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WO2010095651A1 - Composition de polymère conducteur composite, son procédé de production, solution contenant la composition, et utilisation de la composition - Google Patents

Composition de polymère conducteur composite, son procédé de production, solution contenant la composition, et utilisation de la composition Download PDF

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Publication number
WO2010095651A1
WO2010095651A1 PCT/JP2010/052355 JP2010052355W WO2010095651A1 WO 2010095651 A1 WO2010095651 A1 WO 2010095651A1 JP 2010052355 W JP2010052355 W JP 2010052355W WO 2010095651 A1 WO2010095651 A1 WO 2010095651A1
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meth
acrylate
group
conductive polymer
polymer composition
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Japanese (ja)
Inventor
文明 小林
岡本　秀二
目黒　晃
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Soken Kagaku KK
Soken Chemical and Engineering Co Ltd
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Soken Kagaku KK
Soken Chemical and Engineering Co Ltd
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Priority to JP2011500629A priority Critical patent/JP5869880B2/ja
Publication of WO2010095651A1 publication Critical patent/WO2010095651A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005—Photoelectrochemical storage cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants

Definitions

  • the present invention relates to a composite conductive polymer composition, a production method thereof, a solution containing the composition, and a use of the composition, and more specifically, an aromatic system such as aniline, thiophene, and pyrrole, and a heterocyclic ring.
  • a composite conductive polymer composition doped with a polymer compound, a method for producing the same, a solution containing the composition, and The present invention relates to the use of the composition for a dye-sensitized solar electric electrode or an antistatic film.
  • Doping with a dopant is essential for imparting high conductivity in a ⁇ -conjugated polymer.
  • a polymer in which ⁇ conjugation has originally developed has a structure in which the polymer chain has high planarity and crystallinity (stacking property) between polymer chains due to the affinity of ⁇ bond.
  • the ⁇ -conjugated polymer doped with the dopant has higher planarity and higher affinity due to ⁇ -conjugation, and the stacking property becomes more remarkable. For this reason, it is a difficult problem to achieve both the dissolution (by heat or solvent) of the ⁇ -conjugated polymer and the electrical conductivity.
  • Patent Document 1 a polymer in which an alkyl group, an alkoxyl group, or the like is introduced into the side chain of a ⁇ -conjugated polymer has been proposed.
  • Patent Document 1 a polymer in which an alkyl group, an alkoxyl group, or the like is introduced into the side chain of a ⁇ -conjugated polymer.
  • doping is necessary. When this doping is performed, as a result, there is a problem that sufficient solvent solubility cannot be obtained due to the development of the planarity of the conductive polymer and the development of ⁇ -conjugate affinity.
  • a self-supporting film or a self-supporting body that can be dissolved by a solvent or melted by heat, and has sufficient electrical conductivity after molding.
  • a polymer film is formed by electrolytic polymerization or vapor exposure on a substrate to which direct conductivity is desired, an oxidizing agent and a conductive polymer. After being immersed in the precursor monomer solution, a thin film polymerization or the like is performed by heating or the like, and then a treatment such as doping of the obtained polymer film is performed.
  • the electrolytic polymerization requires the substrate to be a semiconductor or a conductor, and corrosion resistance to the electrolytic solution is also required, so that usable substrates are limited.
  • the oxidant homogeneously present in the thin film that becomes the polymerization field, which is not sufficient in terms of film formation control.
  • fine irregularities were formed, and it was difficult to form a conductive polymer on a sufficiently homogeneous surface.
  • Patent Document 2 discloses a method for producing poly (3,4-disubstituted thiophene) in which 3,4-disubstituted thiophene is polymerized using an inorganic ferric salt and an oxidizing agent.
  • 3 discloses a water-dispersible powder having a polymer T having predominantly repeating thiophene units and at least one other polyanionic polymer P.
  • Patent Document 2 is a method for obtaining a powdered material or a method for performing oxidative polymerization directly on the surface of the target adherend, and it is impossible to dissolve the polymer obtained in this method in a solvent or water.
  • Patent Document 3 is only a dispersion having good water dispersibility, and is not such that it is molecularly soluble in an organic solvent.
  • Patent Document 4 polyaniline, which is essentially insoluble in a solvent, is pulverized and pulverized to a nano-size level and has an affinity for polyaniline and the solvent.
  • a high sulfonic acid anion emulsifier such as SDS (dodecylbenzenesulfonic acid) or PTS (paratoluenesulfonic acid) is used as a dispersant, it is disclosed to provide a fine dispersion solution at a nano level.
  • the surface of the coating film is uneven because it is not substantially soluble in a solvent, and is also a self-supporting film made of only polyaniline (also called a homogeneous film. It is impossible to form a film after coating unless it is combined with a binder or the like.
  • polythiophene having a molecular weight in the range of 2,000 to 500,000 and oxidized and chemically polymerized in the presence of a polyanion of polystyrene sulfonate and a molecular weight of 2,000 to 500,000 are disclosed.
  • a solution of polythiophene comprising a polyanion derived from polystyrene sulfonic acid in water or a mixed solvent of water and a water-miscible organic solvent is disclosed.
  • This patent document proposes a method for producing poly (ethylene dioxide substituted thiophene) (PEDOT) that can be dissolved or dispersed in water or an alcohol solvent by oxidative polymerization in the presence of polystyrene sulfonic acid (PSS) and an oxidizing agent.
  • PEDOT poly(ethylene dioxide substituted thiophene)
  • PSS polystyrene sulfonic acid
  • the PEDOT / PSS obtained here is dispersed in water, it is not completely dissolved, it is difficult to suppress stacking between partial PEDOTs, and it is difficult to dissolve the conductive polymer. It was enough.
  • Patent Document 6 discloses precipitation, isolation, and purification by oxidative polymerization of aniline or aniline derivatives in a solvent containing an organic acid or an inorganic acid in the presence of a highly hydrophobic anionic surfactant. And then extracting with an organic solvent immiscible with water to form an organic solution.
  • the emulsifier used in this patent document is a low molecular sulfonic acid type, and aniline is converted to hydrochloric acid before polymerization, and then aniline salt substitution is performed with the sulfonic acid type emulsifier.
  • the exchange hardly occurs, and the polyaniline obtained by the synthesis method of this patent document does not actually dissolve in the solvent, and there is a problem that only a finely dispersed solvent dispersion can be obtained.
  • Patent Document 7 a solution in which (A) a monomer having a sulfonic acid functional group and a radical polymerizable functional group and (B) a monomer soot made of aniline or a derivative thereof is dissolved in water or an organic solvent is emulsified. ), The sulfonic acid structure derived from the monomer (A) is introduced into the monomer, the polymerization initiator (A) and the monomer (B) are polymerized in the coexistence of the following, and the polymer (B): A method for producing a conductive polymer in an intertwined state with the polymer (A) is disclosed.
  • Patent Document 8 discloses a conductive material containing (a) a protonated substituted or unsubstituted polyaniline complex and (b) a compound having a phenolic hydroxyl group dissolved in an organic solvent that is substantially immiscible with water.
  • a functional polyaniline composition is disclosed.
  • Non-Patent Document 1 This is a technique described in Non-Patent Document 1, although the description is not sufficient, and by adjusting the donor strength in the polyaniline coating, the affinity of the phenolic compound is remarkable, and the conductivity in the polyaniline coating is It is disclosed that it is useful for improving the performance. In other words, by mixing non-volatile additives that have good solubility in toluene and good compatibility with polyaniline, such as phenols, not only improve the conductivity of the dried coating, but also allow toluene.
  • Patent Document 10 discloses a counter electrode of a dye-sensitized solar cell in which a conductive polymer layer is provided on a plastic film provided with a transparent conductive layer.
  • a dispersion containing conductive polymer is applied and the solvent is removed to form a conductive polymer layer.
  • the conductive polymer is a dispersion film of fine particles, it is transparent. Adhesion to the conductive layer is poor, and it is necessary to increase the surface energy of the transparent conductive layer by performing plasma treatment or the like in advance.
  • Patent Document 11 discloses an antistatic film in which an antistatic material containing a polythiophene compound, an acidic polymer, and a sugar alcohol is applied to a thermoplastic resin film.
  • the antistatic film obtained has good transparency and antistatic properties, but polystyrene sulfonic acid is used as a doping agent for polythiophene compounds. Since only an acidic polymer such as the above is used, the antistatic film absorbs moisture over time, and there is a problem that adhesion and antistatic properties are lowered.
  • the present invention provides a conductive polymer composition that is excellent in solubility in a solvent and is a self-supporting film, that is, a homogeneous film or a molded body that is free from pinholes, and a method for producing the same. Is an issue.
  • the present inventors have found that when a polymer compound copolymerized with a specific monomer is used as an additive during the polymerization of a ⁇ -conjugated polymer, the function of making the polymerization field as an emulsifier uniform. In addition, it exhibits a function as a doping material and has an appropriate steric hindrance to a ⁇ -conjugated polymer, so that a composite conductive polymer composition excellent in solubility in a specific solvent can be obtained. I found. In addition, the present inventors have found that the composite conductive polymer composition can be used for a dye-sensitized solar counter electrode, an antistatic film, and the like, and have completed the present invention.
  • the present invention provides the following components (a-1) to (a-3) (A-1) Monomer having sulfonic acid group and polymerizable vinyl group 20 to 50 mol% (A-2) Monomer having aromatic group or alicyclic group and polymerizable vinyl group 20 to 50 mol% (A-3) Alkyl (meth) acrylate 30 to 60 mol%
  • the polymer compounds obtained by polymerizing are represented by the following formulas (I) to (III) (In each formula, R 1 to 7 represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms)
  • a composite conductive polymer composition obtained by doping a ⁇ -conjugated polymer ( ⁇ ) having a monomer component as a monomer constituent.
  • the present invention also provides the following components (a-1) to (a-3) (A-1) Monomer having sulfonic acid group and polymerizable vinyl group 20 to 50 mol% (A-2) Monomer having aromatic group or alicyclic group and polymerizable vinyl group 20 to 50 mol% (A-3) Alkyl (meth) acrylate 30 to 60 mol% Characterized by coexisting a polymer compound obtained by polymerizing the compound and a compound selected from the formulas (I) to (III) in an electrolytic substrate solvent and performing chemical oxidative polymerization using an oxidizing agent. This is a method for producing a composite conductive polymer composition.
  • the present invention relates to the above composite conductive polymer composition in an aromatic solvent selected from toluene, benzene and xylene and / or an ester solvent selected from ethyl acetate, propyl acetate and butyl acetate.
  • aromatic solvent selected from toluene, benzene and xylene
  • ester solvent selected from ethyl acetate, propyl acetate and butyl acetate.
  • the present invention provides a counter electrode for a dye-sensitized solar cell using the above composite conductive polymer composition.
  • the present invention is an antistatic film using the composite conductive polymer composition.
  • the composite conductive polymer compound obtained by polymerization by the action of an oxidizing agent in the presence of the polymer compound of the present invention is stably dissolved in an aromatic solvent such as toluene or an ester solvent such as ethyl acetate. Is.
  • the polymer compound (A) used in the present invention comprises a monomer having a sulfonic acid group and a polymerizable vinyl group as component (a-1), an aromatic group or alicyclic group as component (a-2) according to a conventional method. And a monomer having a polymerizable vinyl group and an alkyl (meth) acrylate of component (a-3) are polymerized in the presence of a polymerization initiator.
  • the monomer having a sulfonic acid group and a polymerizable vinyl group as the component (a-1) is a monomer having a sulfonic acid group such as a styrene sulfonic acid group or a sulfoethyl group. Examples thereof include styrene sulfonic acid and styrene sulfone.
  • Styrene sulfonates such as sodium acrylate, potassium styrene sulfonate, calcium styrene sulfonate, ethyl 2-methacrylate (meth) acrylate, ethyl 2-methacrylate (sodium acrylate), ethyl (meth) acrylate 2 -Ethyl (meth) acrylate 2-sulfonates such as potassium sulfonate, ethyl (meth) acrylate 2-calcium sulfonate, etc.
  • Examples of the monomer (a-2) having an aromatic group or alicyclic group and a polymerizable vinyl group include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, ethyl (meth) acrylate 2 -Methyl phthalate, ethyl (meth) acrylate 2-ethyl phthalate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate , T-butylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate morpholine, styrene, dimethylstyrene, naphthalene (meth) acrylate, vinyl naphthalene, vinyl n-ethylc
  • alkyl (meth) acrylate of component (a-3) examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl.
  • (Meth) acrylate, i-butyl (meth) acrylate, i-propyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (Meth) acrylate etc. are mentioned.
  • the molar ratio of the monomer (a-1), the monomer (a-2) and the monomer (a-3) is important.
  • the polymer compound of the present invention acts on the conductive polymer composition by appropriately balancing the hydrophobicity due to the aromatic group or alicyclic group and the hydrophilicity due to the sulfonic acid group, and this is incorporated into the solvent. This is to enable dissolution.
  • the amount of component (a-1) for producing the polymer compound (A) of the present invention is 20 to 50 mol%, preferably 25 to 40 mol%.
  • the amount of component (a-2) is 20 to 50 mol%, preferably 30 to 45 mol%.
  • the amount of component (a-3) is 30 to 60 mol%, preferably 35 to 50 mol%.
  • the polymer compound of the present invention may contain a polymerizable component other than the monomers (a-1), (a-2) and (a-3).
  • this polymerizable component include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methoxyethyl (meth) Acrylate, butoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, (meth) acrylic acid, acetoacetoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N, N- Examples thereof include dimethylaminoethyl (meth) acrylate, vinylpyridine, and the blending amount when blending is about 0 to 20 mol%.
  • the polymerization reaction of the component (a-1), the component (a-2), the component (a-3) and the polymerizable component added as necessary can be carried out by a known method. For example, after mixing each of these components, a polymerization initiator can be added thereto and polymerization can be started by heating, light irradiation, or the like.
  • the polymerization method that can be employed to produce the polymer compound (A) is not particularly limited as long as it is a method that can be carried out without the component (a-2) being separated from the monomer mixture.
  • a polymerization method, a bulk (bulk) polymerization method, a precipitation polymerization method, or the like is employed.
  • the polymerization initiator used in the polymerization reaction is not particularly limited as long as it can be dissolved in each of the above components and the solvent used during the reaction.
  • this polymerization initiator include oil-soluble peroxide-based thermal polymerization initiators such as benzoyl peroxide (BPO), oil-soluble azo-based thermal polymerization initiators such as azobisisobutyronitrile (AIBN), azobiscyano Examples thereof include water-soluble azo-based thermal polymerization initiators such as herbal acid (ACVA).
  • water-soluble peroxide thermal polymerization initiators such as ammonium persulfate and potassium persulfate, hydrogen peroxide water, and the like can also be used.
  • redox agents such as ferrocene and amines are possible.
  • polymerization initiators can be used arbitrarily in the range of 0.001 to 0.1 mol per 1 mol of the above compound, and any method of batch charging, dropping charging and sequential charging can be used. . Further, in the case of bulk polymerization or solution polymerization using a small amount of solvent (50 wt% or less based on the monomer), a polymerization method using a combination of mercaptan and metallocene (Patent Document 9) is also possible.
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol
  • ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • methyl cellosolve ethyl cellosolve
  • propylene glycol methyl ether propylene
  • glycol solvents such as glycol ethyl ether
  • lactic acid solvents such as methyl lactate and ethyl lactate.
  • a chain transfer agent may be used in addition to the polymerization initiator at the time of polymerization, and can be appropriately used when adjusting the molecular weight.
  • the chain transfer agent that can be used any compound can be used as long as it is soluble in the above-mentioned monomers and solvents.
  • polar thiols such as alkylthiols such as dodecyl mercaptan and heptyl mercaptan, and mercaptopropionic acid (BMPA).
  • a water-soluble thiol having a group, an oily radical inhibitor such as ⁇ -styrene dimer (ASD), and the like can be used as appropriate.
  • this polymerization reaction is preferably carried out below the boiling point of the solvent used (except for bulk polymerization), for example, about 65 ° C. to 80 ° C. is preferable.
  • it is preferably performed at 25 ° C. to 80 ° C.
  • the polymer thus obtained can be purified as necessary to obtain a polymer compound (A).
  • an oily poor solvent such as hexane is used to remove oily low molecular impurities and residual monomers and low molecular impurities, and then polymer precipitation with an aqueous poor solvent such as acetonitrile, methanol, ethanol, acetone, etc. And removing water-based impurities and residues.
  • the polymer compound (A) is introduced as a dopant into the conductive polymer composition and acts as a stack inhibitor and a solvent solubilizer. If other polymerization initiator residue, monomer, oligomer, heterogeneous composition, etc. remain as a product, the functional degradation of the conductive polymer composition becomes a problem, and it is necessary to remove these. As a result of such purification, the heterogeneous radical polymer as in Patent Document 7 is not mixed, and the composition of the uniform conductive polymer composition and the composition of the polymer compound (A) are uniformly matched. A solubilized state can be expressed.
  • the polymer compound (A) obtained as described above preferably has a GPC equivalent weight average molecular weight of 3,000 to 100,000.
  • the weight average molecular weight is less than 3,000, the function as a polymer compound is insufficient.
  • the solubility in the polymerization field (acidic aqueous solution) at the time of synthesis of the conductive polymer may not be sufficient, and the solvent solubility of the polymer compound itself may deteriorate, and the conductive polymer may be used. May significantly affect solubilization.
  • the composite conductive polymer composition of the present invention is produced as follows using the polymer compound (A) obtained as described above. That is, the compound represented by the above formulas (I) to (III), which is a raw material for the ⁇ -conjugated polymer ( ⁇ ), which is obtained by dissolving the polymer compound (A) in an electrolytic substrate solvent. Is added to the ⁇ -conjugated polymer ( ⁇ ) containing the compounds represented by the formulas (I) to (III) as monomer constituents. ) Can be obtained.
  • the compound represented by the formula (I) is aniline whose substituent is a hydrogen atom or an alkyl group.
  • this compound include aniline, o-toluidine, m-toluidine, 3,5-dimethylaniline, 2,3-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, and 2-ethylaniline.
  • the compound represented by the formula (II) is a thiophene whose substituent is hydrogen or an alkyl group, and specific examples thereof include thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3- Examples thereof include butylthiophene, 3-pentylthiophene, 3-hexylthiophene, 3-heptylthiophene, and 3-n-octylthiophene.
  • the compound represented by the formula (III) is pyrrole whose substituent is hydrogen or an alkyl group, and specific examples thereof include pyrrole, 3-methylpyrrole, 3-heptylpyrrole, 3-n-octylpyrrole and the like. Can be mentioned.
  • ion-exchanged water as an electrolytic substrate solvent is acidified as necessary, and then, as described above, The polymer compound (A) thus obtained is added, and then one or more of the compounds of the formulas (I) to (III) as raw materials are added thereto, and an oxidant is further added for oxidative polymerization.
  • an oxidant is further added for oxidative polymerization.
  • a ketone solvent such as acetone or methyl ethyl ketone
  • an alcohol solvent such as methanol, ethanol or isopropyl alcohol
  • a highly hydrophilic organic solvent such as acetonitrile
  • Examples of the acidic component used for acidifying the electrolytic substrate solvent in the above reaction include hydrochloric acid, sulfuric acid, perchloric acid, periodic acid, iron (II) chloride, iron (II) sulfate, and the like.
  • the amount may be about 0.5 to 3.0 mol with respect to 1 mol of the compounds of formulas (I) to (III).
  • the oxidizing agent used in the reaction also needs to be appropriately adjusted depending on the redox potential of the aromatic compound (monomer) forming the composite conductive polymer composition.
  • ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxodisulfate Iron (III) chloride, iron (III) sulfate, iron (III) tetrafluoroborate, iron (III) hexafluorophosphate, copper (II) sulfate, copper (II) chloride, copper (II) tetrafluoroborate
  • copper (II) hexafluorophosphate can be used.
  • the ratio of the polymer compound (A) to the compounds (I) to (III) in the reaction depends on the properties of the finally obtained composite conductive polymer composition, and therefore cannot be determined simply.
  • an example of a preferable range can be shown as follows by the number of sulfonic acid groups in the polymer compound (A) and the molar ratio of the compounds (I) to (III) used.
  • the polymer compound (A) is present in an amount such that the molar ratio of the sulfonic acid groups in the compound is 0.2 to 1.5 with respect to 1 mol of the compound selected from the formulas (I) to (III). You just have to let them know.
  • the amount of the oxidizing agent used is usually about 1.5 to 2.5 mol (monovalent conversion) per 1 mol of the compounds (I) to (III), depending on the oxidation degree (acidity) in the system.
  • the polymerization can be sufficiently carried out even with 1 mol or less per 1 mol of the monomer.
  • the temperature of the polymerization reaction for obtaining the composite conductive polymer composition varies depending on the types of the compounds (I) to (III)
  • the calorific value after the oxidation reaction and the ease of extracting hydrogen vary depending on the types of the compounds (I) to (III). The range is different.
  • the temperature is preferably 40 ° C. or lower
  • the compound (II) is preferably 90 ° C. or lower
  • the compound (III) is preferably 20 ° C. or lower.
  • the reaction temperature should be relatively low and the reaction time should be relatively long, and vice versa. It ’s fine.
  • the polymer obtained in this manner can be made into a composite conductive polymer composition as a target product after further washing and the like as necessary. As described later, this dissolves stably in an aromatic solvent such as toluene and an ester solvent such as ethyl acetate in which the conventional conductive polymer composition did not dissolve.
  • Examples of methods of using the composite conductive polymer composition of the present invention thus obtained include a composite conductive polymer composition solution in which this is dissolved in an aromatic solvent and an ester solvent in a homogeneous state. Can do.
  • This composite conductive polymer composition solution is uniformly applied to the target portion by applying it to the portion where the formation of the conductive film is required and then volatilizing the aromatic solvent in the composition by means such as drying. A conductive film can be formed.
  • the composite conductive polymer composition is preferably an aromatic solvent such as toluene, benzene or xylene and / or an ester such as ethyl acetate, propyl acetate or butyl acetate. It is dissolved in a solvent of about 0.1 to 10% by mass.
  • aromatic solvent such as toluene, benzene or xylene and / or an ester such as ethyl acetate, propyl acetate or butyl acetate. It is dissolved in a solvent of about 0.1 to 10% by mass.
  • the above composite conductive polymer composition solution further includes benzyl alcohol, phenol, m-cresol, o-cresol, 2-ethyl alcohol for the purpose of improving the stability of the solution and improving the conductivity in the coating film state.
  • Aromatic compounds having a hydroxyl group such as naphthanol, 1-naphthanol, guaicol, 2,6-dimethylphenol can be added. These hydroxyl group-containing compounds are preferably added in an amount of about 0.01 to 45 parts by weight with respect to 100 parts by weight of the solvent in the composite conductive polymer composition solution.
  • the above composite conductive polymer composition solution further includes copper, silver, aluminum for the purpose of improving the conductivity of a self-supporting film as an antistatic coating and improving the catalytic performance as a counter electrode material for solar cells.
  • Metals such as platinum, titanium oxide, indium tin oxide, fluorine-doped tin oxide, metal oxides such as alumina and silica, conductive polymer compositions, carbon powders such as carbon nanotubes (CNT), fullerenes, carbon black, or dispersion
  • the body can be included as a filler component. These powders or dispersions are preferably added in an amount of 0.01 to 50 parts by weight with respect to 100 parts by weight of the solid content of the composite conductive polymer composition solution.
  • the composite conductive polymer composition can be used for a counter electrode for a dye-sensitized solar cell.
  • the counter electrode for dye-sensitized solar cell is formed by laminating the composite conductive polymer composition on one side of a transparent substrate when transparency is required, or by providing a light transmissive electrode on one side of the transparent substrate. It can be formed by arranging and laminating the composite conductive polymer composition on the light transmissive electrode. Moreover, when transparency is not requested
  • the thickness of the composite conductive polymer composition is usually in the range of 0.01 to 100 ⁇ m, preferably 0.1 to 50 ⁇ m.
  • a film or plate having a light transmittance of usually 50% or more, preferably 80% or more can be used.
  • transparent substrates include inorganic transparent substrates such as glass, polyethylene terephthalate (PET), polycarbonate (PC), polyphenylene sulfide, polysulfone, polyester sulfone, polyalkyl (meth) acrylate, polyethylene naphthalate (PEN), Examples thereof include polymer transparent substrates such as polyethersulfone (PES) and polycycloolefin.
  • metal foil metal foil, such as gold
  • the thickness of these transparent substrates is usually in the range of 200 to 7000 ⁇ m in the case of the inorganic transparent substrate, and is usually in the range of 20 to 4000 ⁇ m, preferably in the range of 20 to 2000 ⁇ m in the case of the polymer transparent substrate. It is in. In the case of a metal foil substrate, it is in the range of 0.1 ⁇ m to 1000 ⁇ m, preferably 1 ⁇ m to 500 ⁇ m.
  • the polymer transparent substrate and the metal foil substrate having a thickness within this range can impart flexibility to the resulting dye-sensitized solar cell.
  • a transparent electrode as needed to one side of the said transparent substrate.
  • the light transmissive electrode used here include a film-like conductive metal electrode and a mesh-like conductive metal electrode.
  • the film-like conductive metal electrode is formed by forming a film of tin oxide, tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO) or the like.
  • This film-like conductive metal electrode can be formed by vapor-depositing or sputtering tin oxide, ITO, FTO or the like on the surface of the transparent substrate. ⁇
  • the thickness of the film-like conductive metal electrode is usually in the range of 0.01 to 1 ⁇ m, preferably 0.01 to 0.5 ⁇ m.
  • the mesh-like conductive metal electrode is formed by forming a conductive metal such as copper, nickel, or aluminum in a mesh shape.
  • the mesh-like conductive metal electrode has a line width of usually 10 to 70 ⁇ m, preferably 10 to 20 ⁇ m, using a conductive metal such as copper, nickel, and aluminum, for example, by photolithography, and a pitch width. Is usually formed by etching to a mesh of 50 to 300 ⁇ m, preferably 50 to 200 ⁇ m.
  • the thickness of the conductive wire of the mesh-like conductive metal electrode is substantially the same as the thickness of the conductive metal used, and is usually in the range of 8 to 150 ⁇ m, preferably 8 to 15 ⁇ m.
  • This mesh-like conductive metal electrode can be attached to the surface of the transparent substrate using an adhesive or the like.
  • the counter electrode for dye-sensitized solar cell as a method of laminating the composite conductive polymer composition on the light transmissive electrode disposed on one side of the transparent substrate or one side of the transparent substrate, for example, A method of applying the composite conductive polymer composition solution to a light transmissive electrode disposed on one surface of the transparent substrate or one surface of the transparent substrate and removing the solvent in the solution one or more times is mentioned. It is done.
  • a known coater such as a dip coater, a micro bar coater, a roll coater, a comma coater, a die coater, or a gravure coater can be applied.
  • the solvent can be removed by a method such as natural drying by standing or forced drying under heating conditions using hot air or infrared rays.
  • the composite conductive polymer composition used for the dye-sensitized solar cell counter electrode is soluble in an organic solvent, the conventional composite conductive polymer composition is dispersed in an aqueous medium. Compared with the liquid, the coating process is easy and the productivity is excellent. Moreover, the corrosion deterioration of the metal in the counter electrode preparation stage originating in acidic aqueous solution can be suppressed.
  • the composite conductive polymer composition used for the counter electrode has components (a-1), (a-2) and (a-3) in a predetermined range.
  • the composite electroconductive polymer composition used for the counter electrode comprises components (a-1), (a-2) and (a-3) in a predetermined range.
  • the counter electrode for the dye-sensitized solar cell is a composite conductive polymer film as a uniform oxidation resistant film against an expensive platinum electrode which has been used as an electrode having oxidation resistance with respect to an electrolytic solution. Since various metals can be used as a result of the action, it can be provided at a low price.
  • the antistatic film using the composite conductive polymer composition can be formed as a self-supporting film by applying and drying the composite conductive polymer composition alone, so that it has a low resistance charge. Preventive film can be processed. Moreover, when mixing a composite conductive polymer composition and a thermoplastic resin and / or a thermosetting resin as needed, (1) what was melt-kneaded with an extruder, an extruder, etc. T-die etc. (2) Applying the composite conductive polymer composition solution to one or both surfaces of a thermoplastic resin, a thermosetting resin, and a glass film, and removing the solvent in the solution Can be obtained by a method of forming an antistatic layer.
  • thermoplastic resin used in the antistatic film is polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, polyacrylonitrile butadiene styrene, polyacrylonitrile styrene, polymethacryl, polyacryl, saturated.
  • examples thereof include polyester, polyamide, polycarbonate, poly-modified phenylene ether, polyphenylene sulfide, polysulfone, polyarylate, liquid crystal polymer, polyether ether ketone, polyamide imide, and the like, and polymer alloys and thermoplastic elastomers of these thermoplastic resins are also included.
  • thermosetting resin used in the antistatic film of the present invention examples include polyphenol, polyepoxy, unsaturated polyester, polyurethane, polyimide, polyurea, silicone resin, melamine resin, fluororesin, and alkyd resin.
  • the antistatic film is obtained by using the polymer compound (A) obtained by copolymerizing the component (a-1), the component (a-2) and the component (a-3) within a predetermined range. It is possible to form an antistatic film having high permeability with little performance variation under various high and low humidity conditions.
  • AIBN azobisisobutyronitrile
  • Coating film evaluation The finely dispersed solution of the comparative conductive polymer composition of the above (6) was filtered through a 200 mesh filter, and the filtrate was coated on a glass substrate and dried to obtain a uniform film ( ⁇ -7) was obtained, but the film quality was such that it would fall off when the surface was rubbed with a finger, and it was not a uniform free-standing coating film as obtained in Example 1 and its surface resistance was 1 M ⁇ / It was ⁇ .
  • Examples 2 to 5 and Comparative Examples 2 to 4 Polymer compounds ⁇ -2 to ⁇ -5 having the compositions shown in Table 1 below were prepared by the method shown in (1) and (2) of Example 1. Further, comparative polymer compounds ⁇ -7 to ⁇ -9 were prepared by the method shown in (1) and (2) of Comparative Example 1 with the composition shown in Table 1. Table 1 shows the molecular weight and water solubility of each polymer compound, including those obtained in Example 1 and Comparative Example 1.
  • Examples 6 to 10 and Comparative Examples 5 to 10 Using the polymer compounds ⁇ -2 to ⁇ -5 obtained in Examples 2 to 5, the composite conductive polymer composition ⁇ having the composition shown in Table 2 by the method shown in (3) and (4) of Example 1 was used. - ⁇ to ⁇ -6 were prepared (however, in the preparation of ⁇ -4, 100 g of ion-exchanged water and 100 g of 25 ° C. saturated saline were used instead of 200 g of ion-exchanged water at the time of re-dissolution of the polymer compound).
  • Comparative Examples 2 to 4 were used, and by the method shown in Comparative Examples 1 (1) and (2), the compositions shown in Table 2 were used for comparative conductivity.
  • Polymer compositions ⁇ -8 to ⁇ -13 were prepared.
  • Table 2 including those obtained in Example 1 and Comparative Example 1, the monomer composition of each conductive polymer, the type and amount of polymer compound used, the amount of hydrochloric acid used, the amount of oxidizing agent and the amount thereof, and the reaction Conditions (reaction temperature and reaction time) are shown.
  • Examples 11 to 15 and Comparative Examples 11 to 16 The composite conductive polymer compositions ⁇ -1 to ⁇ -6 obtained in Examples 1 and 6 to 10 were prepared from various aromatic solvents and / or esters according to (6) and (7) of Example 1. It was dissolved in a system solvent and dried to form a composite conductive polymer composition film of ⁇ -2 to ⁇ -6.
  • the comparative conductive polymer compositions obtained in Comparative Examples 1 and 5 to 10 were similarly dissolved in various aromatic solvents and / or ester solvents and then dried to try to form a film. ( ⁇ -8 to ⁇ -13).
  • Table 3 shows the dissolved state of each conductive polymer composition in the solvent, the state of the dry film produced using the conductive polymer composition, and the surface resistance value. In the table, the film obtained in Example 1 and Comparative Example 1 and the film using water as the solvent ( ⁇ -17) are also shown.
  • the composite conductive polymer composition obtained by oxidizing the aromatic compound using the polymer compound ( ⁇ -1 to ⁇ -5) of the present invention is aromatic.
  • a film that is soluble in a solvent and an ester solvent, and obtained after volatilization of the solvent was highly conductive.
  • the comparative conductive polymer composition obtained by using a polymer compound having a composition different from that of the polymer compound of the present invention has no solubility in an aromatic solvent or an ester solvent.
  • the film prepared by using the film had almost no conductivity.
  • Examples 16 to 22 and Comparative Examples 12 to 14 The counter electrode (opened copper mesh electrode) and the counter electrode substrate (80 ⁇ m thick PET film) used in Example 1 of International Publication No. WO / 2009/013942 were prepared in Examples 1 to 4. SUS foil, ITO PEN film, glass substrate, ITO glass substrate or FTO glass so that the thickness after drying the molecular composition solution or the conductive polymer composition solution prepared in Comparative Example 2 is 5 ⁇ m using a doctor blade It replaced with what was coated on the board
  • the dye-sensitized solar cell element using the composite conductive polymer composition of the present invention showed high photoelectric conversion efficiency.
  • Examples 23 to 24 and Comparative Examples 15 to 16 The composite conductive polymer composition solution prepared in Examples 1 and 2 or the conductive polymer composition solution prepared in Comparative Example 2 was readjusted to a solid content of 2.5%, respectively, and these were prepared by spin coating. The coating was applied to a glass substrate having a thickness of 1000 ⁇ m and a PET film substrate having a thickness of 1000 ⁇ m under a condition of 4000 rpm-15 sec, and the solvent was removed by a hot air dryer to produce an antistatic film having an antistatic layer formed thereon. In addition, when the film thickness of the antistatic layer was measured with a stylus type surface shape measuring instrument (Dektak 6M: manufactured by ULVAC), the thickness of each antistatic layer was approximately 25 nm.
  • Dektak 6M manufactured by ULVAC
  • the composite conductive polymer composition of the present invention uses a polymer compound (A) whose main component is a highly hydrophobic aromatic ring or alicyclic group as a dopant, and an aromatic solvent such as toluene, It can be stably solubilized in an ester solvent such as ethyl acetate.
  • a conductive polymer-forming composition solution obtained by dissolving the composite conductive polymer composition thus obtained in an aromatic solvent or an ester solvent in a transparent state can be easily applied to a portion requiring conductivity. It is possible to form a conductive film on the surface, and it can be used very advantageously in the field of electronic parts and the like.
  • a dye-sensitized solar electrode or an antistatic film using the composite conductive polymer composition of the present invention has excellent performance.

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Abstract

La présente invention a pour objet une composition de polymère conducteur composite qui est obtenue par le dopage d'un polymère π-conjugué qui contient, en tant que composant constitutif de monomère, un composé qui est facultativement substitué par un groupe alkyle et choisi parmi l'aniline, le thiophène et le pyrrole, avec un composé de type polymère qui est composé de 20 à 50 % en moles d'un monomère ayant un groupe acide sulfonique et un groupe vinyle polymérisable, de 20 à 50 % en moles d'un monomère ayant un groupe aromatique ou un groupe alicyclique et un groupe vinyle polymérisable, et de 30 à 60 % en moles d'un (méth)acrylate d'alkyle. La présente invention concerne également un procédé de production de la composition de polymère conducteur composite, et une solution qui est obtenue par la dissolution de la composition dans un solvant aromatique et/ou un solvant de type ester.
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