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WO2010095650A1 - Composition de polymère conducteur complexe, son procédé de fabrication, solution contenant ladite composition, et applications pour ladite composition - Google Patents

Composition de polymère conducteur complexe, son procédé de fabrication, solution contenant ladite composition, et applications pour ladite composition Download PDF

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Publication number
WO2010095650A1
WO2010095650A1 PCT/JP2010/052354 JP2010052354W WO2010095650A1 WO 2010095650 A1 WO2010095650 A1 WO 2010095650A1 JP 2010052354 W JP2010052354 W JP 2010052354W WO 2010095650 A1 WO2010095650 A1 WO 2010095650A1
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Prior art keywords
conductive polymer
meth
polymer composition
acrylate
composite conductive
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English (en)
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 JP2011500628A priority Critical patent/JP5738178B2/ja
Publication of WO2010095650A1 publication Critical patent/WO2010095650A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/30—Sulfur
    • 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
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—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 sulfur atoms as the only heteroatom, e.g. thiophene
    • 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
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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. More specifically, the present invention relates to an aromatic system such as aniline, thiophene, and pyrrole, and a heterocyclic ring. In order to impart solvent solubility to a ⁇ -conjugated polymer having a monomer compound as a monomer component, a composite conductive polymer composition doped with a polymer emulsifier, a production method thereof, a solution containing the composition, and the The present invention relates to the use of the composition for a dye-sensitized solar 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 In order to increase the electrical conductivity up to, doping is necessary. If this doping is performed, 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 does not cause pinholes alone, 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) and (a-2) (A-1) Monomer containing sulfonic acid group and polymerizable vinyl group 20 to 45 mol% (A-2) Monomer having aromatic group or alicyclic group and polymerizable vinyl group 55 to 80 mol% (A-2) Monomer having aromatic group or alicyclic group and polymerizable vinyl group 55 to 80 mol% A polymer compound (A) having the following components (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) and (a-2) (A-1) Monomer having sulfonic acid group and polymerizable vinyl group 20 to 45 mol% (A-2) Monomer having aromatic group or alicyclic group and polymerizable vinyl group 55 to 80 mol% Characterized in that the polymer compound (A) obtained by radical polymerization of the compound and a compound selected from the formulas (I) to (III) are coexisted in an electrolytic substrate solvent and chemically oxidatively polymerized using an oxidizing agent. This is a method for producing a composite conductive polymer composition.
  • the present invention provides a composite conductive polymer composition
  • a composite conductive polymer composition comprising the composite conductive polymer composition described above in a dissolved state of 0.1 to 10% by weight in an aromatic solvent selected from toluene, benzene and xylene. It is a solution.
  • 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 obtained by polymerization by the action of an oxidizing agent in the presence of the polymer emulsifier of the present invention is one that dissolves stably in an aromatic solvent such as toluene.
  • a conductive film can be easily obtained by applying a solution obtained by dissolving this composite conductive polymer in an aromatic solvent to a site requiring conductivity and drying it. .
  • the polymer compound (A) used in the present invention comprises a monomer having a sulfonic acid group and a polymerizable vinyl group in component (a-1) and an aromatic group or alicyclic component in component (a-2) according to a conventional method. It is produced by radical polymerization of a monomer having an aromatic group and a polymerizable vinyl group.
  • Examples of the monomer (a-1) having a sulfonic acid group and a polymerizable vinyl group include monomers having a sulfonic acid group such as a styrenesulfonic acid group and a sulfoethyl group.
  • Examples thereof include styrenesulfonic acid and Styrene sulfonates such as sodium styrene sulfonate, potassium styrene sulfonate, calcium styrene sulfonate, ethyl 2-methacrylate (meth) acrylate, ethyl 2-methacrylate (sodium 2-sulfonate), (meth) acrylic acid Examples thereof include ethyl 2-methacrylate (sulfonate) such as potassium ethyl 2-sulfonate, ethyl (meth) acrylate 2-calcium sulfonate, and the like.
  • Styrene sulfonates such as sodium styrene sulfonate, potassium styrene sulfonate, calcium styrene sulfonate, ethyl 2-methacrylate (meth) acrylate, ethyl 2-
  • 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- Phthalic acid methyl ester, (meth) acrylic acid ethyl 2-phthalic acid ethyl ester, 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-ethyl
  • the molar ratio of the component (a-1) to the component (a-2) is important. That is, the polymer emulsifier 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. This is to enable dissolution.
  • the amount of component (a-1) for producing the polymer compound (A) used in the present invention is 20 to 45 mol%, preferably 25 to 40 mol%.
  • the amount of component (a-2) is 55 to 80 mol%, preferably 60 to 75 mol%.
  • the polymer compound (A) of the present invention may contain a polymerizable component other than the above components (a-1) and (a-2).
  • the polymerizable component include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, alkyl (meth) acrylate such as lauryl (meth) acrylate, (meth) Acrylic acid, 2-hydroxy (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, tetrahydrofurfuryl ( Examples thereof include meth) acrylate and N, N-dimethylaminoethyl (meth) acrylate, and the blending amount when blended is about 0 to 20 mol%.
  • the radical polymerization reaction of the component (a-1), the component (a-2) and the polymerizable component added as necessary can be performed 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 for producing the polymer compound (A) is not particularly limited as long as it can be carried out in a state where the component (a-1) is not 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 with respect to 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.
  • solvent used in the above polymerization reaction examples include 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
  • examples of the solvent include glycol solvents such as glycol ethyl ether, and 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 emulsifier 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 emulsifier itself deteriorates. 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.
  • a specific method for producing a composite conductive polymer composition by the method of the present invention first, ion-exchanged water is acidified as necessary, and then the polymer compound obtained as described above is used.
  • examples thereof include a method in which one or more of the compounds of the formulas (I) to (III), which are raw materials, are added to this, and an oxidant is further added for oxidative polymerization after adding (A).
  • 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 in which the conventional conductive polymer composition has not dissolved.
  • An example of a method of using the composite conductive polymer composition of the present invention thus obtained includes a composite conductive polymer composition solution in which this is dissolved in an aromatic solvent in a homogeneous state.
  • 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 dissolved in an aromatic solvent such as toluene, benzene, xylene or the like at about 0.1 to 10% by mass. Is.
  • 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 and 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 light transmissive electrode may be disposed on one surface of the transparent substrate as necessary.
  • Examples of 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 with 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 examples include polyphenol, polyepoxy, unsaturated polyester, polyurethane, polyimide, polyurea, silicone resin, melamine resin, fluorine resin, alkyd resin, and the like.
  • 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.
  • A-1 (2-sodium sulfoethyl me
  • aniline was added to the emulsifier solution and stirred to obtain a uniform emulsion.
  • a solution prepared by dissolving 50 g of iron (III) sulfate in 150 g of ion-exchanged water was dropped into a flask kept at 25 ° C. over 10 hours. After completion of the dropwise addition, the temperature was raised to 50 ° C. and the polymerization reaction was continued for 48 hours.
  • the toluene solution was applied onto a glass substrate using a doctor blade so that the thickness after drying was 10 ⁇ m, and then dried, whereby a uniform green coating film was obtained.
  • the surface resistance value of the coating film was 100 k ⁇ / ⁇ .
  • aniline was added to the emulsifier solution and stirred to obtain a uniform emulsion.
  • a solution prepared by dissolving 10 g of ammonium peroxodisulfate in 30 g of ion-exchanged water was added dropwise over 10 hours while maintaining the inside of the flask at 0 ° C. After completion of the dropping, the temperature was returned to room temperature (25 ° C.), and the polymerization reaction was continued for 48 hours.
  • the composite conductive polymer composition (E-2) solution was applied onto a glass substrate with a doctor blade so that the thickness after drying was 10 ⁇ m, and then dried. A membrane was obtained.
  • the surface resistance value of the coating film was 250 k ⁇ / ⁇ .
  • A-3 (2-sodium sulfoethy
  • aniline was added to the emulsifier solution and stirred to obtain a uniform emulsion.
  • a solution prepared by dissolving 10 g of ammonium peroxodisulfate in 30 g of ion-exchanged water was added dropwise over 8 hours while maintaining the inside of the flask at 5 ° C. After completion of the dropping, the temperature was returned to room temperature (25 ° C.), and the polymerization reaction was continued for 36 hours.
  • This toluene solution of the composite conductive polymer composition (E-3) was applied on a glass substrate using a doctor blade so that the thickness after drying was 10 ⁇ m, and then dried. A coating film was obtained.
  • the surface resistance value of the coating film was 500 k ⁇ / ⁇ .
  • aniline was added to the emulsifier solution and stirred to obtain a uniform emulsion.
  • a solution prepared by dissolving 10 g of ammonium peroxodisulfate in 30 g of ion-exchanged water was added dropwise over 8 hours while maintaining the inside of the flask at 0 ° C. After completion of the dropwise addition, the polymerization reaction was continued for 30 hours while maintaining the temperature at 0 ° C.
  • This composite conductive polymer composition (E-5) was coated on a glass substrate with a doctor blade so that the thickness after drying was 10 ⁇ m and then dried. A coating film was obtained. The surface resistance value of the coating film was 30 k ⁇ / ⁇ .
  • This composite conductive polymer composition (E-6) was coated on a glass substrate with a doctor blade so that the thickness after drying was 10 ⁇ m and then dried. A coating film was obtained. The surface resistance value of the coating film was 70 k ⁇ / ⁇ .
  • A-7 comparative polymer compound (A-7) (2-sodium
  • the polymer (C-1) dispersion was filtered through a 200 mesh filter, and the filtrate was applied onto a glass substrate using a doctor blade so that the thickness after drying was 10 ⁇ m, followed by drying. As a result, a uniform film as a fine particle film was obtained. However, when the surface was rubbed with a finger, the film quality was such that it would fall off, and the uniform free-standing coating film obtained in Examples 1 to 6 was not obtained.
  • the resistance value was 10 7 ⁇ / ⁇ or more.
  • A-8 comparative polymer compound (A
  • aniline was added to the emulsifier solution and stirred to obtain a uniform emulsion.
  • a solution obtained by dissolving 10.0 g of ammonium peroxodisulfate in 30 g of ion-exchanged water was dropped into a flask kept at 0 ° C. over 10 hours. After completion of the dropwise addition, the polymerization reaction was continued for 30 hours while maintaining the temperature at 0 ° C.
  • the obtained reaction solution (CS-2) was a uniform solution.
  • the reaction solution (CS-2) was dried with a hot air circulating dryer at 80 ° C. to recover the solid content.
  • the obtained solid was redispersed in isopropyl alcohol (IPA), washed, and filtered again. This IPA washing and filtration was repeated 4 times to obtain a solid containing water.
  • This solid was dried under reduced pressure at 40 ° C. for 72 hours to obtain a polymer (C-2).
  • the volatile content was 2% or less.
  • the polymer (C-2) dispersion was filtered through a 200 mesh filter, and the filtrate was applied onto a glass substrate using a doctor blade so that the thickness after drying was 10 ⁇ m, followed by drying. As a result, a uniform film as a fine particle film was obtained. However, when the surface was rubbed with a finger, the film quality was such that it would fall off, and the uniform free-standing coating film obtained in Examples 1 to 6 was not obtained.
  • the resistance value was 10 7 ⁇ / ⁇ or more.
  • reaction solution (CS-2) was applied directly on a glass substrate so that the thickness after drying was 10 ⁇ m and dried, a non-uniform coating film was obtained, and the surface resistance was It was 10 6 ⁇ / ⁇ or more.
  • A-9 comparative polymer compound (A-9) (2-s
  • aniline was put into the emulsifier solution and stirred to obtain a uniform emulsion.
  • a solution obtained by dissolving 10.0 g of ammonium peroxodisulfate in 30 g of ion-exchanged water was added dropwise over 10 hours while maintaining the inside of the flask at 0 ° C. After completion of the dropwise addition, the polymerization reaction was continued for 30 hours while maintaining the temperature at 0 ° C.
  • the polymerization solution after the completion of the polymerization reaction was filtered off, and the resulting solid content was redispersed in water, washed, and filtered again. Further, washing with water and filtration were repeated 4 times to obtain a solid containing water. This solid was dried under reduced pressure at 40 ° C. for 72 hours to obtain a polymer (C-3). As a result of measuring the volatile content of this polymer (C-3), the volatile content was 1% or less.
  • the polymer (C-3) dispersion was filtered through a 200 mesh filter, and the filtrate was applied onto a glass substrate using a doctor blade so that the thickness after drying was 10 ⁇ m, followed by drying. As a result, a uniform film as a fine particle film was obtained. However, when the surface was rubbed with a finger, the film quality was such that it would fall off, and the uniform free-standing coating film obtained in Examples 1 to 6 was not obtained.
  • the surface resistance value was 10 7 ⁇ / ⁇ or more.
  • Comparative Example 4 Polymerization of comparative polymer compound (A-10) (sodium polystyrene sulfonate): 150 g of sodium p-styrenesulfonate, 150 g of ion-exchanged water and 300 g of isopropyl alcohol were charged into a four-necked flask having a capacity of 1000 cm 3 equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, a charging port and a thermometer. While introducing nitrogen gas into the flask, the mixture in the flask was heated to the reflux temperature. Next, 0.7 g of azobisisobutyronitrile was put into the flask, and the polymer was obtained by carrying out a polymerization reaction for 18 hours while maintaining the reflux state.
  • A-10 sodium polystyrene sulfonate
  • aniline was added to the emulsifier solution and stirred to obtain a uniform emulsion.
  • a solution obtained by dissolving 10.0 g of ammonium peroxodisulfate in 30 g of ion-exchanged water was added dropwise over 10 hours while maintaining the inside of the flask at 0 ° C. After completion of the dropwise addition, the polymerization reaction was continued for 30 hours while maintaining the temperature at 0 ° C.
  • the polymer (C-4) dispersion was filtered through a 200 mesh filter, and the filtrate was applied onto a glass substrate using a doctor blade so that the thickness after drying was 10 ⁇ m, followed by drying. As a result, a uniform film as a fine particle film was obtained. However, when the surface was rubbed with a finger, the film quality was such that it would fall off, and the uniform free-standing coating film obtained in Examples 1 to 6 was not obtained.
  • the resistance value was 10 7 ⁇ / ⁇ or more.
  • Comparative Example 5 Polymerization of comparative polymer compound (A-11) (polystyrene sulfonate sodium): 150 g of sodium p-styrenesulfonate, 150 g of ion-exchanged water and 300 g of isopropyl alcohol were charged into a four-necked flask having a capacity of 1000 cm 3 equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, a charging port and a thermometer. While introducing nitrogen gas into the flask, the mixture in the flask was heated to the reflux temperature. Subsequently, 0.7 g of azobisisobutyronitrile was put into the flask, and the refluxed state was maintained, and a polymerization reaction was performed for 20 hours to obtain a polymer.
  • A-11 polystyrene sulfonate sodium
  • aniline was put into the emulsifier solution and stirred to obtain a uniform emulsion.
  • a solution obtained by dissolving 10.0 g of ammonium peroxodisulfate in 30 g of ion-exchanged water was dropped into a flask kept at 0 ° C. over 10 hours. After completion of the dropwise addition, the polymerization reaction was continued for 30 hours while maintaining the temperature at 0 ° C.
  • the obtained reaction solution (CS-5) was a uniform solution.
  • the reaction solution (CS-5) was dried with a hot air circulating dryer at 80 ° C. to recover the solid content.
  • the obtained solid was re-dispersed in water, washed, and filtered again. This washing with water and filtration were repeated four times to obtain a solid containing water.
  • This solid was dried under reduced pressure at 100 ° C. for 72 hours to obtain a polymer (C-5).
  • the volatile content was 1% or less.
  • the polymer (C-5) aqueous dispersion was filtered through a 200 mesh filter, and the filtrate was applied onto a glass substrate using a doctor blade so that the thickness after drying was 10 ⁇ m, and then dried. As a result of drying, a green uniform coating film was obtained. When the surface resistance value of the coating film was measured, it was 3 M ⁇ / ⁇ .
  • Examples 7 to 11 and Comparative Examples 6 to 9 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 14 to 15 and Comparative Examples 9 to 10 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) mainly composed of a highly hydrophobic aromatic ring or alicyclic group as a dopant, and is stable in an aromatic solvent such as toluene. Solubilized in water.
  • a composite conductive polymer forming composition solution obtained by dissolving the composite conductive polymer composition thus obtained in an aromatic solvent in a transparent state can easily be applied to a portion where conductivity is required.
  • a film can be formed and can be used very advantageously in the field of electronic components 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 technique qui permet la dissolution d'une large gamme de compositions de polymère conducteur dans un solvant organique et qui permet la formation aisée d'un film conducteur sur une partie ciblée. La présente invention concerne une composition de polymère conducteur complexe formulée par le dopage d'un polymère conducteur π-conjugué (β) ayant un composé choisi parmi les formules (I) à (III) en tant qu'élément de type monomère avec un composé de type polymère (A), qui est composé de 20 à 45 % en moles d'un monomère comprenant (a-1) un groupe sulfonate et un groupe vinyle polymérisable, et de 55 à 80 % en moles d'un monomère ayant (a-2) un groupe aromatique ou un groupe alicyclique et un groupe vinyle polymérisable. La présente invention concerne également un procédé de fabrication de celle-ci, et une solution obtenue par la dissolution de ladite composition dans un solvant aromatique. (I) (II) (III) (Dans les formules, R1 à R7 représentent un atome d'hydrogène ou un groupe alkyle ayant de 1 à 12 atomes de carbone).
PCT/JP2010/052354 2009-02-17 2010-02-17 Composition de polymère conducteur complexe, son procédé de fabrication, solution contenant ladite composition, et applications pour ladite composition Ceased WO2010095650A1 (fr)

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