JP6010389B2 - Method for producing conductive polymer, method for producing conductive composition, and method for producing film - Google Patents

Description

  The present invention relates to a conductive polymer that is a complex of poly (3,4-dialkoxythiophene) and a polyanion, a conductive composition containing the same, and a coating using the conductive polymer or the conductive composition. The present invention relates to a film having a membrane.

  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 as described above and a method for producing the same, for example, a method for producing a complex of poly (3,4-dialkoxythiophene) having good water dispersibility and a polyanion is known (for example, (See Patent Document 1). Further, a compound having a functional group selected from the group consisting of a dihydroxy group, a polyhydroxy group, an amide group, and a lactam group is added to an aqueous dispersion of a complex of poly (3,4-dialkoxythiophene) and a polyanion. There is also a report that the conductivity of a thin film formed by adding the obtained coating composition on a substrate can be improved by adding (see, for example, Patent Document 2). Furthermore, when the coating composition containing an aprotic compound having a dielectric constant of ε ≧ 15 is applied to the substrate, the conductivity of the thin film formed by drying at a temperature of less than 100 ° C. can be improved. There is also a report (for example, refer patent document 3).

  In addition, when polymerizing 3,4-dialkoxythiophene in the presence of polyanion, transparency and conductivity can be achieved by using peroxodisulfuric acid as an oxidizing agent or by adding an acid during polymerization to lower the pH. There is also a report that a complex-containing aqueous dispersion capable of forming an excellent thin film can be obtained (see, for example, Patent Document 4). Further, in order to form a thin film excellent in transparency and conductivity, a method of adding a basic organic compound to a π-conjugated conductive polymer in the production of a polymer aqueous dispersion for forming a thin film (for example, Patent Document 5) (See), a method of containing a conductive polymer, water, an organic solvent compatible with the conductive polymer, and carbon dioxide in the pressure vessel, and heating and pressurizing the pressure vessel so that the carbon dioxide is in a supercritical state ( For example, see Patent Document 6), or a method of oxidative polymerization of 3,4-ethylenedioxythiophene (EDOT) in the presence of a high molecular carboxylic acid (for example, see Patent Document 7). Yes.

  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 8). Also known is a method of adding an acetylene glycol surfactant after the production of a conductive polymer (see, for example, Patent Document 9 and Patent Document 10). Furthermore, a monomer that can be a conductive polymer such as 3,4-ethylenedioxythiophene is added to an aqueous solution containing a dopant such as benzenesulfonic acid, and emulsified using a nonionic surfactant such as an acetylene glycol derivative. A method is also known in which a conductive polymer is synthesized by chemical oxidative polymerization using an oxidizing agent in an emulsified liquid (see, for example, Patent Document 11). Further, it has been reported that when the amount of the polyanion is twice or less than that of ethylenedioxythiophene, the conductivity of the conductive polymer is lowered (for example, see Non-Patent Document 1).

JP-A-7-090060 JP-A-8-048858 JP 2000-153229 A JP 2004-059666 A JP 2007-254730 A JP 2009-215422 A JP 2011-093993 A JP 2009-245935 A Japanese Patent Laid-Open No. 6-049246 JP 2005-527048 A JP 2011-153224 A

Material properties and device application of PEDOT (Science & Technology, published on March 5, 2012)

  However, the above known techniques have the following problems. The technique described in Patent Document 1 is sufficient for the antistatic function, but is insufficient for enhancing transparency and conductivity. With the techniques described in Patent Documents 2 to 7, although the conductivity of the thin film can be improved to some extent, the level of conductivity required by the market cannot be achieved.

  As in the techniques described in Patent Documents 8 to 10, when a surfactant is added afterwards in the conductive paint, depending on the type and amount of the surfactant to be added, the conductivity of the thin film is lowered, and sufficient performance is obtained. Cannot be obtained. Further, as in the technique described in Patent Document 9, when a sufficient amount of surfactant is present to emulsify the monomer, the conductivity of the thin film is lowered, and this also provides sufficient performance. Disappear. In addition, about the addition amount of the polyanion of a nonpatent literature 1, it is with respect to the conventional manufacturing technique, and the restriction | limiting of this addition amount is not necessarily correct.

  The present invention has been made to solve the above-described problems, and an object thereof is to greatly improve the conductivity of a formed thin film while maintaining the performance of a conventional conductive polymer.

  As a result of intensive studies to achieve the above object, the inventors of the present invention chemically synthesized 3,4-dialkoxythiophene in an aqueous solvent in the presence of a polyanion and a specific acetylene glycol surfactant. It has been found that by conducting selective oxidative polymerization, the conductivity of the thin film can be greatly improved, and the present invention has been completed. In this invention, even if the quantity of polyanion becomes 2 times or less of the quantity of 3, 4- dialkoxy thiophene, the high electroconductivity which can endure practically can be exhibited. The specific solution in the present invention is as follows.

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 May be substituted.)
A polyanion; and
The following formulas (2) and (3)
^(Wherein, shows the ^{R 3, R 4, R 5} , R 6, R 7, R 8 are each an alkyl group having 1 to 5 carbon atoms.)
A conductive polymer obtained by chemical oxidative polymerization in an aqueous solvent in the presence of at least one of the acetylene glycol surfactants represented by the formula: The conductive polymer is 0.001 to 0.5 mol per 1 mol of alkoxythiophene.

  Another embodiment of the present invention is a conductive polymer obtained by further using 10 to 300 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 polymer in which the polyanion is polystyrene sulfonic acid.

  One embodiment of the present invention is a conductive composition containing any of the above-described conductive polymers.

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

  According to the present invention, the conductivity of the thin film can be greatly improved.

  Hereinafter, preferred embodiments of a film having a conductive polymer, a conductive composition, and a coating film according to the present invention will be described.

1. Conductive polymer and method for producing the same The conductive polymer 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 May be substituted.)
A polyanion; and
The following formulas (2) and (3)
(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent an alkyl group having 1 to 5 carbon atoms), at least one of acetylene glycol surfactants represented by Is a conductive polymer obtained by chemical oxidative polymerization in an aqueous solvent, wherein the acetylene glycol surfactant is 0.001 to 0.5 mol per mol of 3,4-dialkoxythiophene. It is.

  Materials essential for manufacturing the conductive polymer according to this embodiment are the following (1) to (5).

(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 polyanion used is preferably 10 to 300 parts by weight, more preferably 50 to 250 parts by weight, and more preferably 100 to 200 parts by weight with respect to 100 parts by weight of 3,4-dialkoxythiophene. is there. By using 10 parts by mass or more of 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 expressed. When 300 parts by mass or less is used, the surface resistance value is suppressed by not adding an excessive amount of polyanion, and the maintenance of the conductive performance can be expected. In particular, the amount of polyanion that is generally said to decrease in electrical conductivity, that is, the condition that the polyanion is 200 parts by mass or less, which corresponds to twice the amount of 100 parts by mass of 3,4-dialkoxythiophene, is sufficient. Performance can be demonstrated. Moreover, by reducing the ratio of the polyanion, the hygroscopicity derived from the polyanion can be reduced, and the corrosiveness to the metal by the polyanion can be reduced.

(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 and a specific acetylene glycol surfactant, 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) Acetylene glycol-based surfactant In the embodiment of the present invention, as the acetylene glycol-based surfactant, at least one of those represented by the following formulas (2) and (3) is used.

^(Wherein, shows the ^{R 3, R 4, R 5} , R 6, R 7, R 8 are each an alkyl group having 1 to 5 carbon atoms.)

  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, Preferred examples include 5,8,11-tetramethyl-6-dodecin-5,8-diol and 3,5-dimethyl-1-hexyn-3-ol. The amount of the acetylene glycol surfactant used is preferably 0.001 to 0.5 mol, more preferably 0.005 to 0.1 mol, and more preferably 1 mol of 3,4-dialkoxythiophene. Preferably it is 0.01-0.06 mol. By using the acetylene glycol surfactant in the range of 0.001 to 0.5 mol with respect to 1 mol of 3,4-dialkoxythiophene, the conductivity when formed into a coating film can be maintained high.

(5) 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.

(6) Manufacturing method of conductive polymer The conductive polymer which concerns on this Embodiment can be manufactured with the following method, for example. First, a polyanion is dispersed or dissolved in an aqueous solvent, and 3,4-dialkoxythiophene and acetylene glycol surfactant as precursor monomers are 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 method for producing the same The conductive composition according to this embodiment refers to a liquid or solid containing the above-described conductive polymer. In the conductive composition, a water-miscible organic solvent, a conductivity improver, a binder resin, and the like can be mixed with the above-described conductive polymer. 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.

(1) Water-miscible organic solvent The water-miscible organic solvent as one component of the conductive composition is the same as the water-miscible organic solvent that can be mixed with the aqueous solvent used in the production of the conductive polymer described above. You can choose from types. 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) Conductivity improver One or more conductivity improvers selected from the following compounds (2a) to (2h) in order to further improve the conductivity of the conductive coating film during the production of the conductive polymer. Is preferably added.
(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.

(4) Others Other components that can be included in the conductive composition include, for example, a filler, a crosslinking agent, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a surface modifier, a defoaming agent, a plasticizer, and an antibacterial agent. Preferable examples include agents, surfactants, 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 Manufacturing Method Thereof The conductive polymer or conductive composition according to this embodiment can be used for a film having a coating film formed thereon. The conductive polymer or the conductive composition not only exhibits excellent conductivity, but also retains performance such as transparency and high heat resistance with little decrease in conductivity due to standing at high temperatures. From this, the conductive polymer or 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, It can also be used for conductive polymer fibers.

  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 polymer or the conductive composition as a conductor, after applying a dispersion of the conductive polymer or conductive composition to the base film, or A film having a coating film can be obtained by immersing the base film in the dispersion and then 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 dispersion 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. Method, kneader coating method and the like. 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 dispersion of the conductive polymer or the conductive composition is not particularly limited and is appropriately selected depending on the purpose. For example, it can be suitably set in the range of 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 mass parts and 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. Production of Conductive Polymer (1) Examples Tables 1 to 4 collectively show the production conditions of each example and the evaluation results after film formation.
<Example 1>
5 g of 3,4-ethylenedioxythiophene (EDOT) and a solution of 100 g (solid content: 5 g) of the polystyrenesulfonic acid aqueous solution obtained in Production Example 1 in 1000 ml of ion-exchanged water, 0.25 g 2,4,7,9-Tetramethyl-5-decyne-4,7-diol (a kind of acetylene glycol surfactant) was mixed (equivalent to 0.06 mol with respect to 1 mol of EDOT). Next, while keeping the mixed solution 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 is slowly added and stirred for 4 hours. And reacted. The reaction solution thus obtained was treated twice with 100 g each of cation exchange resin and anion exchange resin, and then ion exchange water was added so that the solid content in the solution was 1%. The solid content concentration of the conductive polymer was adjusted.
<Example 2>
As shown in Table 1, the acetylene glycol surfactant was replaced with 3,6-dimethyl-4-octyne-3,6-diol, and a solution having a solid content of 1% was prepared in the same manner as in Example 1 except for the other conditions. Obtained.
<Example 3>
As shown in Table 1, the acetylene glycol surfactant was replaced with 3,5-dimethyl-1-hexyn-3-ol, and other conditions were obtained in the same manner as in Example 1 to obtain a solution having a solid content of 1%. .
<Example 4>
As shown in Table 1, the polystyrene sulfonic acid aqueous solution was increased to 150 g, and the other conditions were the same as in Example 1 to obtain a solution having a solid content of 1%.
<Example 5>
As shown in Table 1, the polystyrene sulfonic acid aqueous solution was increased to 150 g, the acetylene glycol surfactant was replaced with 3,6-dimethyl-4-octyne-3,6-diol, and other conditions were the same as in Example 1. To obtain a 1% solids solution.
<Example 6>
As shown in Table 1, the polystyrene sulfonic acid aqueous solution was increased to 150 g, the acetylene glycol surfactant was replaced with 3,5-dimethyl-1-hexyn-3-ol, and other conditions were the same as in Example 1. A 1% solids solution was obtained.
<Example 7>
As shown in Table 2, the polystyrene sulfonic acid aqueous solution was increased to 200 g, and the other conditions were the same as in Example 1 to obtain a solution having a solid content of 1%.
<Example 8>
As shown in Table 2, the polystyrene sulfonic acid aqueous solution was increased to 200 g, the acetylene glycol surfactant was replaced with 3,6-dimethyl-4-octyne-3,6-diol, and other conditions were the same as in Example 1. To obtain a 1% solids solution.
<Example 9>
As shown in Table 2, the polystyrene sulfonic acid aqueous solution was increased to 200 g, the acetylene glycol surfactant was replaced with 3,5-dimethyl-1-hexyn-3-ol, and other conditions were the same as in Example 1. A 1% solids solution was obtained.
<Example 10>
As shown in Table 2, the acetylene glycol surfactant was reduced to 0.01 mol with respect to 1 mol of EDOT, and the other conditions were the same as in Example 1 to obtain a solution having a solid content of 1%.
<Example 11>
As shown in Table 2, the acetylene glycol surfactant was replaced with 3,6-dimethyl-4-octyne-3,6-diol and reduced to 0.01 mol with respect to 1 mol of EDOT, and other conditions were carried out. In the same manner as in Example 1, a solution having a solid content of 1% was obtained.
<Example 12>
As shown in Table 2, the acetylene glycol surfactant was replaced with 3,5-dimethyl-1-hexyn-3-ol and reduced to 0.01 mol with respect to 1 mol of EDOT. In the same manner, a solution having a solid content of 1% was obtained.
<Example 13>
As shown in Table 3, the polystyrene sulfonic acid aqueous solution was increased to 200 g, the acetylene glycol surfactant was reduced to 0.01 mol with respect to 1 mol of EDOT, and the other conditions were the same as in Example 1 with a solid content of 1%. Solution was obtained.
<Example 14>
As shown in Table 3, the polystyrene sulfonic acid aqueous solution was increased to 200 g, the acetylene glycol surfactant was replaced with 3,6-dimethyl-4-octyne-3,6-diol, and 0.01 mol per 1 mol of EDOT. A solution having a solid content of 1% was obtained in the same manner as in Example 1 except that the number of moles was reduced.
<Example 15>
As shown in Table 3, the polystyrene sulfonic acid aqueous solution was increased to 200 g, the acetylene glycol surfactant was replaced with 3,5-dimethyl-1-hexyn-3-ol, and 0.01 mol relative to 1 mol of EDOT. A solution having a solid content of 1% was obtained in the same manner as in Example 1 except for the above.
<Example 16>
As shown in Table 3, the polystyrene sulfonic acid aqueous solution was replaced with the one having Mw = 400,000 obtained in Production Example 2 and increased to 150 g, and the acetylene glycol surfactant was reduced to 0.01 mol with respect to 1 mol of EDOT. A solution having a solid content of 1% was obtained in the same manner as in Example 1 under the other conditions.
<Example 17>
As shown in Table 3, the polystyrene sulfonic acid aqueous solution was replaced with the Mw = 400,000 obtained in Production Example 2 and increased to 150 g, and the acetylene glycol surfactant was changed to 3,6-dimethyl-4-octyne-3. , 6-diol, and reduced to 0.01 mol with respect to 1 mol of EDOT, and the other conditions were the same as in Example 1 to obtain a solution having a solid content of 1%.
<Example 18>
As shown in Table 3, the polystyrene sulfonic acid aqueous solution was replaced with the Mw = 400,000 obtained in Production Example 2 and increased to 150 g, and the acetylene glycol surfactant was changed to 3,5-dimethyl-1-hexyne-3. -It replaced with oar and reduced to 0.01 mol with respect to 1 mol of EDOT, and the other conditions were carried out similarly to Example 1, and obtained the solution of 1% of solid content.
<Example 19>
As shown in Table 4, the polystyrene sulfonic acid aqueous solution was replaced with the one having Mw = 400,000 obtained in Production Example 2, and the acetylene glycol surfactant was reduced to 0.01 mol with respect to 1 mol of EDOT, and other conditions were changed. A solution having a solid content of 1% was obtained in the same manner as in Example 1.
<Example 20>
As shown in Table 4, the polystyrene sulfonic acid aqueous solution was replaced with the one having Mw = 400,000 obtained in Production Example 2, and the acetylene glycol surfactant was changed to 3,6-dimethyl-4-octyne-3,6-diol. The solution was reduced to 0.01 mol with respect to 1 mol of EDOT.
<Example 21>
As shown in Table 4, the polystyrene sulfonic acid aqueous solution was replaced with the one having Mw = 400,000 obtained in Production Example 2, and the acetylene glycol surfactant was replaced with 3,5-dimethyl-1-hexyn-3-ol. And it reduced to 0.01 mol with respect to 1 mol of EDOT, and other conditions were carried out similarly to Example 1, and obtained the solution of 1% of solid content.

In Tables 1 to 4 and Table 5 described later, surfactants A to C are as follows.
A to C: Acetylene glycol surfactant A: 2,4,7,9-tetramethyl-5-decyne-4,7-diol B: 3,6-dimethyl-4-octyne-3,6-diol C : 3,5-dimethyl-1-hexyn-3-ol

(2) Comparative Example Table 5 summarizes the manufacturing conditions of each comparative example and the evaluation results after film formation.
<Comparative Example 1>
5 g of 3,4-ethylenedioxythiophene (EDOT) was mixed with a solution obtained by dissolving 200 g (solid content: 10 g) of the polystyrenesulfonic acid aqueous solution obtained in Production Example 1 in 1000 ml of ion-exchanged water. Subsequent steps were performed in the same manner as in Example 1.
<Comparative example 2>
As shown in Table 5, the polystyrenesulfonic acid aqueous solution was reduced to 100 g, and the other conditions were the same as in Comparative Example 1 to obtain a solution having a solid content of 1%.
<Comparative Example 3>
As shown in Table 5, 0.05 g of 2,4,7,9-tetramethyl-5-decyne-4,7-diol was added to 300 g of the sample prepared in Comparative Example 1 (0.06 with respect to 1 mol of EDOT). In addition, stirring was performed for 30 minutes to obtain a sample for evaluation.
<Comparative example 4>
As shown in Table 5, the acetylene glycol surfactant was reduced to 0.0005 mol with respect to 1 mol of EDOT, and the other conditions were the same as in Example 1 to obtain a solution having a solid content of 1%.
<Comparative Example 5>
As shown in Table 5, the acetylene glycol surfactant was increased to 0.6 mol with respect to 1 mol of EDOT, and the other conditions were the same as in Example 1 to obtain a solution having a solid content of 1%.

3. 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).

(3) Heat resistance measurement method Formula: Heat resistance (%) = (initial conductivity-conductivity after heat treatment) x 100 / initial conductivity Conductivity measurement sample is heated at 150 ° C for 40 hours The electrical conductivity after the heat treatment was measured using a Loresta (Mitsubishi Chemical Analytech Co., Ltd .: Loresta GP MCP-T610). The heat resistance was calculated by the above formula.

(4) Method for measuring surface resistance value After adding 5% by mass of dimethyl sulfoxide (DMSO) to each 1% solution, the solution was diluted with methanol and diluted to a double amount on a PET film (manufactured by Mitsubishi Chemical Corporation, DIAFOIL T680E100). After the diluted liquid was applied with an 8 bar coater, 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 Loresta (Mitsubishi Chemical Analytech Co., Ltd .: Loresta GP MCP-T610).

(5) 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). Evaluation results Tables 1 to 5 show various evaluation results of samples prepared under the conditions of Examples 1 to 21 and Comparative Examples 1 to 5.

  As is clear from the evaluation results in Tables 1 to 5, the coating films formed from the conductive compositions obtained in Examples 1 to 21 were compared with those obtained in Comparative Examples 1 to 5, and the surface relative to the transmittance. The resistance value was low. That is, by using the conductive polymer produced in each example, it was possible to obtain a coating film in which the contradictory performances of improvement in transmittance and reduction in surface resistance value were compatible.

  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 (5)

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 May be substituted.)
A polyanion; and
The following formulas (2) and (3)
^(Wherein, shows the ^{R 3, R 4, R 5} , R 6, R 7, R 8 are each an alkyl group having 1 to 5 carbon atoms.)
In at least one presence of acetylene glycol surfactant represented, in an aqueous solvent to chemical oxidation polymerization, the upper Symbol acetylene glycol surfactant in the 3,4-dialkoxythiophene 1 mole The manufacturing method of the conductive polymer made into 0.001-0.5 mol with respect to. The method for producing a conductive polymer according to claim 1, wherein the polyanion is used in an amount of 10 to 300 parts by mass with respect to 100 parts by mass of the 3,4-dialkoxythiophene. The method for producing a conductive polymer according to claim 1, wherein the polyanion is polystyrene sulfonic acid. Method for producing a conductive composition a conductive polymer obtained by the production method of the conductive polymer according to any one of claims 1 to 3 for producing a are dispersed in a liquid conductive composition . Obtained conductive obtained by the production method of the conductive composition according to the conductive polymer or Claim 4 obtained by the method for producing a conductive polymer according to any one of claims 1 to 3 A method for producing a film in which a composition is supplied to a base film and volatile components are removed by drying to form a coating film .