JP6010390B2 - Film production method - Google Patents

Description

  The present invention relates to a conductive composition comprising a conductive polymer which is a complex of poly (3,4-dialkoxythiophene) and a polyanion and a specific surfactant, and a coating film using the same. It relates to the film which has.

  The conductive polymer is a solid electrolyte of a solid electrolytic capacitor; a conductor for an antistatic agent; a transparent electrode formed on a liquid crystal display, an electroluminescent display, a plasma display, an electrochromic display, a solar cell, a touch panel, etc .; and an electromagnetic wave Widely used for coating of base materials such as shielding materials. Usually, the most versatile transparent electrode is an indium-tin composite oxide (ITO) vapor-deposited film, but it requires a high temperature for film formation, which has a problem of high film formation cost. . On the other hand, as a transparent electrode made of an organic material, a film using a conductive polymer that can be formed at low temperature and low cost has been proposed. As a conductive polymer in this application, for example, a polymer obtained by polymerizing a polymerizable monomer such as thiophene or a derivative thereof by chemical oxidative polymerization or electrolytic oxidative polymerization is known. Oxidative polymerization is performed.

  As the conductive polymer and the method for producing the same, for example, a complex of poly (3,4-dialkoxythiophene) and polyanion having good water dispersibility and a method for producing the same are known (for example, , See Patent Document 1). Further, an antistatic film comprising an antistatic layer containing a specific resin and compound and a π-conjugated conductive polymer is known (see, for example, Patent Document 2). Furthermore, a step (A) of forming a protective layer satisfying specific conditions on the norbornene-based resin film, a conductive paint containing polyethylenedioxythiophene is applied on the protective layer and cured to form a transparent conductive layer In the method for producing a transparent conductive laminated film including the step (C) of forming, the conductive paint further includes a glycol surfactant and / or a glycol surfactant having an acetylene group in the molecule. It has been reported that the surface tension of the paint can be lowered, thereby improving the in-plane uniformity of the resistance value (see, for example, Patent Document 3). Also known is a method of adding an acetylene glycol surfactant after the production of a conductive polymer (see, for example, Patent Document 4 and Patent Document 5).

JP-A-7-090060 JP 2012-016876 A JP 2009-245935 A Japanese Patent Laid-Open No. 6-049246 JP 2005-527048 A

  However, the above known techniques have the following problems. Even if a thin film is formed using the conductive polymer described in Patent Document 1, the surface resistance value is significantly increased under a high voltage. For this reason, it is difficult to mount the component in which the thin film is formed on a device exposed to a high voltage. The performance of the antistatic film described in Patent Document 2 is not at a sufficient level. Further, Patent Documents 3 to 5 do not disclose that the increase in the surface resistance value can be suppressed even under high voltage, and the surface resistance of the thin film even under high voltage while maintaining the performance of the conventional conductive polymer. There is a need for a conductive composition that can suppress an increase in value.

  The present invention has been made to solve the above-described problems, and aims to suppress an increase in the surface resistance value of a thin film even under a high voltage while maintaining the performance of a conventional conductive polymer. .

One form of the present invention for achieving the above object is a 3,4-dialkoxythiophene represented by the following formula (1):
Wherein R ¹ and R ² are independently of each other hydrogen or a C _1-4 alkyl group, or together form a C _1-4 alkylene group, the alkylene group optionally A conductive polymer obtained by chemical oxidative polymerization in an aqueous solvent in the presence of a polyanion,
The following formulas (2) and (3)
(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ each represent an alkyl group having 1 to 5 carbon atoms, l and m are positive numbers each having an average of 0 to 25, and l + m is an average of 0 to 40. is there.)
(Wherein R ⁷ and R ⁸ each represent an alkyl group having 1 to 5 carbon atoms, and n is a positive number having an average of 0 to 25). At least one of acetylene glycol surfactants represented by And the acetylene glycol surfactant is 0.001 to 1 mol of the conductive composition with respect to 1 mol of 3,4-dialkoxythiophene.

  Another embodiment of the present invention is a conductive composition comprising 50 to 2000 parts by mass of a polyanion with respect to 100 parts by mass of 3,4-dialkoxythiophene.

  Another embodiment of the present invention is a conductive composition in which the polyanion is polystyrene sulfonic acid.

  One embodiment of the present invention is a film having a coating film using any of the above-described conductive compositions as a conductor.

  ADVANTAGE OF THE INVENTION According to this invention, the raise of the surface resistance value of a thin film can be suppressed even under high voltage, maintaining the performance of the conventional conductive polymer.

  Hereinafter, preferred embodiments of a conductive composition according to the present invention and a film having a coating film using the same will be described. In the description of the following embodiment, first, after describing the conductive polymer and the manufacturing method thereof contained in the conductive composition according to the embodiment of the present invention, the conductive composition and the manufacturing method thereof, A film having a coating film and a method for producing the film will be described.

1. Conductive polymer and production method thereof The conductive polymer contained in the conductive composition according to this embodiment is a 3,4-dialkoxythiophene represented by the following formula (1).
Wherein R ¹ and R ² are independently of each other hydrogen or a C _1-4 alkyl group, or together form a C _1-4 alkylene group, the alkylene group optionally Which may be substituted) is chemically oxidatively polymerized in an aqueous solvent in the presence of a polyanion.

  Materials essential for producing the conductive polymer are the following (1) to (4).

(1) 3,4-dialkoxythiophene In the 3,4-dialkoxythiophene represented by the above formula (1), the C _1-4 alkyl group of R ¹ and R ² is preferably a methyl group, ethyl Group, n-propyl group and the like. Preferred examples of the C _1-4 alkylene group in which R ¹ and R ² are combined include a 1,2-alkylene group and a 1,3-alkylene group. Specifically, a methylene group 1,2-ethylene group, 1,3-propylene group, etc., among which 1,2-ethylene group is particularly preferable. The C _1-4 alkylene group may be substituted, and preferred substituents in that case include a C _1-12 alkyl group or a phenyl group. Preferred _examples of the substituted C _1-4 alkylene group include a 1,2-cyclohexylene group and a 2,3-butylene group. As representative examples of such alkylene groups, 1,2-alkylene groups in which both R ¹ and R ² are substituted with a C _1-12 alkyl group include ethene, propene, hexene, octene, decene, dodecene, styrene, and the like. Derived from 1,2-dibromoalkanes obtained by bromination of α-olefins.

(2) Polyanion Examples of compounds capable of forming a polyanion used in the embodiment of the present invention (hereinafter sometimes referred to as polyanions) include polycarboxylic acids such as polyacrylic acid, polymethacrylic acid, and polymaleic acid; And polysulfonic acids such as acid and polyvinyl sulfonic acid; Of these, polystyrene sulfonic acid is particularly preferred. The molecular weight of the polyanion compound is not particularly limited, but usually the weight average molecular weight (Mw) is in the range of 1,000 to 2,000,000, more preferably in the range of 2,000 to 1,000,000. More preferably, it is in the range of 10,000 to 500,000. In particular, it is preferable to use polystyrene sulfonic acid having the above molecular weight range. The sulfonation rate of polystyrene sulfonic acid is not particularly limited, but is preferably in the range of 80 to 100%, more preferably 85 to 95%. Here, the “sulfonation rate” refers to the total (A + B) of styrene units (A) having a sulfonic acid group and styrene units (B) having no sulfonic acid group in the polystyrene sulfonic acid. It refers to the ratio (%) of A).

  Examples of the method for obtaining polystyrene sulfonic acid include a method for sulfonating polystyrene and a method for polymerizing sodium styrene sulfonate. The latter method of polymerizing sodium styrenesulfonate makes it easier to obtain polystyrene sulfonic acid having a higher purity than the former method of sulfonating polystyrene. In this method, sodium styrenesulfonate is dissolved in an appropriate amount of ion-exchanged water, polymerized using a water-soluble initiator, and polymerized. Preferable examples of the water-soluble initiator include oxidants such as persulfate, hydrogen peroxide, and transition metals. The polymerization temperature is not particularly limited, but is preferably 10 to 90 ° C. The resulting reaction solution can be treated with a cation exchange resin and an anion exchange resin to obtain polystyrene sulfonic acid. The molecular weight of the sodium polystyrene sulfonate obtained can be adjusted by the coexistence of the oxidizing agent as described above during the polymerization.

  The amount of the polyanion used is preferably 50 to 2000 parts by mass, more preferably 100 to 1000 parts by mass, and more preferably 200 to 500 parts by mass with respect to 100 parts by mass of 3,4-dialkoxythiophene. is there. By using 50 parts by mass or more of the polyanion with respect to 100 parts by mass of 3.4-dialkoxythiophene, the effect of improving the conductivity due to the addition of the polyanion can be sufficiently exhibited. By using 2000 parts by mass or less with respect to parts, the resistance value can be suppressed by not adding polyanion excessively, and maintenance of conductive performance can be expected.

(3) Polymerization initiator Examples of the polymerization initiator (hereinafter simply referred to as “initiator”) used in the embodiment of the present invention include oxidizing agents such as persulfates, hydrogen peroxide, and transition metals. it can. As the initiator, more preferably, the ferrous salt or the ferric salt can be used alone or in combination. In that case, ferrous chloride, ferrous sulfate, ferrous nitrate, ferrous toluenesulfonate, ferrous dodecylbenzenesulfonate, ferrous naphthalenesulfonate are preferred examples of ferrous salts. it can. Moreover, as a ferric salt, ferric chloride, ferric sulfate, ferric nitrate, ferric toluenesulfonate, ferric dodecylbenzenesulfonate, ferric naphthalenesulfonate can be illustrated suitably. . Further, it is more preferable to use a persulfate as a polymerization initiator in combination with the ferrous salt and the ferric salt. As the persulfate, for example, ammonium persulfate, sodium persulfate, potassium persulfate, calcium persulfate, barium persulfate and the like can be preferably used. Among them, a combination of ammonium persulfate and ferric sulfate is preferable. Moreover, as a ratio of a persulfate and a ferric salt, 1-5000: 1 are preferable at molar ratio, and 5-100: 1 are further more preferable. The amount of ferric salt used is preferably 1 to 400 parts by weight, more preferably 5 to 200 parts by weight, and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of 3,4-dialkoxythiophene. Part. When the ferric salt is used in an amount of 1 part by mass or more with respect to 100 parts by mass of 3,4-dialkoxythiophene, the conductivity can be improved, and the ferric salt is 400 parts by mass with respect to 100 parts by mass of 3,4-dialkoxythiophene. When the amount is less than or equal to the amount, the reactivity can be increased. In the case of using a plurality of initiators, the plurality of initiators may be mixed and used in advance, but the mixing in advance is not essential, as long as it is in a mixed state when the conductive polymer is synthesized.

  When polymerizing 3,4-dialkoxythiophene in the presence of a polyanion, the polymerization temperature is preferably from 5 to 90 ° C, particularly preferably from 10 to 50 ° C. The polymerization time is preferably 1 to 48 hours, particularly 1 to 24 hours.

(4) Aqueous solvent The aqueous solvent is preferably water or a mixture of water and a water-miscible organic solvent, and more preferably water. When mixing a water-miscible organic solvent with water, it is preferable that a water-miscible organic solvent shall be 10 mass% or less with respect to the total amount of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols such as methanol, ethanol, propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; N-methyl-2-pyrrolidone, N-methylacetamide, N, N-dimethylformamide, N , N-dimethylacetamide, hexamethylene phosphortriamide, N-vinylpyrrolidone, N-vinylformamide, amide compounds such as N-vinylacetamide; phenols such as cresol, phenol, xylenol; ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin, D-glucose, D-glucitol, iso Polyhydric aliphatic alcohols such as prene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol and neopentyl glycol; carbonate compounds such as ethylene carbonate and propylene carbonate; Ether compounds such as diethyl ether; chain ethers such as dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, and polypropylene glycol dialkyl ether; heterocyclic compounds such as 3-methyl-2-oxazolidinone; acetonitrile, glutarodinitrile Nitrile compounds such as methoxyacetonitrile, propionitrile, benzonitrile; sulfoxides represented by dimethyl sulfoxide; Can be. These water-miscible organic solvents may be used alone or in a mixture of two or more. Among the above-mentioned water-miscible organic solvents, ethanol and isopropanol are preferred because they are less likely to damage the working environment and have a boiling point lower than that of water and can easily form a coating film.

(5) Manufacturing method of conductive polymer The conductive polymer contained in the conductive composition according to this embodiment can be manufactured, for example, by the following method. First, the polyanion is dispersed or dissolved in an aqueous solvent, and 3,4-dialkoxythiophene as a precursor monomer is added to the resulting solution to obtain a monomer dispersion. Next, an initiator is added to the monomer dispersion to chemically oxidatively polymerize 3,4-dialkoxythiophene. Thereafter, excess oxidant and unreacted monomer are removed and purified to obtain an aqueous dispersion of a conductive polymer having a structure in which poly (3,4-dialkoxythiophene) and polyanion are complexed. The solid content concentration of the aqueous dispersion of the conductive polymer thus obtained is preferably 0.1 to 4.0% by mass, more preferably 0.5 to 2.0% by mass, and still more preferably. 1.0 to 1.5% by mass.

2. Conductive Composition and Manufacturing Method Thereof The conductive composition according to this embodiment is manufactured by blending at least a specific acetylene glycol-based surfactant with the above-described aqueous dispersion of conductive polymer.

(1) Acetylene glycol surfactant In the embodiment of the present invention, as the acetylene glycol surfactant, at least one of those represented by the following formulas (2) and (3) is used.
In the formula, R ³ , R ⁴ , R ⁵ , and R ⁶ each represent an alkyl group having 1 to 5 carbon atoms, l and m are positive numbers having an average of 0 to 25, and l + m is an average of 0 to 40. .
^Wherein, R 7, ^{R 8} each represents an alkyl group having 1 to 5 carbon atoms, n represents a positive number having an average 0-25.

  Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2, Preferable examples include 5,8,11-tetramethyl-6-dodecin-5,8-diol, 3,5-dimethyl-1-hexyn-3-ol, and ethoxylated compounds thereof. When an ethoxylated product is used, the preferred number of moles of ethylene oxide (hereinafter referred to as EO) is 1 to 40, more preferably 1 to 30 in the above formula (2), more preferably 1 to 30, and n in the above formula (3). It is 0.5-25, Preferably it is 1-20.

  The amount of the acetylene glycol surfactant used is preferably 0.001 to 1 mol, more preferably 0.002 to 0.1 mol, still more preferably 1 mol of 3,4-dialkoxythiophene. 0.004 to 0.04 mol. By using 0.001 mol or more of acetylene glycol-based surfactant with respect to 1 mol of 3,4-dialkoxythiophene, an increase in resistance value under a high voltage can be effectively suppressed. On the other hand, by using 1 mol or less of acetylene glycol surfactant per 1 mol of 3,4-dialkoxythiophene, the electrical conductivity can be kept high.

(2) Other Additives The conductive composition according to this embodiment includes, for example, a water-miscible organic solvent and conductivity improvement in addition to the above-described aqueous dispersion of conductive polymer and acetylene glycol surfactant. An agent, a binder resin, or the like can also be mixed. In order to uniformly mix the conductivity improver and / or the binder resin with the aqueous dispersion of the conductive polymer, it is preferable to use a mixing and dispersing machine capable of imparting a high shearing force. Examples of the mixing and dispersing machine include a homogenizer, a high-pressure homogenizer, and a bead mill. Among them, a high-pressure homogenizer is preferable. Examples of the dispersion process using the high-pressure homogenizer include a process in which the complex solution before the dispersion process is subjected to a high-pressure opposing collision, a process in which the complex solution is passed through an orifice or a slit at a high pressure, and the like. When the dispersion treatment is performed by the mixing and dispersing machine, in principle, the temperature of the conductive polymer solution obtained by the treatment becomes high. Therefore, the temperature of the complex solution before the dispersion treatment is preferably -20 to 60 ° C, more preferably -10 to 40 ° C, and particularly preferably -5 to 30 ° C. Freezing can be prevented if the temperature of the complex solution is −20 ° C. or higher, and alteration of the conductive polymer or polyanion can be prevented if the temperature is 60 ° C. or lower. In addition, the aqueous dispersion of the conductive polymer after the dispersion treatment may be cooled by passing through a heat exchanger having a refrigerant temperature of −30 to 20 ° C., for example.

  In the dispersion step as described above, the dispersion treatment is performed such that the cumulant average particle size of the composite is preferably 2000 nm or less, more preferably 500 nm or less, and particularly preferably 200 nm or less. If the dispersion treatment is performed so that the average particle size of the cumulant of the composite is 2000 nm or less, the stability of the obtained conductive polymer solution is increased, and precipitation of the composite can be prevented. The cumulant average particle size can be determined from the measurement of particle size distribution by the dynamic light scattering method. The cumulant average particle size is adjusted by mixing conditions (for example, pressure) in the dispersion step. Specifically, the higher the pressure, the smaller the average particle size.

(2.1) Water-miscible organic solvent The water-miscible organic solvent as one component of the conductive composition is a water-miscible organic solvent that can be mixed with the aqueous solvent used in the production of the above-described conductive polymer. You can choose from the same type. The water-miscible organic solvent has a water content of preferably 4% by mass or less, more preferably 3% by mass or less, and more preferably 2% by mass or less. The amount of the water-miscible organic solvent is not particularly limited, but is preferably 10 to 5000 parts by mass, more preferably 50 to 3000 parts by mass with respect to 100 parts by mass of the solid content according to this embodiment. Part. When the amount of the water-miscible organic solvent is 3000 parts by mass or less with respect to 100 parts by mass of the solid content, the conductivity of the conductive coating film obtained from the conductive composition can be further increased. On the other hand, when the amount of the water-miscible organic solvent is 50 parts by mass or more with respect to 100 parts by mass of the solid content, the solution of the conductive composition becomes difficult to gel, and adjustment with an appropriate viscosity becomes possible.

(2.2) Conductivity improver In order to further improve the conductivity of the conductive coating film, it is preferable to add one or more conductivity improvers selected from the following compounds (2a) to (2h).
(2a) a nitrogen-containing aromatic cyclic compound (2b) a compound having two or more hydroxy groups (2c) a compound having two or more carboxy groups (2d) one or more hydroxy groups and one or more carboxys A compound having a group (2e) a compound having an amide group (2f) a compound having an imide group (2g) a lactam compound (2h) a compound having a glycidyl group

(2a) Nitrogen-containing aromatic cyclic compound As the nitrogen-containing aromatic cyclic compound, pyridines containing one nitrogen atom and derivatives thereof, imidazoles containing two nitrogen atoms and their Derivatives, pyrimidines and derivatives thereof, pyrazines and derivatives thereof, triazines containing three nitrogen atoms and derivatives thereof, and the like. From the viewpoint of solvent solubility and the like, pyridines and derivatives thereof, imidazoles and derivatives thereof, and pyrimidines and derivatives thereof are preferable.

  Specific examples of pyridines and derivatives thereof include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, N-vinylpyridine, 2,4-dimethylpyridine, 2,4 , 6-trimethylpyridine, 3-cyano-5-methylpyridine, 2-pyridinecarboxylic acid, 6-methyl-2-pyridinecarboxylic acid, 4-pyridinecarboxaldehyde, 4-aminopyridine, 2,3-diaminopyridine, 2 , 6-diaminopyridine, 2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 4-pyridinemethanol, 2,6-dihydroxypyridine, 2,6-pyridinedimethanol, methyl 6-hydroxynicotinate, 2 -Hydroxy-5-pyridinemethanol, ethyl 6-hydroxynicotinate, 4- Pyridinemethanol, 4-pyridineethanol, 2-phenylpyridine, 3-methylquinoline, 3-ethylquinoline, quinolinol, 2,3-cyclopentenopyridine, 2,3-cyclohexanopyridine, 1,2-di (4- Pyridyl) ethane, 1,2-di (4-pyridyl) propane, 2-pyridinecarboxaldehyde, 2-pyridinecarboxylic acid, 2-pyridinecarbonitrile, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, Examples include 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, and 3-pyridinesulfonic acid.

  Specific examples of imidazoles and derivatives thereof include imidazole, 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, N-vinylimidazole, and N-allylimidazole. 1- (2-hydroxyethyl) imidazole (N-hydroxyethylimidazole), 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazole dical Acid, dimethyl 4,5-imidazole dicarboxylate, benzimidazole, 2-aminobenzimidazole, 2-aminobenzimidazole-2-sulfonic acid, 2-amino-1-methylbenzimidazole, 2-hydroxybens Examples include imidazole and 2- (2-pyridyl) benzimidazole.

  Specific examples of pyrimidines and derivatives thereof include 2-amino-4-chloro-6-methylpyrimidine, 2-amino-6-chloro-4-methoxypyrimidine, 2-amino-4,6-dichloropyrimidine, 2-amino-4,6-dihydroxypyrimidine, 2-amino-4,6-dimethylpyrimidine, 2-amino-4,6-dimethoxypyrimidine, 2-aminopyrimidine, 2-amino-4-methylpyrimidine, 4,6 -Dihydroxypyrimidine, 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4,6-triaminopyrimidine, 2,4-dimethoxypyrimidine, 2,4,5-trihydroxypyrimidine, 2,4-pyrimidinediol, etc. Is mentioned.

  Specific examples of pyrazines and derivatives thereof include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5-methylpyrazinecarboxylic acid, pyrazineamide, 5 -Methylpyrazine amide, 2-cyanopyrazine, aminopyrazine, 3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2,3-diethylpyrazine and the like.

  Specific examples of triazines and derivatives thereof include 1,3,5-triazine, 2-amino-1,3,5-triazine, 3-amino-1,2,4-triazine, and 2,4-diamino. -6-phenyl-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine, 2,4,6-tris (trifluoromethyl) -1,3,5-triazine, 2,4,6-tri-2-pyridine-1,3,5-triazine, 3- (2-pyridine) -5,6-bis (4-phenylsulfonic acid) -1,2,4-triazine disodium 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine, 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine-ρ, ρ′- Disodium disulphonate, 2-hydroxy-4,6-dichloro And ro-1,3,5-triazine.

  The content of the nitrogen-containing aromatic cyclic compound is preferably in the range of 0.1 to 100 mol, more preferably in the range of 0.5 to 30 mol, with respect to 1 mol of the anion group unit of the polyanion. The range of 1 to 10 mol is particularly preferable from the viewpoint of conductivity. When the content of the nitrogen-containing aromatic cyclic compound is 0.1 mol or more, the interaction between the nitrogen-containing aromatic cyclic compound and the polyanion and poly (3,4-dialkoxythiophene) becomes strong. Tend to exhibit sufficient electrical conductivity. Moreover, when the nitrogen-containing aromatic cyclic compound is 100 mol or less, the content of the conductive polymer is relatively increased, and the conductivity can be further increased.

(2b) Compound having two or more hydroxy groups Examples of the compound having two or more hydroxy groups include propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin, D- Glucose, D-glucitol, isoprene glycol, dimethylolpropionic acid, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, Polyhydric aliphatic alcohols such as pentaerythritol, dipentaerythritol, thiodiethanol, glucose, tartaric acid, D-glucaric acid and glutaconic acid; high molecular alcohols such as cellulose, polysaccharide and sugar alcohol; 1,4-dihydroxybenze 1,3-dihydroxybenzene, 2,3-dihydroxy-1-pentadecylbenzene, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,4-dihydroxybenzophenone, 2,6-dihydroxybenzophenone, 3, 4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 2,4′-dihydroxydiphenylsulfone, 2,2 ′, 5,5′-tetrahydroxydiphenylsulfone, 3,3 ′, 5,5′-tetramethyl-4 , 4′-dihydroxydiphenylsulfone, hydroxyquinonecarboxylic acid and its salts, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3, 5-dihydroxybenzoic acid, 1, -Hydroquinonesulfonic acid and its salts, 4,5-hydroxybenzene-1,3-disulfonic acid and its salts, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7- Dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene-2,6-dicarboxylic acid, 1,6-dihydroxynaphthalene-2,5-dicarboxylic acid, 1,5-dihydroxynaphthoic acid, 1,4- Dihydroxy-2-naphthoic acid phenyl ester, 4,5-dihydroxynaphthalene-2,7-disulfonic acid and its salts, 1,8-dihydroxy-3,6-naphthalenedisulfonic acid and its salts, 6,7-dihydroxy-2 -Naphthalenesulfonic acid and its salts, 1,2,3 -Trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene, 5-methyl-1,2,3-trihydroxybenzene, 5-ethyl-1,2,3-trihydroxybenzene, 5-propyl- 1,2,3-trihydroxybenzene, trihydroxybenzoic acid, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetrahydroxy-p-benzoquinone, tetra Examples include hydroxyanthraquinone, aromatic compounds such as methyl garlic acid (methyl gallate) and ethyl garlic acid (ethyl gallate), and potassium hydroquinone sulfonate.

  The content of the compound having two or more hydroxy groups is preferably in the range of 0.05 to 50 mol and more preferably in the range of 0.3 to 10 mol with respect to 1 mol of the anion group unit of the polyanion. More preferred. When the content of the compound having two or more hydroxy groups is 0.05 mol or more with respect to 1 mol of the anion group unit of the polyanion, conductivity and heat resistance can be further improved. Further, when the content of the compound having two or more hydroxy groups is 50 mol or less with respect to 1 mol of the anion group unit of the polyanion, the content of the conductive polymer in the obtained conductive coating film is relatively The conductivity can be further increased.

(2c) Compound having two or more carboxy groups Examples of the compound having two or more carboxy groups include maleic acid, fumaric acid, itaconic acid, citraconic acid, malonic acid, 1,4-butanedicarboxylic acid, succinic acid, Aliphatic carboxylic acid compounds such as tartaric acid, adipic acid, D-glucaric acid, glutaconic acid, citric acid; phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, 5-sulfoisophthalic acid, 5-hydroxyisophthalic acid, methyl At least one aromatic ring such as tetrahydrophthalic anhydride, 4,4′-oxydiphthalic acid, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, etc. Aromatic carboxylic acid compounds with two or more carboxy groups attached ; Diglycolic acid, oxy two acid, thiodiacetic acid (thiodiacetic acid), thiodiacetic acid, iminodiacetic acid, etc. imino acid are exemplified.

  The compound having two or more carboxy groups is preferably in the range of 0.1 to 30 mol, more preferably in the range of 0.3 to 10 mol, relative to 1 mol of the anion group unit of the polyanion. When the content of the compound having two or more carboxy groups is 0.1 mol or more with respect to 1 mol of the anion group unit of the polyanion, conductivity and heat resistance can be further improved. In addition, when the content of the compound having two or more carboxy groups is 30 mol or less with respect to 1 mol of the anion group unit of the polyanion, the content of the conductive polymer in the conductive coating film is relatively large. Thus, the conductivity can be further increased.

(2d) Compound having one or more hydroxy groups and one or more carboxy groups Examples of the compound having one or more hydroxy groups and one or more carboxy groups include tartaric acid, glyceric acid, dimethylolbutanoic acid, dimethylol Examples include propanoic acid, D-glucaric acid, and glutaconic acid.

  The content of the compound having one or more hydroxy groups and one or more carboxy groups is 1 to 5,000 parts by mass with respect to 100 parts by mass in total of the polyanion and poly (3,4-dialkoxythiophene). It is preferably 50 to 500 parts by mass. When the content of the compound having one or more hydroxy groups and one or more carboxy groups is 1 part by mass or more, conductivity and heat resistance can be further improved. Further, when the content of the compound having one or more hydroxy groups and one or more carboxy groups is 5,000 parts by mass or less, the content of the conductive polymer in the conductive coating film is relatively increased. , Conductivity can be further increased.

(2e) Amide Compound The compound having an amide group is a monomolecular compound having an amide bond represented by —CO—NH— (wherein the CO portion is a double bond) in the molecule. That is, as the amide compound, for example, a compound having functional groups at both ends of the bond, a compound in which a cyclic compound is bonded to one end of the bond, urea and a urea derivative in which the functional groups at both ends are hydrogen Etc. Specific examples of amide compounds include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluamide, formamide, N-methylformamide, propionamide , Propioluamide, butyramide, isobutylamide, methacrylamide, palmitoamide, stearylamide, oleamide, oxamide, glutaramide, adipamide, cinnamamide, glycolamide, lactamide, glyceramide, tartaramide, citrulamide, glyoxylamide, pyruvamide, acetoacetamide, dimethyl Acetamide, benzylamide, anthranilamide, ethylenediamine Laacetamide, diacetamide, triacetamide, dibenzamide, tribenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1,3-diethylurea and These derivatives are mentioned.

  Moreover, acrylamide can also be used as an amide compound. As acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, Examples thereof include N-diethyl methacrylamide, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like. The molecular weight of the amide compound is preferably 46 to 10,000, more preferably 46 to 5,000, and particularly preferably 46 to 1,000.

  The content of the amide compound is preferably 1 to 5,000 parts by mass and more preferably 50 to 500 parts by mass with respect to 100 parts by mass in total of the polyanion and poly (3,4-dialkoxythiophene). preferable. When the content of the amide compound is 1 part by mass or more, conductivity and heat resistance can be further improved. Moreover, when content of an amide compound will be 5,000 mass parts or less, content of the conductive polymer in a conductive coating film will increase relatively, and electroconductivity can be improved more.

(2f) Imide compound Examples of the imide compound include phthalimide and phthalimide derivatives, succinimide and succinimide derivatives, benzimide and benzimide derivatives, maleimide and maleimide derivatives, naphthalimide and naphthalimide derivatives based on the skeleton.

Moreover, although an imide compound is classified into an aliphatic imide, an aromatic imide, etc. according to the kind of functional group of both terminal, an aliphatic imide is preferable from a soluble viewpoint. Furthermore, the aliphatic imide compound is classified into a saturated aliphatic imide compound having an unsaturated bond between carbons in the molecule and an unsaturated aliphatic imide compound having an unsaturated bond between carbons in the molecule. The saturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and is a compound in which both R ¹ and R ² are saturated hydrocarbons. Specifically, cyclohexane-1,2-dicarboximide, allantoin, hydantoin, barbituric acid, alloxan, glutarimide, succinimide, 5-butylhydantoic acid, 5,5-dimethylhydantoin, 1-methylhydantoin, 1,5 , 5-trimethylhydantoin, 5-hydantoin acetic acid, N-hydroxy-5-norbornene-2,3-dicarboximide, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimidooxycarbonyloxy) Ethyl] sulfone, α-methyl-α-propylsuccinimide, cyclohexylimide and the like. An unsaturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and one or both of R ¹ and R ² are one or more unsaturated bonds. Specific examples thereof include 1,3-dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 1,8 -Bismaleimide octane, N-carboxyheptylmaleimide and the like.

  The molecular weight of the imide compound is preferably 60 to 5,000, more preferably 70 to 1,000, and particularly preferably 80 to 500.

  The content of the imide compound is preferably 10 to 10,000 parts by mass, and 50 to 5,000 parts by mass with respect to 100 parts by mass in total of poly (3,4-dialkoxythiophene) and polyanion. Is more preferable. It is more preferable that the amount of the imide compound added is equal to or greater than the lower limit because the effect of adding the imide compound is increased. Further, if it is not more than the above upper limit value, it is more preferable because conductivity is increased due to an increase in the concentration of the conductive polymer.

(2g) Lactam Compound A lactam compound is an intramolecular cyclic amide of an aminocarboxylic acid, and a part of the ring is —CO—NR— (where R is hydrogen or an arbitrary substituent). However, one or more carbon atoms in the ring may be replaced with an unsaturated or heteroatom. Examples of the lactam compound include pentano-4-lactam, 4-pentanelactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexane lactam and the like.

  The content of the lactam compound is preferably 10 to 10000 parts by mass, and more preferably 50 to 5000 parts by mass with respect to 100 parts by mass in total of poly (3,4-dialkoxythiophene) and polyanion. Since the effect by addition of a lactam compound becomes high as the addition amount of a lactam compound is more than the said lower limit, it is preferable. Moreover, since it will become the electroconductivity improvement resulting from the raise of the density | concentration of a conductive polymer when it becomes below the said upper limit, it is more preferable.

(2h) Compound having glycidyl group Examples of the compound having glycidyl group include ethyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl phenyl ether, bisphenol A, and diglycidyl ether. And glycidyl compounds such as glycidyl acrylate and glycidyl methacrylate.

  The content of the compound having a glycidyl group is preferably 10 to 10000 parts by mass, and preferably 50 to 5000 parts by mass with respect to 100 parts by mass in total of poly (3,4-dialkoxythiophene) and polyanion. More preferred. It is preferable that the addition amount of the compound having a glycidyl group is equal to or more than the lower limit because the effect of the addition of the compound having a glycidyl group is increased. Moreover, since it will become the electroconductivity improvement resulting from the raise of the density | concentration of a conductive polymer when it becomes below the said upper limit, it is more preferable.

(3) Binder resin The binder resin is not particularly limited and may be appropriately selected depending on the purpose, and may be a thermosetting resin or a thermoplastic resin. For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyimides such as polyimide and polyamideimide; polyamides such as polyamide 6, polyamide 6,6, polyamide 12, and polyamide 11; polyvinylidene fluoride, polyvinyl fluoride, poly Fluororesin such as tetrafluoroethylene, ethylenetetrafluoroethylene copolymer, polychlorotrifluoroethylene; Vinyl resin such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride; Epoxy resin; Oxetane resin; Xylene resin; Aramid resin; Polyimide silicone; Polyurethane; Polyurea; Melamine resin; Phenol resin; And it can be exemplified copolymers thereof suitably. Further, the binder resin can be used by adding a curing agent such as a cross-linking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity adjusting agent, and the like as necessary.

  Among the binder resins, one or more of polyurethane, polyester, acrylic resin, polyamide, polyimide, epoxy resin, and polyimide silicone that can be easily mixed are preferable. Acrylic resins are suitable for applications such as optical filters because of their high hardness and excellent transparency. The binder resin preferably contains a liquid polymer that is cured by thermal energy and / or light energy. Here, examples of the liquid polymer that is cured by thermal energy include a reactive polymer and a self-crosslinking polymer. A reactive polymer is a polymer in which a monomer having a substituent is polymerized, and examples of the substituent include a hydroxy group, a carboxy group, an acid anhydride, an oxetane group, a glycidyl group, and an amino group. Specific monomers include polyfunctional alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol and glycerin; malonic acid, succinic acid, glutamic acid, pimelic acid, ascorbic acid, phthalic acid, acetylsalicylic acid, adipic acid, isophthalic acid Carboxylic acid compounds such as acid, benzoic acid and m-toluic acid; acid anhydrides such as maleic anhydride, phthalic anhydride, dodecyl succinic anhydride, dichloromaleic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, pimelic anhydride Products; Oxetane compounds such as 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-methyl-3-hydroxymethyloxetane, azidomethylmethyloxetane; bisphenol A diglycidyl ether, bisphenol F diglycol Zyl ether, phenol novolac polyglycidyl ether, N, N-diglycidyl-p-aminophenol glycidyl ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (ie 2,2-bis (4-glycidyloxy) Glycidyl ether compounds such as cyclohexyl) propane); N, N-diglycidylaniline, tetraglycidyldiaminodiphenylmethane, N, N, N, N-tetraglycidyl-m-xylylenediamine, triglycidyl isocyanurate, N, N-diglycidyl Glycidylamine compounds such as -5,5-dialkylhydantoin; diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, N-aminoethylpiperazine, benzene Dimethylamine, tris (dimethylaminomethyl) phenol, DHP30-tri (2-ethylhexoate), metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, boron trifluoride, monoethylamine, methanediamine, xylenediamine And amine compounds such as ethyl methyl imidazole; among compounds containing two or more oxirane rings in one molecule, glycidyl compounds by epichlorohydrin of bisphenol A, or the like;

In the reactive polymer, at least a bifunctional or higher functional crosslinking agent is used. Examples of the crosslinking agent include melamine resin, epoxy resin, metal oxide and the like. Examples of the metal oxide include basic metal compounds Al (OH) ₃ , Al (OOC · CH ₃ ) ₂ (OOCH), Al (OOC · CH ₃ ) ₃ , ZrO (OCH ₃ ), Mg (OOC · CH _3). ) ₂ , Ca (OH) ₂ , Ba (OH) _{3 and the} like can be used as appropriate.

  Self-crosslinking polymers are those that self-crosslink between functional groups by heating, and examples include those containing a glycidyl group and a carboxy group, and those containing both an N-methylol and a carboxy group.

  Examples of the liquid polymer that is cured by light energy include oligomers or prepolymers such as polyester, epoxy resin, oxetane resin, polyacryl, polyurethane, polyimide, polyamide, polyamideimide, and polyimide silicone. Examples of monomer units constituting a liquid polymer that is cured by light energy include bisphenol A / ethylene oxide-modified diacrylate, dipentaerythritol hexa (penta) acrylate, dipentaerythritol monohydroxypentaacrylate, and dipropylene glycol diacrylate. Acrylate, trimethylolpropane triacrylate, glycerin propoxytriacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, Pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, trimethylolpropane tria Acrylates such as relate and tripropylene glycol diacrylate; tetraethylene glycol dimethacrylate, alkyl methacrylate, allyl methacrylate, 1,3-butylene glycol dimethacrylate, n-butyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol dimethacrylate, 2- Such as ethylhexyl methacrylate, glycidyl methacrylate, 1,6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, t-butyl methacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, etc. Methacrylates Glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, higher alcohol glycidyl edel, 1,6-hexanediol glycidyl ether, phenyl glycidyl ether, stearyl glycidyl ether; diacetone acrylamide, N, N-dimethylacrylamide, dimethylaminopropyl Acrylamide, dimethylaminopropyl methacrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylformamide, N-methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N- Acrylics such as phenylacrylamide, acryloylpiperidine, 2-hydroxyethylacrylamide, etc. (Meth) amides; vinyl ethers such as 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether; vinyl carboxylates such as vinyl butyrate, vinyl monochloroacetate and vinyl pivalate Examples thereof include monofunctional monomers and polyfunctional monomers of esters.

  A liquid polymer that is cured by light energy is cured by a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthones and the like. Furthermore, n-butylamine, triethylamine, tri-n-butylphosphine, or the like can be mixed as a photosensitizer. Examples of the cationic polymerization initiator include aryldiazonium salts, diarylhalonium salts, triphenylsulfonium salts, silanol / aluminum chelates, α-sulfonyloxyketones, and the like.

  The amount of the binder resin is not particularly limited, but is solid with respect to 100 parts by mass of a conductive polymer solid (poly (3,4-dialkoxythiophene) and polyanion complex). It is preferably 10 to 10,000 parts by mass, particularly 50 to 4,000 parts by mass in terms of minutes.

  Other components that can be included in the conductive composition include, for example, fillers, crosslinking agents, ultraviolet absorbers, antioxidants, polymerization inhibitors, surface modifiers, defoaming agents, plasticizers, antibacterial agents, and surfactants. Preferable examples include agents and metal fine particles. These components may be used alone or in combination of two or more. Furthermore, only one type of material belonging to the above components may be used, or two or more types may be used in combination.

3. Film having Coating Film and Method for Producing the Same The conductive composition according to this embodiment can be used for a film having a coating film formed thereon. The conductive composition not only exhibits excellent conductivity and transparency, but also retains performance capable of suppressing an increase in resistance value under high voltage. Therefore, the conductive composition includes an antistatic film, a conductive paint, a solid electrolytic capacitor, a touch screen, an organic LED, an organic EL, a lithium secondary battery, an organic thin film solar battery, a conductive polymer fiber, and the like. Can also be used.

  The film having a coating film according to this embodiment includes a film serving as a base material (referred to as a base film) and a conductive coating film formed on at least one surface of the base film. When manufacturing a film having a coating film using the conductive composition as a conductor, after applying the conductive composition solution to the base film, or after immersing the base film in the solution, A film having a coating film can be obtained by removing volatile components by drying. The drying temperature is not particularly limited, but is preferably 40 ° C. or higher and not higher than the temperature at which the coating film or the substrate film is not damaged.

  Specific examples of the method for supplying the solution to the base film include spin coating, roller coating, bar coating, dip coating, gravure coating, curtain coating, die coating, spray coating, and doctor blade coating. And a kneader coating method. The base film is not particularly limited, and is preferably a base made of a transparent material. The type of the material, the shape, structure, size, thickness, etc. of the base are appropriately selected according to the purpose. it can. In this specification, “transparent” is broadly interpreted to include any of transparent and colorless, colorless and translucent, and colored and translucent. As a material for the transparent substrate, for example, a resin can be preferably cited. The type of the resin is not particularly limited and can be appropriately selected depending on the purpose. For example, polyethylene terephthalate resin (crystalline or amorphous), polybutylene terephthalate resin (crystalline or amorphous), polyethylene naphthalate. Phthalate resin (crystalline or amorphous), polyvinyl chloride resin, polyether sulfone resin, polycarbonate resin, polystyrene resin, polyimide resin, polyetherimide resin, polyvinyl acetate resin, polyvinylidene chloride resin, polyvinylidene fluoride resin , Polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polyacrylonitrile resin, polyolefin resin, polystyrene resin, polyamide resin, polybutadiene resin, cellulose acetate, cellulose nitrate, acrylonitrile-butane Ene - styrene copolymer resin (ABS resin) can be mentioned, with one of these, or may be used in combination of two or more. When the sheet is stretched, a resin film having a low glass transition temperature, such as an amorphous polyethylene terephthalate film or a polystyrene film, is preferably used. When using a resin film having a low glass transition temperature as the substrate film, it is preferable to set the drying temperature to 80 ° C. or lower in order to prevent deterioration of the surface appearance.

  In the film having the coating film according to this embodiment, the thickness of the coating film formed by the solution of the conductive composition is not particularly limited and can be appropriately selected according to the purpose. , 0.01 to 10 μm. When the thickness of the coating film is 0.01 μm or more, the surface resistivity of the film having the coating film can be further stabilized, and when the thickness of the coating film is 10 μm or less, the adhesion between the transparent substrate and the coating film Can be further enhanced.

  Next, although a manufacture example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to a following example. In the following examples, parts and% mean parts by mass and% by mass, respectively.

1. Synthesis of polyanion <Production Example 1>
In 1000 ml of ion-exchanged water, 206 g of sodium styrenesulfonate was dissolved. While stirring at 80 ° C., 3 g of ammonium persulfate solution previously dissolved in 10 ml of water was added dropwise for 2 hours, and the solution was stirred for 6 hours. The obtained sodium polystyrene sulfonate solution was treated twice with 200 g of cation exchange resin. Then, ion-exchange water was added and adjusted so that solid content might be 5%. The obtained polystyrene sulfonic acid was analyzed using a HPLC (high performance liquid chromatography) system using a GPC (gel filtration chromatography) column. As a result of measuring the weight average molecular weight (Mw) using pullulan manufactured by Showa Denko KK as a standard substance, the Mw of polystyrene sulfonic acid was about 200,000.
<Production Example 2>
A polystyrene sulfonic acid solution having a solid content of 5% was obtained in the same manner as in Production Example 1 except that 3 g of ammonium persulfate in Production Example 1 was changed to 1 g. The obtained polystyrene sulfonic acid was analyzed using a HPLC (high performance liquid chromatography) system using a GPC (gel filtration chromatography) column. As a result of measuring the weight average molecular weight (Mw) using pullulan manufactured by Showa Denko KK as a standard substance, the Mw of polystyrene sulfonic acid was about 400,000.

2. Synthesis of conductive polymer <Production Example 3>
5 g of 3,4-ethylenedioxythiophene (EDOT) was mixed with a solution obtained by dissolving 300 g of the polystyrenesulfonic acid aqueous solution (solid content: 15 g) obtained in Production Example 1 in 1000 ml of ion-exchanged water. While maintaining the mixed solution thus obtained at 30 ° C. while stirring, an oxidation catalyst solution prepared by dissolving 3 g of ferric sulfate and 10 g of ammonium persulfate in 50 ml of ion-exchanged water was slowly added and stirred for 4 hours. Reacted. The reaction solution thus obtained was treated twice with 100 g each of cation exchange resin and anion exchange resin. Next, the solid content concentration was adjusted by adding ion-exchanged water so that the solid content in the solution was 1%.

3. Production of Conductive Composition (1) Examples <Example 1>
0.08 g of 3,5-dimethyl-1-hexyn-3-ol (equivalent to 0.04 mol per mol of 3,4-dialkoxythiophene) to 1000 g of the conductive polymer obtained in Production Example 3 above In addition, a conductive composition was obtained.
<Example 2>
As shown in Table 1, the conductive composition was obtained in the same manner as in Example 1 except that the acetylene glycol surfactant was replaced with 3,6-dimethyl-4-octyne-3,6-diol. .
<Example 3>
As shown in Table 1, the acetylene glycol surfactant was replaced with 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and the other conditions were the same as in Example 1. A composition was obtained.
<Example 4>
As shown in Table 1, the acetylene glycol surfactant was converted into an ethoxylated 2,4,7,9-tetramethyl-5-decyne-4,7-diol (EO average added mole number: 1.3). Instead, a conductive composition was obtained in the same manner as in Example 1 except for the other conditions.
<Example 5>
As shown in Table 1, the acetylene glycol surfactant was replaced with an ethoxylated product of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (EO average added mole number: 30). Other conditions were the same as in Example 1 to obtain a conductive composition.
<Example 6>
As shown in Table 1, the acetylene glycol surfactant was replaced with 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and the amount added was 3,4-dialkoxythiophene 1 The conductive composition was obtained in the same manner as in Example 1 except that the amount was reduced to 0.004 mol with respect to mol.
<Example 7>
As shown in Table 1, the polystyrene sulfonic acid aqueous solution was increased to 500 g (solid content: 25 g), and the acetylene glycol surfactant was changed to 2,4,7,9-tetramethyl-5-decyne-4,7-diol. Instead, a conductive composition was obtained in the same manner as in Example 1 except for the other conditions.
<Example 8>
As shown in Table 1, the polystyrene sulfonic acid aqueous solution was reduced to 200 g (solid content: 10 g), and the acetylene glycol surfactant was changed to 2,4,7,9-tetramethyl-5-decyne-4,7-diol. Instead, a conductive composition was obtained in the same manner as in Example 1 except for the other conditions.
<Example 9>
As shown in Table 1, the polystyrene sulfonic acid aqueous solution of Production Example 3 was replaced with 300 g (solid content: 15 g) of Mw = 400,000 obtained in Production Example 2, and acetylene glycol surfactants were replaced with 2, 4, In place of 7,9-tetramethyl-5-decyne-4,7-diol, the amount added was reduced to 0.004 mole per mole of 3,4-dialkoxythiophene, and other conditions were as described in Example 1. In the same manner, a conductive composition was obtained.
<Example 10>
As shown in Table 1, the polystyrene sulfonic acid aqueous solution of Production Example 3 was replaced with 300 g (solid content: 15 g) of Mw = 400,000 obtained in Production Example 2, and acetylene glycol surfactants were replaced with 2, 4, A conductive composition was obtained in the same manner as in Example 1 except that 7,9-tetramethyl-5-decyne-4,7-diol was used.

In Table 1 and Table 2 shown later, surfactants A to H are as follows.
A to E: Acetylene glycol surfactant A: 3,5-dimethyl-1-hexyn-3-ol B: 3,6-dimethyl-4-octyne-3,6-diol C: 2,4,7, 9-Tetramethyl-5-decyne-4,7-diol D: Ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (EO average added mole number: 1.3 )
E: Ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (EO average addition mole number: 30)
F, G: Nonionic surfactant F: DKS NL-50 (HLB10.6) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
G: DKS NL-15 (HLB5.0) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
H: Anionic surfactant, New Call 271-A manufactured by Nippon Emulsifier Co., Ltd.

(2) Comparative Example <Comparative Example 1>
As shown in Table 2, a conductive composition was obtained in the same manner as in Example 1 except that no surfactant was added.
<Comparative example 2>
As shown in Table 2, 0.04 mol of DKS NL-50 (HLB10.6) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. is added to 1 mol of 3,4-dialkoxythiophene as a surfactant. A conductive composition was obtained under the same conditions as in Comparative Example 1.
<Comparative Example 3>
As shown in Table 2, as a surfactant, 0.04 mol of DKS NL-15 (HLB5.0) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. is added to 1 mol of 3,4-dialkoxythiophene. A conductive composition was obtained under the same conditions as in Comparative Example 1.
<Comparative example 4>
As shown in Table 2, as a surfactant, 0.04 mol of New Coal 271-A manufactured by Nippon Emulsifier Co., Ltd. was added to 1 mol of 3,4-dialkoxythiophene, and other conditions were compared with Comparative Example 1. Similarly, a conductive composition was obtained.
<Comparative Example 5>
As shown in Table 2, as a surfactant, 0.0004 mol of 2,4,7,9-tetramethyl-5-decyne-4,7-diol per mol of 3,4-dialkoxythiophene was used. A conductive composition was obtained in the same manner as in Comparative Example 1 except that the other conditions were added.
<Comparative Example 6>
As shown in Table 2, as a surfactant, 1.5 mol of 2,4,7,9-tetramethyl-5-decyne-4,7-diol is used per 1 mol of 3,4-dialkoxythiophene. A conductive composition was obtained in the same manner as in Comparative Example 1 except that the other conditions were added.

4). Evaluation Method (1) Method for Measuring Solid Concentration About 1 g of a sample was weighed on an aluminum foil dish, placed in a dryer maintained at 105 to 110 ° C. and heated for 1 hour, then the sample was taken out of the dryer. It was allowed to cool in a desiccator. The weight of the sample after drying was measured, and the solid content concentration was calculated by the following formula.

(2) Conductivity measurement method After adding 5% by mass of dimethyl sulfoxide (DMSO) to each 1% solution, it was coated on glass with a doctor blade, and the coated film was dried in an oven at 150 ° C. to a thickness of about A 1 μm coating film was obtained. The electrical conductivity of the obtained coating film was measured using a Loresta (Mitsubishi Chemical Analytech Co., Ltd. product: Loresta GP MCP-T610). A preferable electric conductivity is 150 S / cm or more.

(3) Measuring method of transmittance The transmittance of the film used for measuring the surface resistance value was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku).

(4) Measuring method of surface resistance value After each 1% solution was diluted with methanol twice, and the above diluted solution was applied on a PET film (Mitsubishi Chemical Corporation, DIAFOIL T680E100) with a # 8 bar coater. Then, it was dried at 100 ° C. for 1 minute using a hot air dryer. The surface resistance value of the obtained film was measured using Hiresta (manufactured by Mitsubishi Chemical Analytech Co., Ltd .: Hiresta UP MCP-HT450) under both conditions of applied voltage of 10V and 500V. A preferred resistance value change magnification (surface resistance value when applied voltage is 500 V / surface resistance value when applied voltage is 10 V) is 10 or less, preferably 5 or less.

5. Evaluation results Tables 1 and 2 show various evaluation results of samples prepared under the conditions of Examples 1 to 10 and Comparative Examples 1 to 6.

  As is clear from comparison between Table 1 and Table 2, the conductive compositions obtained in Examples 1 to 10 were compared with those in Comparative Examples 1 to 6, such as conventional conductivity and transparency. It was found that the conductive composition can suppress an increase in the surface resistance value of the thin film even under a high voltage while maintaining the performance. Therefore, when the electroconductive composition of each Example is used for an antistatic film, it is advantageous in that it can be used for a device having a high voltage.

  The present invention can be effectively used for, for example, an antistatic film, a conductive paint, a solid electrolytic capacitor, a touch screen, an organic LED, an organic EL, a lithium secondary battery, an organic thin film solar battery, and a conductive polymer fiber.

Claims (3)

3,4-dialkoxythiophene represented by the following formula (1)
Wherein R ¹ and R ² are independently of each other hydrogen or a C _1-4 alkyl group, or together form a C _1-4 alkylene group, the alkylene group optionally Which may be substituted) is chemically oxidatively polymerized in an aqueous solvent in the presence of a polyanion to produce a conductive polymer,
In the conductive polymer,
The following formulas (2) and (3)
(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ each represent an alkyl group having 1 to 5 carbon atoms, l and m are positive numbers each having an average of 0 to 25, and l + m is an average of 0 to 40. is there.)
(In the formula, R ⁷ and R ⁸ each represent an alkyl group having 1 to 5 carbon atoms, and n is a positive number having an average of 0 to 25.)
A conductive composition is prepared by blending 0.004 to 0.04 mol of at least one of the acetylene glycol surfactants represented by the formula (1) with respect to 1 mol of the 3,4-dialkoxythiophene.
The manufacturing method of the film which supplies the said electroconductive composition to a base film, removes a volatile component by drying, and forms a coating film. The method for producing a film according to claim 1, wherein the polyanion is used in an amount of 50 to 2000 parts by mass with respect to 100 parts by mass of the 3,4-dialkoxythiophene. The method for producing a film according to claim 1, wherein the polyanion is polystyrene sulfonic acid.