharmaceutical active agents that can be used in the compositions of the invention, mention may be made of moisturizers, polyols, for example glycerine, and vitamins, especially C, A, E, F, B and B3. , B5, Kl or PP, vitamin derivatives and in particular their esters, essential fatty acids, essential oils, ceramides, sphingolipids, liposoluble or nanoparticulate sunscreens, the specific agents for the treatment of the skin (protective agents, anti-bacterial, anti-wrinkle ...), self-tanning, active agents having an effect on the aging of the skin, in particular keratolytic or prodesquamant agents, chosen in particular from α-hydroxy acids, (3-hydroxy-acids, α-keto acids, 13-keto acids, retinoids and their esters, retinal, retinoic acid and its derivatives, C glycosides and their derivatives and adenosine and its derivatives, free antiradical agents, DHEA and its derivatives, coenzyme Q10, bleaching and depigmenting agents such as kojic acid, para-aminophenol derivatives, arbutin and their derivatives, and mixtures thereof. These active agents can be used, for example, at concentrations of 0 to 20% and in particular from 0.001 to 15% relative to the total weight of the composition.

The composition may also contain other ingredients commonly used in cosmetics, such as, for example, thickeners, tensors, surfactants, trace elements, moisturizers, in particular polyols, for example glycerine, softeners, sequestering agents, perfumes, preservatives, antioxidants, pH adjusters (acids or bases), physical or chemical UV filters and mixtures thereof.

A composition according to the invention may comprise, according to the type of application envisaged, all the constituents conventionally used in the field in question, which are present in an amount appropriate to the desired dosage form. Galenic forms The composition can take various forms, depending on its purpose. Proposed Examples Example 1: Care cream (oil-in-water emulsion) A-Glyceryl stearate (and) PEG-100 stearate: 2.00 g Dimyristyl tartrate (and) cetearyl alcohol (and) C12-5 pareth-7 1.50 g (and) PPG 25-laureth-25: Cyclohexasiloxane: 10.00 g Stearyl alcohol: 1.00 g B-Water: 80.75 g The composition can thus be in any galenical form normally used for topical application and in particular in anhydrous form, in the form of an oily solution or aqueous, a powder, free or compacted, a stick, a serum (thickened aqueous solution), an oily or aqueous gel, an oil-in-water emulsion, water in oil, wax in water or water in wax, a multiple emulsion, an oil dispersion in water through vesicles at the oil / water interface. Phenoxyethanol: 1.00 g Pentasodium ethylene diamine tetramethylene phosphate: 0.05 g Ammonium Polyacryldimethyltauramide: 0.40 g Xanthan gum: 0.20 g C-Holographic Pigment according to the * *: 3.00 g * Pigment obtained by grinding a gelatin-based holographic film Procedure: - heat phase B to about 75 ° C and incorporate Ammonium Polyacryldimethyl tauramide; stir until a homogeneous gel is obtained. - heat phase A to about 75 ° C. realize the emulsion by incorporating phase A into phase B. at 40-45 ° C., incorporate phase C and maintain stirring until complete cooling.

The effect obtained can be visualized as follows. The composition is spread at a rate of 301um on the black part of an Erichsen type 24/5 contrast card by means of an automatic applicator from Braive Instruments. The spreading is then placed in a thermostatted oven and ventilated for 24 hours at 37 ° C. The revelation of the color related to the change of state of the holographic particles is visible to the naked eye.

The parameters L, a and b of the wet film and the parameters L, a and b of the wet film can also be measured using a CR400 Minolta colorimeter. The difference in color AE (AE = [(Aa) 2 + (Ab) 2 + (AL) 2] 0.5) between the two states of the film is greater than 1. Example 2: foundation (water-in-oil emulsion) A-Polymethylcetyl dimethyl methylsiloxane oxyethylene 1.5 g Isotearate polyglycerol 0.5 g Dimethicone 2.05 g Cyclopentasiloxane 4 g Red iron oxide sold under the reference BRO-12 by the company Kobo 0. 76 g Yellow iron oxide sold under the reference BYO-12 by the Kobo company 1.59 g Black iron oxide sold under the reference BBO-12 by the company Kobo 0.31 g Titanium dioxide sold under the reference BTD-401 by the company Kobo 10.68 g Isononyl isononanoate 6.66 g Preservative 0.15 g Bù Water qsp Propylene glycol 3 g Magnesium sulphate 1.75 g Mehtylparaben 0.2 g Preservative 0.3 g C-Nylon 12 3.00 g D Holographic pigment according to the invention ** 5.00 g ** Same pigment as in example 1. Procedure The effect obtained can be visualized as follows. The composition is spread at 30% on the black part of an Erichsen type 24/5 contrast card by means of an automatic applicator from Braive Instruments. The spreading is then placed in a thermostatted oven and ventilated for 24 hours at 37 ° C. The revelation of the color related to the change of state of the holographic particles is visible to the naked eye. The wet film parameters L, a and b, and the wet film parameters L, a and b can also be measured using a Minolta CR400 colorimeter. The color difference AE between the two states of the film is greater than 1.

The expression having one must be understood as being synonymous with having at least one. Homogenize at room temperature with stirring phase A and phase B separately. - Make the emulsion by incorporating phase B into phase A. - Incorporate phases C and D with stirring. 30

Claims (24)

1. Composition to be applied to keratin materials, comprising in a medium acceptable for keratin materials at least one holographic pigment sensitive to a stimulus. 2. Composition according to claim 1, the holographic pigment comprising a polymeric matrix. 3. Composition according to claim 2, at least one volume hologram being recorded in the polymeric matrix. 4. Composition according to one of claims 1 to 3, the stimulus being a content of at least one compound in the environment of the pigment. 5. Composition according to Claim 3, the compound being at least one of the constituents of the composition, in particular a solvent of the composition. 6. Composition according to claim 4, the compound being an analyte present in and / or on keratin materials. 15 7. Composition according to any one of the preceding claims, the pigment having an average size of between 5 and 500 m. 8. Composition according to any one of the preceding claims, the pigment being arranged to reflect in a state at least, encountered in the composition before application or application, wavelengths between 280 and 900 nm. 20 9. Composition according to claim 2, the polymer matrix being hydratable and the optical properties of the hologram depending on the state of hydration of the matrix. 10. A composition according to any one of claims 1 to 9 wherein the holographic pigment is colorless in the composition prior to its application and developing a color upon application. 11. Composition according to claim 2, the polymeric matrix comprising at least one synthetic polymer. 12. Composition according to claim 11, the polymeric matrix comprising at least one polymer chosen from: polyvinyl alcohol, polyvinylpyrrolidone, polyhydroxyethylacrylate, polyhydroxyethylmethacrylate, polyacrylamide, polymethacrylamide and LCST graft polymers. 13. Composition according to any one of claims 1 to 11, the composition comprising at least one polymer selected from gelatin, agarose and cellulose derivatives. 14. Composition according to any one of the preceding claims, the mass content of holographic pigment being between 0.01 and 10%. 15. Composition according to claim 14, the content being between 0.5 and 5%. 16. The composition of claim 14, the content being between 0.5 and 3%. 17. Composition according to claim 2, the polymeric matrix comprising a polymer having a regular structure with at least 50 to 100 repeating units in the primary chain. 18. Composition according to claim 2, wherein the polymer matrix is chosen so as to react chemically with analytes such as sebum, metal ion, heavy metal, sulphide, carbonate / bicarbonate, alcohol, enzyme, glucose, lactose / glutamate, 13-lactose, urea, amylase, protease, oxidase, certain gases (O2, CO2, NO, NH3), pH, lactic acid. 19. Composition according to any one of claims 1 to 18, the acceptable medium comprising water. 20. Composition according to claim 19, the mass content of water ranging from 0.5% to 99%. 21. A composition according to any one of claims 1 to 20, being devoid of any other coloring agent than the holographic pigment. 22. Composition according to any one of claims 1 to 20, comprising at least one other coloring agent. 23. Composition according to any one of the preceding claims, comprising at least one cosmetic or dermatological active agent. 25 24. Cosmetic treatment process comprising the step of applying to the keratin materials a composition according to any one of the preceding claims.