FR2850568A1 - Use of a conductive polythiophene in a composition for imparting an optical effect to human keratin materials e.g. human keratin fibers - Google Patents

Abstract

A composition comprises at least one conductive polythiophene in a cosmetic medium. The polythiophene is present in a soluble or dispersible form in the medium. A composition comprises at least one conductive polythiophene containing at least one repeat unit of formula (2,2')bi-thiophen-5,5'-diyl (substituted at 3, 4, 3' and 4' positions by R 1, R 2, R 3and R 4, respectively) (I), thiophen-2,5-diyl (II) or (III), in a cosmetic medium. The polythiophene is present in a soluble or dispersible form in the medium. [Image] R 1- R 4H, -R, -OR, -COOR or -OCOR; R : 1-20C alkyl optionally containing a heteroatom (preferably O), halo, nitro, cyano, alkylcyano or S1; S1 : a solubilizing group (preferably a carboxyl (-COOH), carboxylate(-COO ->M +>), sulfonic (-SO 3H), sulfonate (-SO 3->M +>), amine, quaternary ammonium (-N(Rb) 3+>Y ->), hydroxyl or poly(2C or 3C alkylene oxide) radical); M : alkali metal, alkaline earth metal, organic amine, alkanolamine or amino acid; Y : Br, Cl, 1-4C alkyl-OSO 3or tosylate; Rb : T; T : linear or branched 1-20C alkyl optionally containing a heteroatom; Rb+Rb : a heterocycle containing nitrogen; Z : -CH-CH- or -Ctriple boundC-. Provided that: at least one of R 1- R 4is a solubilizing group in the repeat units. The solubilizing group is optionally joined to the ring via a spacer group selected from -R'-, -OR'-, -OCOR'- or -COOR'- (where R' is T).

Description

USE OF CONDUCTIVE POLYTHIOPHENES FOR THE TREATMENT OF MATERIALS

HUMAN KERATINICS

  The invention relates to the use of compositions comprising, in a cosmetically acceptable medium, at least one conductive polythiophene, as an agent intended to impart an optical effect to human keratin materials and more particularly to fibers. In addition, when said polythiophene absorbs in the visible, the composition comprising it is used as a coloring agent for said materials. The invention also relates to a composition comprising it.

  Products intended to impart shine effects to the hair are known.

  Such products contain molecules, or even polymers, in the solubilized state, in emulsion or in dispersion, in a cosmetic solvent.

  However, these products do not yet provide the hair with the desired shine.

  To obtain a shine effect on the hair, it is known to use compositions rich in hydrophobic lubricating substances, such as oils or organic waxes or silicones. Here again, however, the shine effect obtained lacks intensity and generally gives the hair an artificial appearance.

  In addition, such compositions, once applied to the hair, have the drawback of providing a greasy or sticky feel to the hair, which is not satisfactory.

  There is therefore a need to find compositions capable of communicating with human keratin materials, more particularly fibers, and advantageously hair, an intense and natural shine without having the drawbacks mentioned above.

  In addition, to obtain particularly aesthetic effects, an addition of shine 30 accompanied by an addition of coloring may sometimes prove advantageous.

  Now, it has been found quite unexpectedly and surprisingly that it was possible to bring to the whole of the hair, and in a uniform manner, an optical effect, and more particularly a substantially more intense, more natural shine, and more aesthetic than with the means of the prior art, using conductive polythiophenes.

  In addition, when said conductive polythiophenes absorb in the visible spectrum, an optical effect, such as brightness and color, is simultaneously obtained.

  Finally, the hair advantageously has a soft and pleasant touch. 40 The first object of the present invention is thus, the use as an agent intended to impart an optical effect to human keratin materials, more particularly to human keratin fibers, of a composition comprising, in a cosmetically acceptable medium, at least one conductive polythiophene being in a form soluble or dispersible in said medium, comprising at least one repeating unit of formulas (1) to (111) below R 3 R4 Ri R2 \ / Z Formulas in which: the radicals R, Ri to R4 are identical or different, are selected from the group formed by hydrogen, a radical -R ', -OR', -COOR ', -OCOR', with R 'representing a linear or branched C0-C20 alkyl radical, an atom of halogen, a nitro radical, a cyano radical, an alkylcyano radical, and solubilizing groups, it being understood that at least one radical from R, R 1 to R 4 denotes a solubilizing group; Z represents -CH = CH- or -C C-.

  A second object of the invention consists of the use as an agent intended for coloring human keratin materials, more particularly human keratin fibers, of a composition comprising, in a cosmetically acceptable medium, at least one conductive, absorbent polythiophene light in the visible spectrum, being in a form soluble or dispersible in said medium, comprising at least one repeating unit of formulas (1) to (111) above. The invention further relates to a dye composition for human keratin fibers and more particularly hair comprising, in a cosmetically acceptable medium, at least one conductive polymer present in a form soluble or dispersible in said absorbent medium in the visible spectrum, comprising at least one repeating unit of formulas (1) to (Ill).

  However, other characteristics, aspects, objects and advantages of the invention will appear more clearly on reading the description and the example which follow.

  Within the meaning of the present invention, the term optical effect covers effects of shine, metallic effects, color, goniochromatic, moiré, fluorescent, thermochrome, electrochromic.

  More particularly, the term gloss is understood to mean the light intensity reflected at an angle ax when the lock of hair is lit at an angle -a. The angle oc conventionally used to measure this specular reflection, in other words the gloss, is equal to 200. This contribution of gloss can be measured by using a gloss meter as it is for example described in standard ISO 2813 -1994 of 1 'AFNOR (August 1994, 15 corrigendum February 1997).

  Conductive polythiophenes The conductive polythiophene used in the context of the invention has a molecular structure in which the monomer (s) have a strong electronic delocalization and the arrangement of which in the polymer backbone allows the iX orbitals to overlap. This chemical characteristic results in an electrical conduction phenomenon which may or may not be accompanied by an absorption phenomenon in the UV-visible spectrum, or even in the infrared.

  When it is indicated in the text that the conductive polythiophene absorbs in the visible, this means that the polymer has a non-zero absorbance in the wavelength range from 400 to 800 nm, even if the absorption maxima of the polymer are outside this range.

  The conductive polymers used in the context of the present invention are conductive polymers which are soluble or dispersible in the cosmetic medium suitable for the application.

  The polymer is said to be soluble in the medium when it forms an isotropic clear liquid at 250 ° C. in the medium comprising water or a water / solvent mixture; this being obtained in all or part of a concentration range of between 0.01 and% by weight of conductive polymer.

  The polymer is said to be dispersible in the medium comprising water or a water / solvent mixture if, at 0.01% by weight, at 250 ° C., it forms a stable suspension of fine particles, generally spherical. The average size of the particles constituting said dispersion is less than 1 μm and, more generally, varies between 5 and 400 nm, preferably from 10 to 250 nm. These particle sizes are measured by light scattering.

  Preferably, the conductive polymers used in the context of the present invention are conductive polymers which are soluble or dispersible in an aqueous medium, advantageously in water.

  It should be noted that advantageously, these polymers do not require the use of a dispersing agent.

  In addition, the polymers advantageously have a conductivity between 10-5 and 5.105 siemens / cm, more particularly between 10-3 and siemens / cm, and preferably between 10-1 and 104 siemens / cm.

  The conductivity is measured using a current generator (RM2 Test Unit marketed by the company Jandel) fitted with a so-called four-point measurement head 15 (Universal four-point probes marketed by the company Jandel). The four aligned and distant tips of the same spacing d are applied by simple pressure on the sample to be analyzed. A current I is injected by the external tips using the current source thus creating a potential variation. The voltage U is measured between the two internal tips connected to the voltmeter of the current generator. 20 In this configuration the conductivity of the sample expressed in S / cm is given by the following expression a = (K x 1) / (U xe) With: K coefficient depending on the position of the contacts on the surface of the sample.

  When the tips are aligned and equidistant, K is equal to: I / log (2) i: value of the injected current expressed in amperes U: value of the measured voltage expressed in volts e: thickness of the sample expressed in cm 30 This expression can only be used when the thickness of the material is negligible compared to the distance d existing between two points (e / d <0.25). To obtain sufficiently small thicknesses and thus be able to calculate the conductivity of the material, it is recommended to carry out the measurement on a non-conductive support (for example, a glass slide) 35 covered with the material to be analyzed obtained by evaporation of a dilute solution . In order to improve the homogeneity of the coating to be analyzed, it is also recommended to use the so-called spin coating deposition technique.

  As indicated above, the polythiophenes used comprise at least 40 a repeating unit of formulas (1) to (Ill) below: R3 R4 1 '2 (1) s R R2 (Il) Ri R2 R1 R2 (Ill) Formulas in which: the radicals R, R1 to R4, identical or different, are chosen from the group formed by hydrogen, a radical -R ', -OR', -COOR ', -OCOR', with R 'representing a linear alkyl radical or branched in C1-C20, a halogen atom, a nitro radical, a cyano radical, an alkylcyano radical, and solubilizing groups, it being understood that at least one radical from R, R1 to 10 R4 denotes a solubilizing group; Z represents -CH = CH- or - CC-C-.

  Preferably, if the radicals R1 and R3 of the repeating unit of formula (I) are identical, then the radicals R2 and R4 are different, and vice versa. The solubilizing groups are preferably chosen from the group formed by: A carboxylic radical (-COOH), carboxylate (-COO-M + with M representing an alkali metal such as sodium, potassium, an alkaline earth metal, an amine organic such as a primary, secondary or tertiary amine, an alkanolamine, an amino acid), * a sulfonic radical (-SO3H), sulfonate (-SO3-M +, M having the same definition as above), * an amine radical primary, secondary or tertiary; more particularly a radical of type -NH2, -NHR, -N (R) 2, with R, identical or different representing an alkyl radical, linear or branched C1 to C20, optionally comprising a heteroatom such as oxygen; as well as their salts with mineral or organic acids (for example NH3 + X-, RNH2 + X-, (R) 2NH + X- respectively, with X representing a halogen atom, preferably chlorine, or an ion coming from a carboxylic acid such as CH3COO-); * a quaternary ammonium radical for example such as -NR'3 + Z- with Z = Br, Cl, (C1-C4) alkyl -OSO3 and R 'alkyl, identical or not, linear or branched in Ci to C20, optionally comprising a heteroatom like oxygen, or forming a heterocycle with nitrogen for two of them; * a hydroxyl radical, * a C2-C3 alkene polyoxide radical.

  The carboxylic or sulfonic acid functions may or may not be neutralized by a base such as sodium hydroxide, 2-amino-2-methylpropanol, triethylamine 10 or even tributylamine.

  The amine radicals may or may not be neutralized by a mineral acid, such as hydrochloric acid, or by an organic acid such as acetic or lactic acids,

for example.

  In addition, it should be noted that said solubilizing radicals can be linked to the ring via a spacer group such as for example a radical -R "-, -OR" -, -OCOR "- or even -COOR" - with R "representing an alkyl radical, linear or branched in Cl-C20, optionally comprising one or more heteroatoms, such as oxygen

for example.

  Preferably, the radicals R, R1 to R4 which are identical or different, are chosen from hydrogen, R ', -OR', -OCOR ', -COOR' with R 'have a linear or branched C1-C6 alkyl radical, and among the following solubilizing groups, neutralized or not, -COOH, -CH2COOH, -CH2OH, (CH2) 6OH, - (CH2) 3SO3H, -O (CH2) 3SO3H, 25 -O (CH2) 3N (CH2CH3) 2, - [(CH2) 20] xCH2CH2OH, - [(CH2) 20] xCH2CH20CH3 with x mean number between 0 and 200.

  In addition, the conductive polythiophene may comprise at least one repeating unit of formulas (I) to (III) indicated above in which the radicals R, R1 to R4, which are identical or different, are chosen from the group formed by hydrogen, a radical -R ', -OR', -COOR ', -OCOR', with R 'representing a linear or branched C1C20 alkyl radical, a halogen atom, a nitro radical, a cyano radical, an alkylcyano radical.

  Furthermore, the total average number of repeating units of the conductive polythiophene is generally between 5 and 500, more particularly between 5 and 450, and preferably between 8 and 400.

  Thus, the polymers advantageously have weight average molecular weights of between 200 and 500,000 g / mol, more particularly between 200 and 40, 200,000 g / mol and preferably between 200 and 100,000 g / mol.

  In accordance with a particular embodiment of the invention, the conductive polymer used comprises at least one repeating unit in which at least one of the radicals is a solubilizing group so that the resulting polymer is soluble or dispersible in the medium of the composition, within the meaning of the invention.

  According to a preferred embodiment of the invention, the conductive polymer used comprises at least one solubilizing group per repeating unit. In the case of this embodiment, the polymers comprising only units of formula (I) in which the radicals other than the solubilizing radicals represent hydrogen atoms, are such that the solubilizing radical or radicals of at least one repeating unit are linked to the ring by a spacer.

  The conductive polythiophenes present in the composition according to the invention are in particular in the book "Handbook of organic conductive molecules and polymers" Wiley 1997- New York, Vol 1, 2, 3; in Can magazine. J. Chem. vol 64, 1986; in 15 the article from Chem. Mater. 1998, Vol.10, N 7 pages 1990-1999 - by the authors RASMUSSEN S.C., PICKENS J.C. and HUTCHISON J.E. "A new, general approach to tuning the properties of functionalized polythiophenes: The oxidative polymerization of monosubstituted bithiophenes"; in the article taken from the journal Macromolecules 1998, 31, pages 933-936, by the same authors "Highly conjugated, 20 water-soluble polymers via direct oxidative polymerization of monosubstituted bithiophenes".

  Thus, the polymerization can be carried out by chemical or electrochemical oxidation of the corresponding thiophene monomer or even by polycondensation. By way of illustration, the polythiophenes of formulas (I) and (II) can be obtained by oxidation polymerization (for example with a FeCl3 catalysis); by polycondensation of dihalogenated thiophene catalyzed by nickel or palladium complexes (eg NiCI2 (dppe) 2); by Suzuki coupling (coupling between a halogen function, bromine for example and a boronic acid, catalysis: palladium complex and base; then there is AA-BB type coupling (reaction of AXA type monomers with B-X'- B) or of type AB (reaction of several monomers of type AXB)); by Stille coupling (formation of carbon-carbon bond in the presence of a catalysis based on Pdtype AA-BB or A-B); by Reike polymerization (organozinc in the presence of a nickel complex); by McCulloch type polymerization, etc. The vinylene polythiophenes of formula (III) with Z representing -CH = CH-, can in particular be obtained by Gilch polymerization in the presence of a strong base (potassium tert-butoxide), of 2,5 bis (bromoalkylene) thiophene; by polymerization 40 by the Wessling method via the use of a precursor based on sulfonium salts and pyrolysis; by reaction of Wittig Wittig-Horner.

  The ethynylenic polythiophenes of formula (III) with Z representing-C-C can be obtained by Heck-Sonogashira coupling (of type AA-BB or AB; formation of carbon-carbon bond between a terminal acetylene function (or true acetylene) 5 and a bromo or iodo function catalyzed by a palladium / copper complex (PdCI2 (PPh3) 3, Cul or Cu (Oac) 2) in the presence of a base such as triethylamine, diisopropylamine, piperidine, etc.); by methathesis of alkynes in the presence of a molybdenum complex (of Mo (CO) 6).

  In general, the functionalization of polythiophenes, in other words, the contribution of the group or groups, whether or not solubilizing, is carried out on the monomer before its polymerization.

  In some cases, obtaining the solubilizing group is obtained as a result of polymer treatment. This is particularly the case for the carboxylic acid function which can be obtained by hydrolysis of the corresponding ester.

  Preferably, the solubilizing groups are chosen from carboxylic acid groups; sulfonic acid; tertiary amine radicals; quaternary ammonium such as -NR'3 + Z- with Z = Br, Cl, (C1-C4) alkyl -OS03 and R ', identical or not, representing a linear or branched C1-C20 alkyl radical; optionally connected to the ring by a spacer, preferably a C1-C20 alkyl radical; as well as their salts.

  The carboxylic or sulfonic acid functions may or may not be neutralized.

  Preferably, the conductive polythiophene corresponds to the formula (II) in which Ri 25 or R2 represents a group -CH2COOH, or -CH2COO-M +, the other representing a hydrogen atom.

  This polymer is soluble in the medium of the composition. More particularly, this polymer is preferably soluble in water. The conductive polymers are generally present in the composition in proportions of at least 0.001% by weight, more particularly at least 0.1% by weight, preferably of at least 0.1% by weight and even more preferably at least 0.5% by weight, relative to the total weight of the composition. Furthermore, the content of conductive polymer is advantageously at most 50% by weight, more particularly at most 30% by weight and preferably at most 10% by weight, relative to the total weight of the composition. .

  According to a particularly advantageous embodiment of the invention, the content of conductive polymer is between 0.1 and 50% by weight, more particularly between 40 0.1 and 30% by weight, and preferably between 0.5 and 10% by weight, relative to the total weight of the composition.

  Medium The cosmetically acceptable medium of the cosmetic composition is preferably an aqueous medium consisting of water and may advantageously comprise cosmetically acceptable organic solvents, including more particularly alcohols such as ethyl alcohol, I ' isopropyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol as well as the diethylene glycol alkyl ethers, for example, monoethyl ether or monobutyl ether of diethylene glycol, or also polyols such as glycerol. Polyethylene glycols and polypropylene glycol and mixtures of all these compounds can also be used as solvent.

  The solvents can then be present in concentrations of between 0.5 and 20% and, preferably, between 2 to 10% by weight relative to the total weight of the composition.

  Additives The cosmetic composition may also comprise an effective amount of other agents, moreover previously known in the treatment of human keratin fibers, such as various usual adjuvants such as surfactants well known in the art and of anionic type , cationic, non-ionic, amphoteric, zwitterionic or mixtures thereof, thickening agents, antioxidants, perfumes, dispersing agents, conditioning agents including in particular cationic or amphoteric polymers, opacifying agents, agents sequestering agents such as EDTA and etidronic acid, UV filters, waxes, silicones, volatile or not, cyclic or linear or branched, organomodified (in particular by amine groups) or not, preservatives, ceramides, pseudoceramides, vegetable, mineral or synthetic oils, vitamins or provitamins such as panthenol, polym non-ionic, anionic, amphoteric or cationic associative eras.

  Surfactants Preferably, the cosmetic composition according to the invention comprises one or more surfactants which can be indifferently chosen, alone or in mixtures, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.

  The surfactants suitable for the implementation of the present invention are in particular the following: (i) Anionic surfactant (s): By way of example of anionic surfactants which can be used, alone or as mixtures, in the context of present invention, there may be mentioned in particular (nonlimiting list) the salts (in particular alkaline salts, in particular sodium salts, ammonium salts, amine salts, amino alcohol salts or magnesium salts) of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamidoethersulfates, alkylaryl polyethersulfates, monoglycerides sulfates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, x-olefin-sulfonates, paraffin-sulfonates; alkyl (C6-024) sulfosuccinates, alkyl (C6024) ethersulfosuccinates, alkyl (C6-C24) amidesulfosuccinates; (C6-C24) alkyl sulfoacetates; acyl (06-C24) sarcosinates and acyl (C6-C24) glutamates. It is also possible to use alkyl esters (C6-C24) carboxylic polyglycosides such as alkylglucoside citrates, alkylpolyglycoside tartrate and alkylpolyglycoside sulfosuccinates., Alkylsulfosuccinamates; acylisethionates and N-acyltaurates, the alkyl or acyl radical of all these different compounds preferably containing from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group. Among the anionic surfactants which can still be used, mention may also be made of the salts of fatty acids such as the salts of oleic, ricinoleic, palmitic, stearic acids, coconut oil or hydrogenated coconut oil acids; acyl-lactylates whose acyl radical contains 8 to 20 carbon atoms. It is also possible to use the alkyl D galactoside uronic acids and their salts, the polyoxyalkylenated alkyl ether acids (06-024), the polyoxyalkylenated alkyl (C6-C24) aryl ether carboxylic acids, the alkyl (C6-C24) acids. polyoxyalkylenated carboxylic amido ether and their salts, in particular those comprising from 2 to 50 alkylene oxide groups, in particular ethylene, and their mixtures.

  (ii) Nonionic surfactant (s): The nonionic surfactants are also compounds well known per se (see in particular in this regard "Handbook of Surfactants" by MR PORTER, Blackie & Son editions ( Glasgow and London), 1991, pp 116-178) and their nature is not, in the context of the present invention, of a critical nature. Thus, they can in particular be chosen from (nonlimiting list) alcohols, alpha-diols, polyethoxylated, polypropoxylated alkylphenols, having a fatty chain comprising for example 8 to 18 carbon atoms, the number of ethylene oxide groups or propylene oxide which may range in particular from 2 to 50. Mention may also be made of copolymers of ethylene oxide and of propylene, condensates of ethylene oxide and of propylene on fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 moles of ethylene oxide, polyglycerolated fatty amides comprising on average 1 to 5 glycerol groups and in particular 1.5 to 4; polyethoxylated fatty amines preferably having 2 to 30 moles of ethylene oxide; fatty acid esters of sorbitan oxyethylenated having from 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglycosides, N-alkyl glucamine derivatives, amine oxides such as alkyl oxides (Co10-C14) amines or N-acylaminopropylmorpholine oxides.

  (iii) Amphoteric or zwitterionic surfactant (s): The amphoteric or zwitterionic surfactants, the nature of which is not critical in the context of the present invention, may in particular be (non-limiting list) of derivatives of aliphatic secondary or tertiary amines, in which the aliphatic radical is a linear or branched chain containing 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example 10 carboxylate, sulfonate, sulfate, phosphate or phosphonate); mention may also be made of alkyl (C8-C20) betanes, sulfobetanes, alkyl (C8-C20) amidoalkyl (C1-C6) betanes or alkyl (C8-C20) amidoalkyl (C1-C6) sulfobetanes.

  Among the amine derivatives, mention may be made of the products sold under the name Miranol, as described in patents US-2,528,378 and US-2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxyglycinates and Amphocarboxypropionates of respective structures: R2 -CONHCH2CH2 -N (R3) (R4) (CH2COO-) in which: R2 denotes an alkyl radical of an R2-COOH acid present in hydrolysed coconut oil, a radical heptyl, nonyl or undecyl, R3 denotes a beta-hydroxyethyl group and R4 denotes a carboxymethyl group; and R2'-CONHCH2CH2-N (B) (C) in which: B represents CH2CH2OX ', C represents - (CH2) z -Y', with z = 1 or 2, X 'denotes the group -CH2CH2-COOH or a hydrogen atom Y 'denotes -COOH or the radical -CH2-CHOH-SO3H R2' denotes an alkyl radical of an acid Rg -COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical , especially C7, Cg, Cl1 or C13, a C17 alkyl radical and its iso form, an unsaturated C17 radical.

  These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Coco-ampho-diacetate, Disodium Lauroampho-diacetate, Disodium Capryl-ampho-diacetate, Disodium Caprylo-amphodiacetate, Disodium Coco35 ampho-dipropionate, Disodium Lauro- amphodipropionate, Disodium Capryl-amphodipropionate, Disodium Caprylo-amphodipropionate, Lauro-ampho-dipropionic acid, Coco-ampho-dipropionic acid.

  By way of example, mention may be made of the cocoamphodiacetate sold under the trade name Miranol C2M concentrated by the company Rhodia Chimie. (Iv) Cationic surfactants: Among the cationic surfactants that may be mentioned in particular (non-limiting list): the salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts such as chlorides or bromides of tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzyl ammonium, trialkylhydroxyalkylammonium or alkylpyridinium; imidazoline derivatives; or cationic amine oxides.

  The amounts of surfactants present in the composition according to the invention can vary from 0.01 to 40% and preferably from 0.5 to 30% of the total weight of the composition.

  Of course, those skilled in the art will take care to choose the optional compound (s) mentioned above, in such a way that the advantageous properties intrinsically attached to the dye composition according to the invention are not, or not substantially, altered by the planned addition (s).

  The composition which has just been described is applied to keratinous material, in particular keratinous fibers, dry or wet. The medium of the composition is then evaporated, or else it is allowed to evaporate between 20 and 120 ° C., preferably between 20 and 80 ° C., until the fibers are dry.

  It is likewise conceivable to apply the composition to dry or wet fibers, then to rinse said fibers and to dry them between 20 and 120 C. A concrete example illustrating the invention is indicated below, without however presenting a limiting character.

EXAMPLE

  Svnthèse de polv (thiophene-3- acetic acid)

O

H \

OH

  Procedure Preparation of the polymer: Dolv (ethyl thiophene-3-acetate) In a schlenk under argon, 25 ml of dry chloroform are introduced, degassing and then the reagents are introduced: 2.5g of thiophene-3-acetate ethyl (14.7 mmol)

S

O-

and 1 g of FeCl3 (6.15 mmol).

  The mixture is stirred for 24 hours under argon at 50 C.

  The poly (thiophene-3-ethyl acetate) polymer is then precipitated in heptane.

  The polymer is then dissolved in a tetrahydrofuran solution. Characterization by infrared: C = O band: 1719 cm-1; CH2 bands, CH3 = 2979 cm-1, 2934 cm-1 and disappearance of the CH band at 3102 cm-1 present in the monomer.

  Hydrolysis of the polymer: poly (thiophene-3-ethyl acetate) to form the poly (thiophene-3-acetic acid).

  The polymer obtained above is then hydrolyzed by an excess of 50 ml of an aqueous solution of sodium hydroxide (2N) for 48 hours at 70 C, followed by acidification with concentrated HCl until precipitation of the product: poly (thiophene -3- acetic acid).

  The polymer is then filtered and washed several times with distilled water in order to remove the traces of catalyst.

  Characterization of the infrared polymer: C = O band: 1740 cm-1; COO 1580 cm-1; OH (wide band 3000-3500 cm-l) Neutralization of the poly (thiophene-3-acetic acid) polymer: The poly (thiophene-3acetic acid) polymer (2g) is dissolved in tetrahydrofuran (30g) and neutralized at the rate of I mol of sodium hydroxide per mole of carboxylic acid.

  Water (30 g) is then added. The tetrahydrofuran is evaporated.

  A 6% aqueous solution of poly (thiophene-3-acetic acid) is thus obtained in the form of a sodium salt.

  Formulation comprising the polymer obtained Composition: Polymer described above 4% Aminomethyl propanol qs pH7 Synthalen K 1% Ethanol 10% Water qs 100 g Composition 1 of conductive polymer obtained was applied to locks of natural brown hair at room temperature (200C) according to the previous example (0.1g per g of hair). Then we dried the locks.

  The locks have a very shiny appearance with a golden reflection, which is especially noticeable when the locks are viewed in a grazing view.

  When touched, the hair has the advantage of not being perceived as oily, the optical properties described above are preserved over time (unchanged after 12 hours).

Claims (22)

  1. Use as an agent intended to impart an optical effect to human keratin materials, more particularly to human keratin fibers, of a composition comprising, in a cosmetically acceptable medium, at least one conductive polythiophene present in a soluble or dispersible form in said medium, comprising at least one repeating unit of formulas (I) to (111) below R3 R4 (ó) R1 R2 (I s \ / ZR R1 R2 (111) Formulas in which: the radicals R, R1 to R4 are identical or different, are selected from the group 15 formed by hydrogen, a radical -R ', -OR', - COOR ', -OCOR', with R 'representing a linear or branched C1-C20 alkyl radical, a d atom halogen, a nitro radical, a cyano radical, an alkylcyano radical, and solubilizing groups, it being understood that at least one radical from R, R1 to R4 denotes a solubilizing group; Z represents -CH = CH- or CC-.   2. Use as an agent intended for coloring human keratin materials, more particularly human keratin fibers, of a composition comprising, in a cosmetically acceptable medium, at least one conductive polythiophene, absorbing light in the visible spectrum, being under a form soluble or dispersible in said medium, comprising at least one repeating unit of formulas (I) to (111) below: R3 R4 S   R1 R2 () \ / Z R1 R2 (11I) Formulas in which: the radicals R, R1 to R4 identical or different, are chosen from the group formed by hydrogen, a radical -R ', -OR', -COOR ', -OCOR', with R 'representing a linear or branched C1-C20 alkyl radical, a halogen atom, a nitro radical, a cyano radical, an alkylcyano radical, and solubilizing groups, it being understood that at least one radical from R, R1 to R4 denotes a solubilizing group; Z represents -CH = CH- or -C = C-.   3. Use according to one of claims I or 2, characterized in that the 15 solubilizing groups are chosen from the group formed by: * a carboxylic radical (-COOH), carboxylate (-COO-M + with M representing an alkali metal , an alkaline earth metal, an organic amine, an alkanolamine, an amino acid), * a sulfonic radical (-SO3H), sulfonate (-SO3- M +, M having the same definition as above), * a radical primary, secondary, tertiary amine, * a quaternary ammonium radical such as -NR'3 + Z- with Z = Br, Cl, (C1-C4) -OSO3 and R 'alkyl, identical or not, representing a linear alkyl radical or branched in C1-C20, optionally comprising a heteroatom, or forming a heterocycle with nitrogen for two of them; * a hydroxyl radical, * a C2-C3 alkene polyoxide radical; it being understood that said solubilizing radicals may or may not be linked to the cycle by means of a spacer group.   4. Use according to claim 3, characterized in that the spacer group 5, identical or not, is a radical -R "-, -OR" -, OCOR "- or -COOR" - with R "representing an alkyl radical , linear or branched in Cl-C20, optionally comprising a heteroatom.   5. Use according to one of the preceding claims, characterized in that the radicals R, R1 to R4 which are identical or different, are chosen from hydrogen, R ', -OR', -OCOR ', -COOR' with R 'have a linear or branched C1-C6 alkyl radical, and among the following solubilizing groups, neutralized or not: -COOH, -COO-M +, -CH2COOH, CH2-COO-M +, -CH2OH, - (CH2) 60H, - (CH2) 3SO3H, - (CH2) 3-SO3- M +, -O (CH2) 3SO3H, -O (CH2) 3-SO3- M *, 15 -O (CH2) 3N (CH2CH3) 2, - [( CH2) 20] xCH2CH2OH, - [(CH2) 20] xCH2CH20CH3 with x mean number between O and 200.   6. Use according to one of the preceding claims, characterized in that the conductive polythiophene comprises at least one repeating unit of the following formulas (I) to (111): R3 R4 Ri R2 (1) R1 R2 (liI) SZ-   Formulas in which: the radicals R, R1 to R4, identical or different, are chosen from the group formed by hydrogen, a radical -R ', -OR', -COOR ', -OCOR', with R 'representing a radical linear or branched C1-C20 alkyl, a halogen atom, a nitro radical, a cyano radical, an alkylcyano radical; Z represents -CH = CH- or -C-C-.   7. Use according to one of claims 1 to 5, characterized in that the polythiophene comprises at least one solubilizing group per repeating unit.   8. Use according to the preceding claims, characterized in that the polythiophene comprises repeating units of formula (II) in which Ri or R2 represents a group -CH2COOH, or -CH2COOH-M +, the other representing a hydrogen atom .   9. Use according to any one of the preceding claims, characterized in that the polythiophene (s) are present in proportions of at least 0.001% by weight, more particularly at least 0.1% by weight, preferably at least 0.1% by weight and even more preferably at least 0.5% by weight, relative to the total weight of the composition.   10. Use according to any one of the preceding claims, characterized in that the poylthiophene (s) are present in proportions of at most 20% by weight, more particularly at most 30% by weight and preferably of at most 10% by weight, relative to the total weight of the composition.   11. Use according to any one of the preceding claims, characterized in that the cosmetically acceptable medium is chosen from the group formed by water or a water-solvent mixture.   12. Use according to claim 11, characterized in that the solvent or solvents are chosen from alcohols, glycols, glycol ethers, polyols, polyethylene glycols, polypropylene glycol and their mixtures.   13. Use according to any one of the preceding claims, characterized in that it further comprises at least one nonionic, anionic, cationic, amphoteric or zwitterionic surfactant. 35 14. Use according to one of the preceding claims, characterized in that the composition is applied to the dry or wet fibers, then the medium is evaporated or allowed to evaporate between 20 and 500C until the fibers are dry .   15. Dyeing composition for human keratin fibers and more particularly hair, characterized in that it comprises, in a cosmetically acceptable medium, an effective amount of at least one conductive polythiophene, absorbing light in the visible spectrum, being 5 in a form soluble or dispersible in said medium, comprising at least one repeating unit of formulas (I) to (111) below R3 R4 Ri R2 1 2 (1) s R1 2 (II) S   \ R / \ R 1 2 (Ill) Formulas in which: the radicals R, R1 to R4 identical or different, are chosen from the group formed by hydrogen, a radical -R ', -OR', -COOR ', -OCOR ', with R' representing a linear or branched C1-C20 alkyl radical, a halogen atom, a nitro radical, a cyano radical, an alkylcyano radical, and solubilizing groups, it being understood that at least one radical among R, R1 to R4 denotes a solubilizing group; Z represents -CH = CH- or -C C-.   16. Composition according to the preceding claim, characterized in that the 20 solubilizing groups are chosen from the group formed by: * a carboxylic radical (-COOH), carboxylate (-COO-M + with M representing an alkali metal, an alkali metal- earthy, an organic amine, an alkanolamine, an amino acid), * a sulfonic radical (-SO3H), sulfonate (-SO3- M +, M having the same definition as above), * a primary, secondary amine radical, tertiary, * a quaternary ammonium radical such as -NR'3 + Z- with Z = Br, Cl, (C1-C4) alkyl -OSO3 and R ', identical or not, representing a linear or branched C1-C20 alkyl radical , optionally comprising a heteroatom, or forming a heterocycle with nitrogen for two of them; * a hydroxyl radical, to a C2-C3 alkene polyoxide radical; it being understood that said solubilizing radicals may or may not be linked to the cycle by means of a spacer group.   17. Composition according to one of claims 13 or 14, characterized in that the radicals R, R1 to R4 identical or different, are chosen from hydrogen, 10 R ', -OR', -OCOR ', -COOR' with R 'have a linear or branched C1-C6 alkyl radical, and among the solubilizing groups, neutralized or not, the following: -COOH, -COO-M +, -CH2COOH, CH2-COO-M +, -CH2OH, - (CH2 ) 60H, - (CH2) 3SO3H, - (CH2) 3-SO3- M +, -O (CH2) 3SO3H, -O (CH2) 3-SO3- M +, -O (CH2) 3N (CH2CH3) 2, - [ (CH2) 20] xCH2CH2OH, - [(CH2) 20] xCH2CH2OCH3 with 15 x average number between O and 200.   18. Composition according to one of claims 15 to 17, characterized in that the conductive polythiophene comprises at least one repeating unit of formulas (I) to (111) below: R3 R4 HER   Ri R2 (I) (l) R1 / R2 (II) \ / Z R1 'R2 (11) Formulas in which: the radicals R, R1 to R4, identical or different, are chosen from the group formed by hydrogen, a radical -R ', -OR', -COOR ', -OCOR', with R 'representing a linear or branched C1-C20 alkyl radical, a halogen atom, a nitro radical, a cyano radical, an alkylcyano radical; Z represents -CH = CH- or - C-- C- 19. Composition according to one of claims 15 to 17, characterized in that the polythiophene comprises at least one solubilizing group per repeating unit.   20. Composition according to the preceding claim, characterized in that the polythiophene comprises repeating units of formula (II) in which Ri or R2 represents a group -CH2COOH, or -CH2COOH-M +, the other representing a hydrogen atom.   21. Composition according to one of claims 15 to 20, characterized in that the polythiophene content is at least 0.001% by weight, more particularly at least 0.1% by weight, preferably at least 0.1% by weight and even more preferably at least 0.5% by weight, relative to the total weight of the composition.   22. Composition according to one of claims 15 to 21, characterized in that the polythiophene content is at most 50% by weight, more particularly at most 30% by weight and preferably at most 10% by weight, relative to the total weight of the composition.