FR2825619A1 - Cosmetic composition for creating optical effect, e.g. electrically controlled variation of appearance of skin, lipids or nails, containing electroluminescent and/or electroconductive polyconjugated polymer - Google Patents

Abstract

A cosmetic composition (A) for creating an optical effect contains at least one electroluminescent and/or electroconductive polyconjugated polymer (I), in an amount such that the electrical and/or electro-optical properties of (A) are due to the presence of (I). Independent claims are included for: (1) a cosmetic film for creating an optical effect, obtained by deposition of (A) on a keratin or other support; (2) the use of (I) for the preparation of a cosmetic composition or film for creating an optical effect or as a cosmetic agent for creating an optical effect; (3) a make-up method comprising applying (A) or a (I)-containing film to the surface to be treated and connecting (A) or the film directly or indirectly to an electrical source; and (4) a device for creating an optical effect, comprising a multilayer structure to be applied to a keratin support (e.g. the skin, lips or nails), including an adhesive support and a layer containing (I).

Description

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The present invention relates to the field of cosmetics and in particular that of the creation of optical effects for a cosmetic purpose.

For several years, polyconjugated polymers, whose skeleton is formed by a succession of single and double bonds have been of increasing interest.

Their particular electronic structure, with the presence of a band gap of 1 to 3 eV and electroaffinity and ionization potential such that they can react with many donor or electron acceptor compounds (so-called doping reaction), confer polyconjugated polymers have remarkable properties.

Thus, the electronic structure of polyconjugated polymers in the doped state allows the displacement of electrons and gives them electroconductivity properties.

On the other hand, when the polyconjugated polymers are in the neutral state and when they are subjected to an electric field, they emit, thanks to their forbidden band, photons whose energy depends on the width of the forbidden band and present electroluminescence properties.

The use of polymer-type compounds has the advantage of facilitating or allowing the production on a relatively large surface of films, in particular thin films, in particular of thickness less than 1 micrometer.

It has already been envisaged to use polyconjugated polymers for their electroconductive properties in order to produce heating fabrics, antistatic coatings, electromagnetic shielding, speaker membranes as well as to constitute microwave absorbing materials.

It has also been envisaged to use polyconjugated polymers for their electro-optical properties, in the field of optoelectronics, in particular for the production of light-emitting diodes.

No application has been proposed, to the knowledge of the applicant, in the field of cosmetics.

The present invention thus relates, in particular, to a cosmetic composition intended to create an optical effect, which comprises at least one polyconjugated polymer, said polymer being an electroluminescent and / or electroconductive polymer, and being present in such a proportion that the electrical properties and / or electro-optics of the composition come essentially from the presence of this

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 electroluminescent and / or electroconductive polymer.

 For the purposes of the present invention, the expression "optical effect" means any modification of the appearance of all or part of the individual, such as in particular the concealment of imperfections presented by the individual and / or the creation. new aesthetic effects, possibly changing over time.

 By the term "polyconjugated polymer, said polymer being an electroluminescent and / or electroconductive polymer" is meant in the sense of the present invention, a polymer comprising conjugated units in a proportion such that this polymer is capable of electroluminescence and / or electroconduction.

 The composition may be film-forming, the film-forming nature being obtainable by the presence of any film-forming agent, which may optionally consist of the electroluminescent and / or electroconductive polymer itself.

 The composition may further comprise any film-forming aid agent such as volatile plasticizers and especially dipropylene glycol N-butyl ether or N-methyl pyrrolidone or such as nonvolatile plasticisers.

 The composition may comprise one or more volatile or non-volatile fluid compounds.

 This or these compounds may be of aqueous or organic type and may be compatible with the use for cosmetic purposes of the composition.

 Thus, this or these fluid compounds may for example be physiologically acceptable for direct contact with the outer surface of the individual on which the composition is intended to be applied.

 However, this or these fluid compounds may also be selected from fluids that are not generally considered physiologically acceptable, provided they are removed for example by evaporation, prior to the application of the composition on the individual.

 Among the fluid compounds that can be included in the formulation of the composition according to the invention, there may be mentioned in particular water, alcohols and in particular lower alcohols such as ethanol, propanol and isopropanol, polyols such as glycerol, propylene glycol, ethylene glycol or propylene glycol ethers, ethylene glycol or propylene glycol ether ethers and ethylene glycol or propylene glycol esters, lower aliphatic esters such as acetates methyl,

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 ethyl, propyl and butyl, ketones such as acetone and methyl ethyl ketone, volatile hydrocarbons, branched or unbranched, hydrocarbon oils, fatty acid esters such as triglycerides of C6 fatty acids at C18, and volatile or nonvolatile silicone oils.

 Electroconductive and / or electroluminescent polyconjugated polymers are known and are described in particular in Kraft. A et al., Angew. Chem. Int. Ed. 1998, 37, 402-428 and in B. François, Conductive Polymers-Chemical Synthesis and Doping, in Initiation to Macromolecular Chemistry and Physico-Chemistry, gfp (French Group for Polymer Studies and Applications) ) p. 87-112.

 According to one embodiment, the electroluminescent and / or electroconductive polymer is present in the form of a dispersion in a fluid medium comprising, for example, one or more of the compounds defined above.

 The electroluminescent and / or electroconductive polymer may in particular be present in the form of a dispersion of particles.

 In particular, the electroluminescent and / or electroconductive polymer may be present in the composition in the form of a dispersion of particles in an aqueous and / or organic liquid phase such as a latex, that is to say a dispersion consisting of of polymer particles obtained directly by polymerization of one or more monomers in a suitable liquid phase or such as a pseudolatex, that is to say a dispersion of particles of the polymer, these being obtained by dispersion of the polymer in a suitable liquid phase, depending on the nature of the polymer and the liquid phase used.

 The composition may also comprise a dispersion of coated particles, that is to say comprising a core surrounded by an envelope, the electroluminescent polymer and / or electroconductive may constitute all or part of the envelope of these particles. The core may consist of any suitable compound and in particular be constituted for example by a polymer other than an electroluminescent or electroconductive polymer, for example polyurethane, and generally any mineral or organic substrate.

 When the core is a polymer, it can be film-forming.

 According to another embodiment, the electroluminescent and / or electroconductive polymer is present in solution in an aqueous and / or organic fluid medium,

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 for example comprising one or more fluid compounds as defined above.

 According to a first embodiment of the invention, the composition comprises at least one electroconductive polymer, the latter having an intrinsic electrical conductivity of between 0.01 and 500,000 S / cm, preferably greater than or equal to 0.05 S / cm, and in particular greater than or equal to 0.1 S / cm.

 As previously indicated, the polyconjugated polymers are electrically conductive only when they are doped, that is to say after reaction with electron donors for n-type doping or with electron acceptors for p-type doping.

The doping reactions can be carried out according to the general scheme of oxidation-reduction reactions:

<Tb>
<tb> doping <SEP> n <SEP>: <SEP> Pol <SEP> + <SEP> y <SEP> D <SEP> Pol <SEP> y <SEP> -, <SEP> y <SEP> D +
<tb> doping <SEP> p <SEP>: <SEP> Pol <SEP> + <SEP> x <SEP> A <SEP> Pol <SEP> x +, <SEP> X <SEP> A <SEP> -
<Tb>
in which: Pol represents the polymer
D represents an electron donor
A represents an electron acceptor and x and y integers or decimals, positive greater than zero.

 The injection or extraction of charges leads to the formation, on the polymer chain, of delocalized ion-radicals (radicals-anions for n-type doping, cation-radicals for p-type doping) and ions. or di-ions (negative or positive depending on the type of doping).

alcalinoterreux et par exemple les contre-ions : Li+, Na+, K+, Ca et Ba, les composés organo alcalins tels que les radicaux-ions comme le naphtalène, des carbanions et des dianions de cétones aromatiques comme par exemple la benzophénone. Among the n-type dopants, mention may in particular be made of alkali metals or

alkaline earth metals and for example the counter-ions: Li +, Na +, K +, Ca and Ba, organo-alkaline compounds such as ion-radicals such as naphthalene, carbanions and aromatic ketone dianions such as, for example, benzophenone.

 Preferred n-type dopants are alkali and alkaline earth metals.

 Among the p-type dopants, mention may be made of oxidants such as halogens and in particular 12 and Br 2, transition metal salts such as FeCl 3, strong acids or else nitrosyl or nitryl salts.

 The doping is carried out during the polymerization when at least a portion of the monomers intended to form the polymer is itself of the doped type, the polymer then being said to be "self-doped" which is the case, for example, of polyaniline and

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 polypyrrole, or when the polymerization medium comprises a doping agent such as for example an oxidant such as ammonium persulfate or transition metal salts.

 In other cases, the doping can be carried out after the polymerization.

 The doping method can be chosen according to the nature of the polyconjugated polymer that one wishes to use as well as the characteristics that one wishes for it, in particular in terms of electroconductivity.

 Such doping methods are known and described in the literature.

 In the present application, the electroconductive polymers are defined by their constituent units, as they result from the polymerization reaction, for the sake of clarity of the disclosure.

 At least one electroconductive polymer selected from the group consisting of homo-and copolymers of the polyparaphenylene, poly (para-phenylene vinylene), poly (heteroarylene vinylene), polyaniline, polypyrrole and polythiophene type, optionally substituted, may be used in the invention as electroconductive polymer. said homo-or copolymers being doped.

 According to one embodiment, the composition comprises, as electroconductive polymer, a homo-or copolymer of the optionally substituted polyparaphenylene type. The electroconductive polymer may in particular be chosen from polyparaphenylene type copolymers and poly (substituted paraphenylene) homo- and copolymers.

 According to another exemplary embodiment, the composition comprises, as electroconductive polymer, a homo-or copolymer of the poly (para-phenylene vinylene) type, optionally substituted.

 The electroconductive polymer may in particular be chosen from poly (paraphenylene vinylene) type copolymers and poly (substituted paraphenylene vinylene) homo-and copolymers. Among these, there may be mentioned in particular those containing (2, 5-dialkoxy-1,4-phenylene) vinylene units in which the identical or different alkoxy radicals have from 1 to 40 carbon atoms, provided that the at least one of said radicals has at least 6 carbon atoms. Such polymers are in particular present in the compositions according to the invention in solution in

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 volatile organic solvents.

 According to another embodiment, the composition of the invention comprises, as electroconductive polymer, an optionally substituted polyaniline homo-or copolymer.

 When the composition comprises polyaniline, the latter can in particular be present in the composition in the form of a latex in an aqueous medium.

 The electroconductive polymer used in the composition may also be a homo-or copolymer of substituted aniline, in particular substituted on the ring by alkyl or alkoxy radicals.

 According to another embodiment, the composition comprises, as electroconductive polymer, a homo-or copolymer of the polypyrrole type.

 Said polymer may in particular be present in the composition in the form of a dispersion in an aqueous-type medium and in particular in the form of a latex in aqueous solution of methylcellulose.

 According to another embodiment, the polypyrrole-type polymer constitutes the envelope surrounding the nucleus of particles dispersed in an aqueous solution. In particular, the polymer of the polypyrrole type may be a homopolymer constituting the envelope of particles whose core consists of polyurethane dispersed in an aqueous medium, such as one of those sold under the names of "CONQUEST" @ by the company DSM.

 The polypyrrole polymer used as electroconductive polymer may also be chosen from poly (substituted pyrrole), for example substituted on the ring or on nitrogen by alkyl radicals.

 According to another embodiment, the composition comprises, as electroconductive polymer, an optionally substituted polythiophene homo-or copolymer, in particular a polymer chosen from polythiophene-type copolymers and homo-or copolymers of the poly (substituted thiophene) type. Among these, mention may be made in particular of: polymers containing 3-alkylthiophene units in which the linear, branched or cyclic alkyl radical has from 4 to 40 carbon atoms, 3-alkoxyalkylthiophene units and 3-alkoxycarbonylthiophene units , in which the alkoxyalkyl or alkoxycarbonyl radical has from 4 to 30 carbon atoms,

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 3-phenylthiophene or ethylenedioxythiophene units, and - polymers having 3-sulfonatoalkyl thiophene-2,5-diyl units in which the alkyl radical has from 1 to 30 carbon atoms.

 According to a particular embodiment of the composition as defined above, the electroconductive polymer comprising ethylenedioxythiophene units is a copolymer comprising styrene sulfonate units.

 In particular, the composition according to the invention comprises an aqueous dispersion of copoly (ethylenedioxythiophene / styrene sulfonate) such as that sold under the name "BAYTRON P" by the company BAYER.

 Among the polymers comprising units derived from a 3-sulphonatoalkyl thiophene defined above, there may be mentioned in particular poly [3- (3-thienyl) propanesulfonate] and in particular sodium poly [3- (3-thienyl) propane sulphonate marketed by SHOWA DENKO, which is a self-doped polymer.

 This polymer may in particular be present in the compositions according to the invention in solution in an aqueous medium.

 According to a second embodiment of the invention, the composition comprises, as polyconjugated polymer, at least one electroluminescent polymer.

 This polymer may be chosen in particular from the group consisting of homo-and copolymers of polyparaphenylene type, poly (para-phenylene vinylene), poly (heteroarylene vinylene), polythiophene, poly (pyridine vinylene), polyfluorene and polyvinylcarbazole, optionally substituted.

 When the electroluminescent polymer is of the polyparaphenylene type, it is in particular chosen from polyparaphenylene type copolymers and poly (substituted paraphenylene) homo or copolymers.

 In particular, when the electroluminescent polymer is a homo-or copolymer of the poly (substituted para-phenylene) type, it may be chosen in particular from the group consisting of polymers containing 2-alkoxy-1,4-phenylene units in which the alkoxy radical of 1 to 40 carbon atoms and in particular 10 carbon atoms or 2, 5-dialkoxy-1,4-phenylene units in which the alkoxy radicals, which are identical or different, have from 1 to 40 carbon atoms.

 Among the polymers containing 2,5-dialkoxy-1,4-phenylene units, those in which the alkoxy radicals are identical, having in particular

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 especially 5 carbon atoms, and for example the polymers having 2,5di (3-methylbutyloxy) -1,4-phenylene units.

 According to another embodiment, the composition comprises, as electroluminescent polymer, a homo-or copolymer of the poly (para-phenylene vinylene) type, optionally substituted, in particular a polymer chosen from poly (paraphenylene vinylene) type copolymers or homo-or copolymers of type poly (substituted para-phenylene vinylene).

 When the electroluminescent polymer is a homo-or copolymer of the poly (substituted paraphenylene vinylene) type, it may be chosen in particular from the group consisting of polymers containing (2,5-dialkoxy-1,4-phenylene) vinylene units. in which the alkoxy radicals, which are identical or different, have from 1 to 40 carbon atoms and provided that at least one of said radicals has at least 6 carbon atoms, or (2,5-dialkoxy-1,4) units; -phenylene) 1-cyano vinylene in which the alkoxy radicals, which may be identical or different, have from 1 to 30 carbon atoms and provided that at least one of said radicals has at least 4 carbon atoms.

 Among the polymers containing (2, 5-dialkoxy-1,4-phenylene) vinylene units, mention may be made in particular of those having at least one alkoxy radical chosen from the group consisting of 2-ethylhexyloxy and 3,7-dimethyloctyloxy radicals. , 2-methylpentyloxy, nonyloxy and dodecyloxy.

 According to another embodiment, the composition comprises, as electroluminescent polymer, an optionally substituted polythiophene homo-or copolymer, in particular a polymer chosen from polythiophene-type copolymers or homo-or copolymers of the poly (substituted thiophene) type.

 When the electroluminescent polymer is a homo-or copolymer of the poly (substituted thiophene) type, it may in particular be chosen from the group consisting of: (i) polymers comprising 3-alkylthiophene units in which the linear alkyl radical , branched or cyclic, has from 4 to 40 carbon atoms, 3-alkoxyalkylthiophene or 3-alkoxycarbonylthiophene units in which the alkoxyalkyl or alkoxycarbonyl radical has from 4 to 30 carbon atoms, and (ii) the polymers comprising 3 units, 4-dialkylthiophene in which the alkyl radicals, which are identical or different, have from 1 to 40 carbon atoms and

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 reserve that at least one of said alkyl radicals has at least 6 carbon atoms.

 The polymer having 3-alkylthiophene units may be chosen in particular from the group consisting of polymers comprising said units in which the alkyl radical has from 6 to 22 carbon atoms and, in particular, is a cyclohexyl radical or a radical of formula: C6H13, -C8H17, -Cl2H25, -Cl8H37 or-C22H45.

 The electroluminescent polymer having 3alkoxyalkylthiophene units may be chosen in particular from the group consisting of polymers comprising said units in which the alkoxyalkyl radical has from 6 to 30 carbon atoms and, in particular, is a radical of formula: -CloH2oOCH3.

 Among the polymers comprising 3-alkoxycarbonylthiophene units that can be used in the composition according to the invention, mention may be made in particular of those selected from the group consisting of polymers comprising said units in which the alkoxycarbonyl radical has from 6 to 30 carbon atoms. and in particular is a radical of formula: -CO-CHis or -CO-OCgHiy.

 Among the polymers comprising 3,4-dialkylthiophene units that can be used in the compositions according to the invention, mention may in particular be made of those comprising 3,4-dioctylthiophene units or 3-methyl-4-cyclohexylthiophene units.

 According to another embodiment of the invention, the composition comprises, as an electroluminescent polymer, a homo-or copolymer of the poly (pyridine vinylene) type, optionally substituted, in particular a polymer chosen from poly (pyridine vinylene) type copolymers or homopolymers or copolymers of poly (substituted pyridine vinylene) type.

 When the electroluminescent polymer is a homo-or copolymer of the poly (substituted pyridine vinylene) type, it is in particular chosen from the group consisting of: (i) polymers comprising 2-vinylene pyridinium-5-yl units or 2-vinylene N-alkylpyridinium-5-yl units in which the alkyl radical has from 1 to 40 carbon atoms, and in particular from 1 to 10 carbon atoms, and (ii) polymers comprising 2-vinylene-3 units -alkylpyridin-5-yl wherein the alkyl radical has from 1 to 30 carbon atoms.

 Among the polymers comprising 2-vinylene N-alkylpyridinium-5yl units that can be used, it is possible to use a polymer comprising said units in

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 wherein the alkyl radical is a lower alkyl radical, that is to say having 1 to 6 carbon atoms, and in particular the methyl radical.

 Among the polymers containing 2-vinylene-3-alkylpyridine-5-yl units that can be used in the composition according to the invention, it is possible to use a polymer comprising said units in which the alkyl radical has from 1 to 20 carbon atoms, in particular the radical of formula: -C4H9.

 According to another embodiment, the composition comprises, as electroluminescent polymer, a homo-or copolymer of polyfluorene type, optionally substituted, in particular a polymer chosen from polyfluorene type copolymers or homo-or copolymers of poly (substituted fluorene) type.

 When the electroluminescent polymer is a homo-or copolymer of the poly (substituted fluorene) type, it is chosen in particular from those which are mono-or disubstituted in the 9-position, in particular by an alkyl radical such as an alkyl radical having from 1 to 20 carbon atoms, for example-C6H13 or-C8H17 or an alkoxyalkoxyalkyl radical having 3 to 20 carbon atoms, for example - CH2CH20CH2CH2OCH3.

 When a copolymer comprises units unable to participate in the conjugation, it may be a graft copolymer or block, comprising one or more polyconjugated sequences and one or more non-polyconjugated sequences.

 Certain units of the copolymer may be chosen so as to allow or improve the passage in solution or the ability to disperse in a fluid medium.

 The proportion of polyconjugated polymers within the composition will be chosen according to the intended application.

 According to a particular embodiment, the composition also contains at least one physiologically acceptable additive.

 Such an additive may be colored or not.

 As an additive, mention may be made especially of those having a cosmetic activity, such as, for example, moisturizing or emollient agents, makeup additives such as dyes or pigments.

 According to a particular embodiment, the composition also contains fibers.

 Among the fibers that can be used, mention may in particular be made of fibers

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 vegetable fibers, for example cellulose fibers, animal fibers, for example silk fibers, or else synthetic fibers, such as polyamide fibers.

 The fibers may be present in the composition without particular organization. They can still be organized in a network, especially in the form of a frame.

 The subject of the present invention is also a cosmetic film for creating an optical effect, comprising a polyconjugated polymer of the electroconductive and / or electroluminescent type, for example one of the polymers defined above.

 The cosmetic film may in particular be obtained by depositing, on a support, keratinous or otherwise, a composition as defined above.

 The thickness of the film depends on the desired application. It can especially be less than 1 m, which allows it in particular to be comfortable to wear, and to marry if necessary the reliefs of the skin.

 The film can be peelable, which facilitates its removal.

 The subject of the present invention is also the use of an electroconductive and / or electroluminescent polyconjugated polymer as defined above for the preparation of a composition or a cosmetic film intended to create an optical effect.

 The subject of the present invention is also the use of an electroconductive and / or electroluminescent polyconjugated polymer as defined above, as a cosmetic agent intended to create an optical effect.

 The present invention also relates to a makeup process comprising the following steps: (a) applying, on the surface to be made up, (i) a cosmetic composition as defined above comprising at least one electroluminescent and / or electroconductive polymer, or ( ii) a film as defined above, comprising at least one electroluminescent and / or electroconductive polymer, and preferably (b) directly or indirectly connecting an electrical source to the composition or to the film thus applied (e).

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 The surface to be makeup may be constituted for example by the skin or superficial body growths.

 The film mentioned in (ii) above may be optionally separated from the surface of the skin or superficial body growths by one or more layers intended for example to allow the film to adhere to the skin or integuments, and / or to allow physiological compatibility of the film with the skin or superficial body growths, and / or supplying electric power to the film.

 According to one embodiment of the makeup process, this comprises the application of a composition or a film comprising at least one electroluminescent polymer. The extent of the surface covered by the composition will depend on the desired optical effect, being for example less than 1 cm 2 for the creation of a local optical effect.

 The electroluminescent polymers are generally photoluminescent so that they may optionally constitute a light source of variable color depending on the external lighting.

 According to another embodiment of the makeup process, this comprises the application of a composition or a film comprising at least one electroconductive polymer, for example to convey electric current from a current source to an electroluminescent polymer or any other electrical or electro-optical device.

 The aforementioned electrical source can be for example a photovoltaic or thermovoltaic cell or a battery.

 According to a particular embodiment of the makeup process, this further comprises the step of varying the electric current applied to said composition or said film in order to obtain a variable optical effect, in particular with the aid of a control device. This control device may in particular vary the intensity of the current delivered as a function of external parameters, such as, for example, temperature, ambient lighting or sound.

 Another subject of the invention is a device intended to create an optical effect comprising a multilayer structure capable of being applied to a keratin support such as the skin, the lips or the nails, this structure comprising an adhesive support and at least one electroluminescent polymer. and / or electrically conductive such as

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 previously defined.

 The multilayer structure may comprise two electrodes, respectively a cathode and an anode, between which an electric current delivered by a power supply source may flow.

 In an exemplary implementation of the invention, the multilayer structure comprises, on an insulating adhesive support capable of adhering to a skin, lips or nails, a first electrode, for example a cathode, one or more layers of polymer electroluminescent, a second transparent electrode, for example an anode, and a transparent substrate.

 In the case where the multilayer structure comprises several layers of conductive polymer, the latter may be of the same type or not.

 The cathode can be based on aluminum, calcium or magnesium.

 The anode may be based on indium-doped tin oxide (ITO).

 The transparent substrate can be based on glass or plastic.

 The electroluminescent polymer layer may be arranged to form a set of pixels each having a size of the order of one micron, each of the pixels having a light emitting polymer selected to emit light of a predetermined color.

 The set of pixels may be deposited on the second transparent electrode so as to form an image.

 A pixel can be defined by a regular surface, for example a square or a circle, or irregular and form a spot having a size of the order of one micron or more.

 It is thus possible to produce a layer of electroluminescent polymer with a set of pixels making it possible, when an electric current flows through this layer, to obtain a light emission which is visible through the transparent electrode and the transparent substrate.

 The electroluminescent polymer (s) may be deposited, in particular on the second transparent electrode, by centrifugation (spincoating) or ink jet.

 In another example of implementation of the invention using not electroluminescent polymers but electroconductive polymers, the multilayer structure may comprise the following layers: an adhesive support,

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 a reflective layer, for example a metal layer, a filtering layer, an analyzer layer, a transparent film, for example based on glass or plastic, a first transparent electrode, for example an ITO anode, , the aforementioned transparent film serving as a support for this anode, a layer based on liquid crystals, a film based on conductive polymer forming a second electrode, for example a cathode, a transparent insulating layer, for example based on glass or plastic, and - a polarizer layer.

 In this example, the color or colors of the multilayer structure come from the surrounding light which is spectrally filtered and polarized.

 The liquid crystals make it possible to change or not the polarization of the light. The arrangement of liquid crystals that allows or not the passage of light is itself a function of the applied electrical stress, including the passage or not of the current.

 Thus, when no electric current is applied between the electrodes, the liquid crystals cause the polarization change of the light, which allows the light to pass through the analyzer layer, and the light filtered by the filter layer is re-emitted by the reflective layer.

 When an electric current is applied between the electrodes, the liquid crystals orient themselves and do not cause a change in the polarization of the light, which can not pass through the analyzer layer. Thus, the light is not re-emitted.

 For example, the liquid crystal layer is sandwiched between the conductive polymer film and the anode.

 The conductive polymer-based film may not have a conductive polymer over its entire surface, the conductive polymer may form image-defining pixels, for example, a still image.

 The conductive polymer film may be, for example, made from a

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 aqueous dispersion of poly (ethylenedioxythiophene / styrene sulfonate) copolymer such as that sold under the name "BAYTRON P" by the company BAYER.

 The characteristics of the re-emitted light, in particular its color, may depend in particular on the one hand on the color of the filter layer at the location of the conductive polymer pixel, this filtering layer having a set, regular or no, one or more different colors, and, secondly, the intensity of the current applied locally to the conductive polymer at the pixel.

 The device can be passive, that is to say that it is necessary to have an external light source.

 Alternatively, the reflective layer is replaced by a film of electroluminescent polymer capable of being electrically excited.

 The device can be connected to a power source arranged so as to be housed in items such as a pin, an earring, a collar, a branch of glasses.

 The device may be devoid of a control system for varying the intensity of the current delivered by the electrical source. In this case, the image obtained is fixed, being for example of a constant appearance when an electric current is applied.

 As a variant, in order to obtain a variable image, the device may comprise a control system that makes it possible, by addressing, to locally control the intensity of the electric current, so as to obtain a modulation, preferably from 0 to 100%, of the brightness of each pixel of the image.

 The control system may be able to selectively excite each pixel, this system may comprise electrical circuits that may be constituted by electrical switches or by transistors.

 The control system may in particular be arranged to selectively excite each pixel to give an impression of displacement of an element of the image.

 The control system can also be arranged to control the intensity of the electric current according to external parameters such as the temperature, the surrounding brightness, the surrounding color, the humidity, the surrounding pH, the secretion of sweat or sebum, heart rate, date and / or time.

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 This control system can thus include or be connected to a thermocouple or a photoelectric cell.

 This system can also include a microprocessor for processing data relating to external parameters and generate an electrical signal based on these data.

 The control system can still be arranged so that it can be controlled by a user.

 The voltage of the electrical source can be chosen so as to be acceptable from a physiological point of view, being for example of the order of a few volts, while providing sufficient electrical excitation to obtain a satisfactory light image. In particular, the chosen voltage may not cause undesirable effects such as heating of the multilayer structure or disturbance of the electromagnetic environment.

 The multilayer structure may form a patch, which may be adhesive for example.

 This patch may be arranged so as to be temporarily applied to a keratin support such as the skin, the lips, or the nails, being easily deformable to conform to the shape of the keratinous support and adhere thereto.

- la figure 2 représente schématiquement un ensemble de pixels formé par la couche de polymère électroluminescent de la figure 1, - la figure 3 représente de manière schématique et partielle, en coupe transversale, un patch comportant un polymère électroconducteur associé à des cristaux liquides, et - la figure 4 représente schématiquement un ensemble de pixels formé par le film à base de polymère électroconducteur de la figure 3. The invention also relates to an adhesive patch as defined above.
Other features and advantages of the present invention will emerge on reading the following detailed description, non-limiting examples of implementation, and on examining the appended drawing, in which: FIG. schematically and partially, in cross section, a patch comprising a layer of electroluminescent polymer,

FIG. 2 diagrammatically represents a set of pixels formed by the electroluminescent polymer layer of FIG. 1; FIG. 3 is a schematic and partial cross-sectional view of a patch comprising an electroconductive polymer associated with liquid crystals, and FIG. 4 schematically represents a set of pixels formed by the electroconductive polymer-based film of FIG. 3.

 FIG. 1 shows a "patch" adhesive 1 intended to create an effect

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 optical on the skin S of a user. The patch 1 is constituted by a multilayer structure comprising, on an insulating adhesive support 2 intended to be fixed on the skin S, a cathode 3, a layer of electroluminescent polymer 4, a transparent anode 5 and a transparent substrate 6.

 In the example described, the cathode 3 is based on aluminum, calcium or magnesium and the anode 5 based on tin oxide doped with indium (ITO).

 The transparent substrate 6 is based on glass or plastic.

 The electrodes 3 and 5 are connected to a power supply 15.

 The electroluminescent polymer layer 4 is arranged to form a set of pixels having a size of the order of one micron, each of the pixels having a light emitting polymer selected to emit light of a predetermined color.

 As can be seen in FIG. 2, the set of pixels is arranged to form an "O" pattern, this set comprising pixels 10 of red, green 11 and blue 12.

 In the example described, a 3,4-dioctylthiophene homopolymer composition is used in order to generate a blue pixel 12.

 A green pixel 11 is obtained from a composition based on homopolymer 3-octylthiophene.

 A red pixel is obtained by using a composition based on a copolymer of 3-octylthiophene and thiophene, the repeating units being constituted by the succession of a 3-octylthiophene unit, of two thiophene units and of a unit 3 -octylthiophène.

 An electroluminescent polymer layer is thus produced with a set of pixels making it possible, when an electric current passes through this layer, to obtain a light image which is visible through the anode 5 and the transparent substrate 6.

 The electroluminescent polymer or polymers are deposited on the anode 5, by spin coating (spincoating) or ink jet.

 FIG. 3 shows an adhesive "patch" 20 according to another embodiment of the invention having a multilayer structure comprising the following layers:

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 an adhesive support 21, a reflective metallic layer 22, a filtering layer 23, an analyzer layer 24, a transparent film 25, based on glass or plastic, an anode 26 made of ITO, layer based on liquid crystals 27, - a film based on conductive polymer 28 forming a cathode, - a transparent insulating layer 29, based on glass or plastic, and - a polarizer layer 30.

 The electrodes of the patch 20 are connected to an electrical source 15.

 In the example described, the color or colors of the multilayer structure come from the surrounding light which is spectrally filtered and polarized.

 The liquid crystals make it possible to change or not the polarization of the light. The arrangement of the liquid crystals is itself a function of the applied electrical stress.

 Thus, when no electric current is applied between the electrodes 26 and 28, the liquid crystals cause the change in polarization of the light, which allows the light to pass through the analyzer layer 30, and the light filtered by the filtering layer 23 is re-emitted by the reflective layer 22.

 When an electric current is applied between the electrodes 26 and 28, the liquid crystals orient themselves and do not cause the change in the polarization of the light, which can not pass through the analyzer layer 30. Thus, the light is not not re-issued.

 The liquid crystal layer 27 is sandwiched between the conductive polymer film 28 and the anode 26.

 The conductive polymer-based film 28 forms a set of pixels, some pixels having a conductive polymer, others 36 being deprived.

 The pixels 35 form an "S" pattern, as can be seen in FIG. 4.

 The conductive polymer film 28 is made from an aqueous dispersion of poly (ethylenedioxythiophene / styrene sulfonate) copolymer such as that sold under the name "BAYTRON P" by the company BAYER.

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 The characteristics of the re-transmitted light depend in particular on the one hand on the color of the filter layer at the location of the conductive polymer pixel, this filtering layer having a set, regular or not, of one or several different colors, and, secondly, the intensity of the current applied locally to the conductive polymer at the pixel.

 In the example described, the patch 20 is passive, that is to say it is necessary to have an external light source.

 Alternatively, the reflective layer 22 is replaced by a film of electroluminescent polymer capable of being electrically excited.

 The power source 15 to which the patches 1 and 20 are connected can be arranged so as to be housed in articles, not shown, such as a pin, an earring, a collar, a branch of glasses.

 In the example described, the patch 1 is not connected to any control system for varying the intensity of the current delivered by the electrical source 15. The image obtained is then fixed, being of a constant appearance when an electric current is applied.

 As a variant, in order to obtain a variable image, the patch may be connected to a control system that makes it possible, by addressing, to locally control the intensity of the electric current, so as to obtain a modulation, preferably from 0 to 100% , the brightness of each pixel of the image.

 The control system may be able to selectively excite each pixel, this system may comprise electrical circuits that may be constituted by electrical switches or by transistors.

 This control system can be arranged to control the intensity of the electric current according to external parameters such as the temperature, the surrounding brightness, the surrounding color, the humidity, the surrounding pH, the secretion of sweat or sebum , heart rate, date and / or time.

 This control system may thus comprise a thermocouple or a photoelectric cell.

 This system can also include a microprocessor for processing data relating to external parameters and generate an electrical signal based on these data.

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 The control system can still be arranged so that it can be controlled by a user.

 The voltage of the electrical source 15 is of course chosen to be acceptable from a physiological point of view, being of the order of a few volts, while providing sufficient electrical excitation to obtain a satisfactory light image. In particular, the chosen voltage must not cause undesirable effects such as heating of the multilayer structure or disturbance of the electromagnetic environment.

 The adhesive patch 1 or 20 may be arranged to be temporarily applied to a keratin support such as skin, lips, or nails, being easily deformable to conform to the shape of the keratinous support and adhere thereto.

 With the aforementioned multilayer structures, images of different types can be generated. These may have for example a single color on a colorless background, different shades of the same color such as for example different shades of red, several colors chosen in particular from the primary colors (yellow, red, blue), or even several levels of gray varying substantially from colorless to black. These images can be variable or not, with a colored pattern or not that can alternately appear and disappear.

 The images formed can have a decorative role or even allow to hide imperfections such as wrinkles, fine lines, pores, local redness, visible blood vessels or even dark circles.

Claims (53)

Cosmetic composition intended to create an optical effect, characterized in that said composition comprises at least one polyconjugated polymer, said polymer being an electroluminescent and / or electroconductive polymer, and being present in a proportion such that the electrical properties and / or The electro-optics of the composition are essentially derived from the presence of this electroluminescent and / or electroconductive polymer.  2. Composition according to claim 1, characterized in that said composition is film-forming.  3. Composition according to Claim 2, characterized in that the electroluminescent and / or electroconductive polymer is film-forming.  4. Composition according to any one of the preceding claims, characterized in that the electroluminescent and / or electroconductive polymer is present in the form of a dispersion in a fluid medium.  5. Composition according to claim 4, characterized in that it comprises coated particles, comprising a core surrounded by an envelope, said electroluminescent and / or electroconductive polymer constituting all or part of the envelope of these particles.  6. Composition according to any one of claims 1 to 3, characterized in that the electroluminescent polymer and / or electroconductive is present in solution in a fluid medium.  7. Composition according to any one of the preceding claims, characterized in that the said composition comprises at least one electroconductive polymer, the latter having an intrinsic electrical conductivity of between 0.01 and 500,000 S / cm, preferably greater than or equal to equal to 0.05 S / cm, and in particular greater than or equal to 0.1 S / cm.  8. Composition according to Claim 7, characterized in that the said electroconductive polymer is chosen from the group consisting of homo-and copolymers of the polyparaphenylene, poly (paraphenylene vinylene), poly (heteroarylene vinylene), polyaniline, polypyrrole and polythiophene type, optionally substituted, said homo-or copolymers being doped. <Desc / Clms Page number 22>  9. Composition according to claim 8, characterized in that said electroconductive polymer is a homo-or copolymer of the poly (substituted paraphenylene vinylene) type having (2,5-dialkoxy-1,4-phenylene) vinylene units in which the Alkoxy radicals, which may be identical or different, have from 1 to 40 carbon atoms, provided that at least one of said radicals has at least 6 carbon atoms.  10. Composition according to claim 8, characterized in that said electroconductive polymer is of the polypyrrole type.  11. Composition according to claim 8, characterized in that said electroconductive polymer is a homo-or copolymer of the poly (substituted thiophene) type, and is selected from the group consisting of: polymers comprising 3-alkylthiophene units in which the linear, branched or cyclic alkyl radical has from 4 to 40 carbon atoms, 3-alkoxyalkylthiophene units and 3-alkoxycarbonylthiophene units, in which the alkoxyalkyl or alkoxycarbonyl radical has from 4 to 30 carbon atoms; phenylthiophene or ethylenedioxythiophene units, and polymers having 3-sulfonatoalkyl thiophene-2,5-diyl units in which the alkyl radical has from 1 to 30 carbon atoms.  12. Composition according to claim 11, characterized in that said polymer comprising ethylenedioxythiophene units is a copolymer comprising styrene sulfonate units.  13. A composition according to claim 11, characterized in that said polymer having 3-sulfonatoalkyl thiophene-2,5-diyl units is poly- [3- (3thienyl) propane sulfonate].  14. Composition according to any one of claims 1 to 6, characterized in that said electroluminescent polymer is selected from the group consisting of homo-and copolymers of polyparaphenylene type, poly (para-phenylene vinylene), poly (heteroarylene vinylene), optionally polythiophene, poly (pyridine vinylene), polyfluorene, and polyvinylcarbazole.  15. Composition according to claim 14, characterized in that said electroluminescent polymer is a homo-or copolymer of the poly (substituted para-phenylene) type, selected from the group consisting of polymers comprising 2-alkoxy-1,4-phenylene units. in which the alkoxy radical has from 1 to 40 carbon atoms or <Desc / Clms Page number 23>  2,5-dialkoxy-1,4-phenylene units in which the alkoxy radicals, which may be identical or different, have from 1 to 40 carbon atoms.  16. A composition according to claim 15, characterized in that said electroluminescent polymer comprises 2-alkoxy-1,4-phenylene units in which the alkoxy radical has 10 atoms or 2,5-di (3-methylbutyloxy) - 1,4-phenylene.  17. A composition according to claim 14, characterized in that said electroluminescent polymer is a homo-or copolymer of the poly (substituted paraphenylene vinylene) type, selected from the group consisting of polymers containing (2, 5-dialkoxy-1) units. , 4-phenylene) vinylene in which the alkoxy radicals, which are identical or different, have from 1 to 40 carbon atoms and provided that at least one of said radicals has at least 6 carbon atoms, or units (2, 5 -dialcoxy-1,4-phenylene) 1-cyano-vinylene in which the alkoxy radicals, which are identical or different, have from 1 to 30 carbon atoms and provided that at least one of said radicals has at least 4 carbon atoms .  18. A composition according to claim 17, characterized in that said polymer containing (2,5-dialkoxy-1,4-phenylene) vinylene units has at least one alkoxy radical selected from the group consisting of 2-ethylhexyloxy radicals, 3,7-dimethyloctyloxy, 2-methylpentyloxy, nonyloxy and dodecyloxy.  19. Composition according to Claim 14, characterized in that the said electroluminescent polymer is a homo-or copolymer of the poly (substituted thiophene) type, selected from the group consisting of: (i) polymers comprising 3-alkylthiophene units in which the linear, branched or cyclic alkyl radical has from 4 to 40 carbon atoms, 3-alkoxyalkylthiophene or 3-alkoxycarbonylthiophene units in which the alkoxyalkyl or alkoxycarbonyl radical has 4 to 30 carbon atoms, and (ii) the polymers comprising 3,4-dialkylthiophene units in which the alkyl radicals, which are identical or different, have from 1 to 40 carbon atoms and provided that at least one of said alkyl radicals has at least 6 carbon atoms.  20. Composition according to Claim 19, characterized in that the said polymer comprising 3-alkylthiophene units is chosen from the group consisting of polymers comprising the said units in which the alkyl radical has from 6 to 22 carbon atoms and, in particular, is a cyclohexyl radical or a radical of formula: <Desc / Clms Page number 24>

21. Composition according to Claim 19, characterized in that the said polymer comprising 3-alkoxyalkylthiophene units is chosen from the group consisting of polymers comprising the said units in which the alkoxyalkyl radical has from 6 to 30 carbon atoms and, in particular, is a radical of formula: - ClOH2oOCH3.  22. Composition according to Claim 19, characterized in that the said polymer comprising 3-alkoxycarbonylthiophene units is chosen from the group consisting of polymers comprising the said units in which the alkoxycarbonyl radical has from 6 to 30 carbon atoms, and in particular , is a radical of formula: -CO-OCsHou-CO-OCgHiy 23. Composition according to Claim 19, characterized in that the said polymer comprising 3,4-dialkylthiophene units is chosen from the group consisting of polymers containing 3,4-dioctylthiophene units, or 3-methyl-4- units. cyclohexylthiophène.  24. A composition according to claim 14, characterized in that said electroluminescent polymer is a homo-or copolymer of the poly (substituted pyridine vinylene) type selected from the group consisting of: (i) polymers comprising 2-vinylene pyridinium-2 units; 5-yl or 2-vinylene N-alkylpyridinium-5-yl units in which the alkyl radical has from 1 to 40 carbon atoms, and (ii) polymers comprising 2-vinylene-3-alkylpyridine-5-yl units in which the alkyl radical has from 1 to 30 carbon atoms.  25. The composition as claimed in claim 24, characterized in that said polymer comprising 2-vinylene N-alkylpyridinium-5-yl units is chosen from the group consisting of polymers comprising said units in which the alkyl radical has from 1 to 10 carbon atoms and, in particular, is a lower alkyl radical.  26. Composition according to Claim 24, characterized in that the said polymer comprising 2-vinylene 3-alkylpyridin-5-yl units is chosen from the group consisting of polymers comprising the said units in which the alkyl radical has from 1 to 20. carbon atoms and, in particular, is the radical of formula: -C 4 H 9.  27. Composition according to claim 14, characterized in that said <Desc / Clms Page number 25>  The electroluminescent polymer is a homo-or copolymer of the poly (substituted fluorene) type chosen from poly (fluorene mono- or disubstituted at the 9-position).  28. Composition according to any one of the preceding claims, characterized in that the said composition also contains at least one physiologically acceptable additive.  29. Composition according to any one of the preceding claims, characterized in that said composition contains fibers.  30. Composition according to claim 29, characterized in that said fibers are organized in a network, in particular in the form of a frame.  31. Cosmetic film for creating an optical effect, obtained by depositing, on a keratinous or non-keratinous support, a composition as defined according to any one of Claims 1 to 30.  32. Use of an electroconductive polyconjugated polymer as defined in any one of claims 7 to 13 and / or electroluminescent as defined in any one of claims 14 to 27, for the preparation of a composition or of a cosmetic film for (e) creating an optical effect.  33. Use of an electroconductive polyconjugated polymer as defined in any one of claims 7 to 13 and / or electroluminescent as defined in any one of claims 14 to 27, as a cosmetic agent intended to create a optical effect.  34. Makeup method, characterized in that it comprises the following steps: a) applying, on the surface to be made up, (i) a cosmetic composition as defined in any one of claims 1 to 30 comprising at least an electroluminescent and / or electroconductive polymer, or (ii) a film as defined in claim 31 comprising at least one electroconductive and / or electroluminescent polymer, and b) directly or indirectly connecting an electrical source to the composition or film thus applied (e).  35. Makeup method according to claim 34, characterized in that it further comprises the step of varying the electric current applied to <Desc / Clms Page number 26>  said composition or said film in order to obtain a variable optical effect.  36. Device for creating an optical effect, characterized in that it comprises a multilayer structure (1; 20) capable of being applied to a keratin support such as the skin (S), the lips or the nails, this structure comprising an adhesive support (2; 21), and a layer comprising at least one electroluminescent and / or electroconductive polymer as defined in any one of claims 1 to 31.  37. Device according to the preceding claim, characterized in that the multilayer structure comprises two electrodes (3; 5; 26; 28), respectively a cathode and an anode, between which can flow an electric current delivered by a power source. electric (15).  38. Device according to the preceding claim, characterized in that the multilayer structure (1) comprises, on an insulating adhesive support (2), a first electrode (3), for example a cathode, a layer of electroluminescent polymer (4). a second transparent electrode (5), for example an anode, and a transparent substrate (6).  39. Device according to the preceding claim, characterized in that the cathode (3) is based on aluminum, calcium or magnesium.  40. Device according to any one of the two preceding claims, characterized in that the anode (5) is based on tin oxide doped with indium.  41. Device according to any one of claims 38 to 40, characterized in that the transparent substrate (6) is based on glass or plastic.  42. Device according to any one of claims 38 to 41, characterized in that the electroluminescent polymer layer (4) is arranged to form a set of pixels each having a size of the order of one micron, each of pixels comprising an electroluminescent polymer selected to emit light of a predetermined color.  43. Device according to the preceding claim, characterized in that the electroluminescent polymer or polymers are deposited, in particular on the second transparent electrode, by spin coating (spincoating) or ink jet.  44. Device according to claim 37, characterized in that the multilayer structure (20) comprises the following layers: <Desc / Clms Page number 27>  an adhesive support (21), a reflective layer (22), for example a metal layer, a filtering layer (23), an analyzer layer (24), a transparent film (25), for example based on glass or plastic, - a first transparent electrode (26), for example an ITO anode, - a layer based on liquid crystals (27), - a film based on a conductive polymer, - a transparent insulating layer (29), for example based on glass or plastic, and - a polarizer layer (30).  45. Device according to the preceding claim, characterized in that the liquid crystal layer (27) is sandwiched between the conductive polymer-based film (28) and the anode (26).  46. Device according to any one of the two preceding claims, characterized in that the conductive polymer-based film may not comprise conductive polymer on its entire surface.  47. Device according to any one of claims 44 to 46, characterized in that the conductive polymer film is made from an aqueous dispersion of poly (ethylenedioxythiophene / styrene sulfonate) copolymer.  48. Device according to any one of claims 44 to 47, characterized in that the reflective layer is replaced by a film of electroluminescent polymer capable of being electrically excited.  49. Device according to any one of claims 36 to 48, characterized in that it is connected to a power supply source arranged to be accommodated in articles such as a pin, a loop of ear, a necklace, a branch of glasses.  50. Device according to the preceding claim, characterized in that it does not have a control system for varying the intensity of the current delivered by the electrical source.  51. Device according to the preceding claim, characterized in that it comprises a control system allowing by addressing to control locally. <Desc / Clms Page number 28>  the intensity of the electric current.  52. Device according to the preceding claim and one of claims 42 and 46, characterized in that the control system is adapted to selectively excite each pixel.  53. Device according to any one of the two preceding claims, characterized in that the control system is arranged to control the intensity of the electric current according to external parameters such as the temperature, the surrounding brightness, the color surrounding, moisture, surrounding pH, secretion of sweat or sebum, heart rate, date and / or time.