JP2008045061A - Electroconductive solid matter, method for producing the same, and electroconductive polymer solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroconductive solid matter dissolvable in an organic solvent in high concentration; to provide a method for producing the solid matter; and to provide an electroconductive polymer solution enabling a drying time for forming a coated film to be shorten, obtained by using a π-conjugated electroconductive polymer compatible with a hydrophobic resin, and capable of providing an electroconductive coated film having high electroconductivity. <P>SOLUTION: The electroconductive solid matter contains the π-conjugated electroconductive polymer and a soluble polymer having an anion group or an electron-withdrawing group, and an amine compound is coordinated to or bonded to the anionic group or the electron-withdrawing group. The method for producing the electroconductive solid matter includes preparing an electroconductive aqueous solution by polymerizing a precursor monomer of the π-conjugated electroconductive polymer in water in the presence of a soluble polymer, and adding the amine compound to the electroconductive aqueous polymer solution. The electroconductive polymer solution is obtained by dissolving the electroconductive solid matter in an organic solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a conductive solid containing a π-conjugated conductive polymer, a production method for producing the conductive solid, and a conductive material in which the π-conjugated conductive polymer is dissolved in an organic solvent. The present invention relates to a polymer solution.

Generally, a π-conjugated conductive polymer whose main chain is composed of a conjugated system containing π electrons is synthesized by an electrolytic polymerization method and a chemical oxidative polymerization method.
In the electropolymerization method, a support such as a previously formed electrode material is immersed in a mixed solution of an electrolyte serving as a dopant and a precursor monomer that forms a π-conjugated conductive polymer, and the π-conjugated system is formed on the support. A conductive polymer is formed into a film. Therefore, it is difficult to manufacture in large quantities.
On the other hand, in the chemical oxidation polymerization method, there is no such limitation, an oxidizing agent and an oxidation polymerization catalyst are added to the precursor monomer of the π-conjugated conductive polymer, and a large amount of π-conjugated conductive polymer is added in the solution. Can be manufactured.
However, in the chemical oxidative polymerization method, as the conjugated system of the π-conjugated conductive polymer main chain grows, the solubility in a solvent becomes poor, so that an insoluble solid powder can be obtained. If it is insoluble, it becomes difficult to uniformly form a π-conjugated conductive polymer film on various substrates such as a plastic sheet by coating.

Therefore, a method of solubilizing by introducing a functional group into a π-conjugated conductive polymer, a method of dispersing and solubilizing in a binder resin, and a method of solubilizing by adding an anionic group-containing polymer acid have been tried. Yes.
For example, in order to improve the solubility in water, 3,4-dialkoxythiophene is used using an oxidizing agent in the presence of polystyrene sulfonic acid, which is an anionic group-containing polymer acid having a molecular weight in the range of 2000 to 500,000. Has been proposed to produce a poly (3,4-dialkoxythiophene) aqueous solution by chemical oxidative polymerization (see Patent Document 1). In addition, a method of producing a π-conjugated conductive polymer colloid aqueous solution by chemical oxidative polymerization in the presence of polyacrylic acid has been proposed (see Patent Document 2).
Japanese Patent No. 2636968 Japanese Patent Laid-Open No. 7-165892

As described above, the conductive polymer solution including the π-conjugated conductive polymer that has been proposed so far is an aqueous solution, but the drying time becomes longer when the aqueous solution is applied to form a coating film. For this reason, the productivity of the conductive coating film was low. Therefore, there is a demand for a conductive polymer solution in which a π-conjugated conductive polymer is dissolved in an organic solvent.
As a method for obtaining a conductive polymer solution in which a π-conjugated conductive polymer is dissolved in an organic solvent, a method of adding an alcohol to an aqueous solution of a π-conjugated conductive polymer can be considered. However, when alcohol is added, the concentration of the π-conjugated conductive polymer decreases, so that when the conductive coating film is formed from the conductive polymer solution, the drying time tends to be long. Therefore, in order to increase the concentration of the π-conjugated conductive polymer, it may be possible to remove water and an organic solvent with an evaporator or the like. In this conductive polymer solution, the concentration of the π-conjugated conductive polymer is increased. Then, the π-conjugated conductive polymer tends to separate and precipitate or gel.
In addition, in the conventional conductive polymer solution, since the π-conjugated conductive polymer is water-soluble, the compatibility between the π-conjugated conductive polymer and a hydrophobic resin such as a hard coat resin is low, and the conductive The application development of the functional polymer solution was limited.
This invention is made | formed in view of the said situation, and it aims at providing the electroconductive solid substance which can be melt | dissolved in an organic solvent at high concentration, and its manufacturing method. Furthermore, a conductive polymer solution capable of shortening the drying time for forming the coating film and forming a highly conductive conductive coating film that is easily compatible with the π-conjugated conductive polymer and the hydrophobic resin. The purpose is to provide.

The present invention includes the following configurations.
[1] A π-conjugated conductive polymer and a solubilized polymer having an anion group or an electron withdrawing group,
A conductive solid, wherein an amine compound is coordinated or bonded to an anion group or electron withdrawing group of a solubilized polymer.
[2] Preparing an aqueous conductive polymer solution by polymerizing a precursor monomer of a π-conjugated conductive polymer in water in the presence of a solubilized polymer, and adding an amine compound to the aqueous conductive polymer solution The manufacturing method of the electroconductive solid substance characterized by these.
[3] A conductive polymer solution, wherein the conductive solid material according to [1] is dissolved in an organic solvent.
[4] The conductive polymer solution according to [3], which contains a binder resin.

The conductive solid of the present invention can be dissolved in an organic solvent at a high concentration. In addition, since the conductive solid of the present invention does not need to store the π-conjugated conductive polymer in the form of an aqueous solution, it has excellent storage stability and can reduce the weight during transportation.
According to the method for producing a conductive solid of the present invention, a conductive solid that can be dissolved in an organic solvent at a high concentration can be easily produced.
The conductive polymer solution of the present invention can shorten the drying time of the coating film formation, and the π-conjugated conductive polymer is easily compatible with the hydrophobic resin and forms a highly conductive coating film. it can.

<Conductive solids>
The conductive solid of the present invention contains a π-conjugated conductive polymer and a solubilized polymer having an anion group or an electron withdrawing group, and an amine compound is contained in the anion group or electron withdrawing group of the solubilized polymer. Coordinated.

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer can be used as long as the main chain is an organic polymer having a π-conjugated system. Examples thereof include polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of easy polymerization and stability in air, polypyrroles, polythiophenes and polyanilines are preferred.
Even if the π-conjugated conductive polymer remains unsubstituted, sufficient conductivity and compatibility with the binder can be obtained, but in order to further improve conductivity and dispersibility or solubility in the binder, It is preferable to introduce a functional group such as a group, a carboxyl group, a sulfo group, an alkoxyl group, a hydroxyl group, or a cyano group into the π-conjugated conductive polymer.

  Specific examples of such π-conjugated conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), and poly (3-n-propylpyrrole). ), Poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4 Dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), Poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly 3-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), poly (thiophene), poly (3-methylthiophene), poly (3- Ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene) ), Poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), Poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-di Butylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyl) Oxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), Poly (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyl) Oxythiophene), poly (3,4-diheptyloxythiophene), poly 3,4-dioctyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4 -Propylene dioxythiophene), poly (3,4-butenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene) , Poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene), polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), poly (3-anilinesulfonic acid) And the like.

Among them, from one or two kinds selected from polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene), poly (3-methoxythiophene), and poly (3,4-ethylenedioxythiophene). The (co) polymer is preferably used from the viewpoints of resistance and reactivity. Furthermore, polypyrrole and poly (3,4-ethylenedioxythiophene) are more preferable because they have higher conductivity and improved heat resistance.
In addition, alkyl-substituted compounds such as poly (N-methylpyrrole) and poly (3-methylthiophene) are more preferable because they improve solvent solubility and compatibility and dispersibility when a hydrophobic resin is added. Among the alkyl groups, a methyl group is preferred because it does not adversely affect the conductivity.
Furthermore, poly (3,4-ethylenedioxythiophene) doped with polystyrene sulfonic acid (abbreviated as PEDOT-PSS) has relatively high thermal stability and low polymerization degree, and thus has transparency after coating film formation. This is preferable because it is advantageous.

(Solubilized polymer)
The solubilized polymer is a polymer that solubilizes the π-conjugated conductive polymer, and examples of the solubilized polymer include polymers having an anion group and / or an electron withdrawing group.

[Polymer having anionic group]
Polymers having an anionic group (hereinafter referred to as polyanions) are substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted Polyester and a copolymer thereof, which have a structural unit having at least an anionic group.
The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.

  A polyalkylene is a polymer whose main chain is composed of repeating methylenes. Examples of the polyalkylene include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly (3,3,3-trifluoropropylene), polyacrylonitrile, polyacrylate, polystyrene, and the like.

Polyalkenylene is a polymer composed of structural units containing one or more unsaturated bonds (vinyl groups) in the main chain. Specific examples of polyalkenylene include propenylene, 1-methylpropenylene, 1-butylpropenylene, 1-decylpropenylene, 1-cyanopropenylene, 1-phenylpropenylene, 1-hydroxypropenylene, 1-butenylene, 1-methyl-1-butenylene, 1-ethyl-1-butenylene, 1-octyl-1-butenylene, 1-pentadecyl-1-butenylene, 2-methyl-1-butenylene, 2-ethyl-1-butenylene, 2- Butyl-1-butenylene, 2-hexyl-1-butenylene, 2-octyl-1-butenylene, 2-decyl-1-butenylene, 2-dodecyl-1-butenylene, 2-phenyl-1-butenylene, 2-butenylene, 1-methyl-2-butenylene, 1-ethyl-2-butenylene, 1-octyl-2-butenylene 1-pentadecyl-2-butenylene, 2-methyl-2-butenylene, 2-ethyl-2-butenylene, 2-butyl-2-butenylene, 2-hexyl-2-butenylene, 2-octyl-2-butenylene, 2- Decyl-2-butenylene, 2-dodecyl-2-butenylene, 2-phenyl-2-butenylene, 2-propylenephenyl-2-butenylene, 3-methyl-2-butenylene, 3-ethyl-2-butenylene, 3-butyl 2-butenylene, 3-hexyl-2-butenylene, 3-octyl-2-butenylene, 3-decyl-2-butenylene, 3-dodecyl-2-butenylene, 3-phenyl-2-butenylene, 3-propylenephenyl- 2-butenylene, 2-pentenylene, 4-propyl-2-pentenylene, 4-butyl-2-pentenylene, 4-he Selected from sil-2-pentenylene, 4-cyano-2-pentenylene, 3-methyl-2-pentenylene, 4-ethyl-2-pentenylene, 3-phenyl-2-pentenylene, 4-hydroxy-2-pentenylene, hexenylene, etc. And a polymer containing one or more structural units.
Among these, substituted or unsubstituted butenylene is preferable because of the interaction between the unsaturated bond and the π-conjugated conductive polymer and the ease of synthesis using substituted or unsubstituted butadiene as a starting material.

As polyimide, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-tetracarboxydiphenyl ether dianhydride, 2,2 ′-[ And a polyimide comprising an anhydride such as 4,4′-di (dicarboxyphenyloxy) phenyl] propane dianhydride and a diamine such as oxydiamine, paraphenylenediamine, metaphenylenediamine, and benzophenonediamine.
Examples of the polyamide include polyamide 6, polyamide 6,6, polyamide 6,10 and the like.
Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate.

When the polyanion has a substituent, examples of the substituent include an alkyl group, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a phenyl group, a phenol group, an ester group, and an alkoxyl group. In view of solubility in a solvent, heat resistance, compatibility with a resin, and the like, an alkyl group, a hydroxyl group, a phenol group, and an ester group are preferable.
Alkyl groups can increase solubility and dispersibility in polar or nonpolar solvents, compatibility and dispersibility in resins, etc., and hydroxyl groups form hydrogen bonds with other hydrogen atoms and the like. It can be made easy, and the solubility in an organic solvent, the compatibility with a resin, the dispersibility, and the adhesiveness can be increased. In addition, the cyano group and the hydroxyphenyl group can increase the compatibility and solubility in the polar resin, and can also increase the heat resistance.
Among the above substituents, an alkyl group, a hydroxyl group, an ester group, and a cyano group are preferable.

  The anion group of the polyanion may be a functional group that can cause chemical oxidation doping to the conjugated conductive polymer. Among these, from the viewpoint of ease of production and stability, a monosubstituted sulfate group, A substituted phosphate group, a phosphate group, a carboxyl group, a sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxyl group are more preferable.

Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene sulfonic acid, polyvinyl Examples thereof include carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly (2-acrylamido-2-methylpropane carboxylic acid), polyisoprene carboxylic acid, polyacrylic acid and the like. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
Of these, polyacrylsulfonic acid and polymethacrylsulfonic acid are preferred. Polyacrylsulfonic acid and polymethacrylsulfonic acid are excellent in heat resistance and environmental resistance because thermal decomposition of the π-conjugated conductive polymer component is relaxed by absorbing thermal energy and decomposing by itself. Furthermore, since it has an ester group, it is excellent in compatibility with the binder and dispersibility.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

[Polymer having electron withdrawing group]
The polymer having an electron withdrawing group includes, for example, a polymer having as a structural unit a compound having at least one selected from a cyano group, a nitro group, a formyl group, a carbonyl group, and an acetyl group. Among these, a cyano group is preferable because it has high polarity and can solubilize a π-conjugated conductive polymer. Moreover, since compatibility with a binder and dispersibility can be made higher, it is preferable.
Specific examples of the polymer having an electron withdrawing group include polyacrylonitrile, polymethacrylonitrile, acrylonitrile-styrene resin, acrylonitrile-butadiene resin, acrylonitrile-butadiene-styrene resin, and hydroxyl group or amino group-containing resin. Resin (for example, cyanoethyl cellulose), polyvinyl pyrrolidone, alkylated polyvinyl pyrrolidone, nitrocellulose and the like.

  To the solubilized polymer, a synthetic rubber for improving impact resistance, an anti-aging agent, an antioxidant, and an ultraviolet absorber for improving environmental resistance characteristics may be added in advance. However, amine compound antioxidants may interfere with the action of the oxidizer used when polymerizing the above conductive polymer, so the antioxidant may be phenolic or mixed after polymerization. It is necessary to take measures such as

  The content of the solubilized polymer is preferably in the range of 0.1 to 10 mol, more preferably in the range of 1 to 7 mol, with respect to 1 mol of the π-conjugated conductive polymer. When the content of the solubilized polymer is less than 0.1 mol, the doping effect on the π-conjugated conductive polymer tends to be weak, and the conductivity may be insufficient. In addition, the solubility in a solvent becomes low, and it becomes difficult to obtain a uniform conductive polymer solution. On the other hand, when the content of the solubilized polymer is more than 10 mol, the content ratio of the π-conjugated conductive polymer decreases, and it is difficult to obtain sufficient conductivity.

(Amine compound)
The amine compound is not particularly limited as long as it is coordinated or bonded to the anion group or electron withdrawing group of the solubilized polymer. Here, the coordination or bond is a bond form in which the intermolecular distance is shortened when the solubilized polymer and the amine compound donate / accept electrons to each other.
Examples of amine compounds include primary amines, secondary amines, tertiary amines, and aromatic amines.
Specifically, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, undecylamine, dodecylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine , Dipentylamine, dihexylamine, diheptylamine, dioctylamine, didecylamine, diundecylamine, didodecylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine , Tridecylamine, triundecylamine, tridodecylamine, imidazole, N-methyl-imidazole, N-ethyl-imidazo N-propyl-imidazole, N-butyl-imidazole, N-pentyl-imidazole, N-hexyl-imidazole, N-heptyl-imidazole, N-octyl-imidazole, N-decyl-imidazole, N-undecyl-imidazole, N-dodecyl-imidazole, 2-heptyl-imidazole, pyridine and the like can be mentioned.
The molecular weight of the amine compound is preferably 50 to 2000 in consideration of solubility in an organic solvent.

The amount of the amine compound is preferably 0.1 to 10 molar equivalents relative to the anion group and electron withdrawing group of the solubilized polymer that does not contribute to the doping of the π-conjugated conductive polymer, More preferably, it is -2.0 equivalent, and it is especially preferable that it is 0.85-1.25 equivalent.
When the amount of the amine compound is equal to or more than the lower limit, the amine compound is coordinated to almost all of the anion group and the electron withdrawing group of the solubilized polymer, so that the solubility in an organic solvent becomes higher. Moreover, if it is below the said upper limit, since an excess amine compound is not contained in a conductive polymer solution, the fall of the electroconductivity and mechanical property of the conductive film obtained can be prevented.

  In the conductive solid described above, since the amine compound is coordinated or bonded to the anion group or electron withdrawing group of the solubilized polymer, the hydrophilicity of the solubilized polymer is lost and the lipophilic property is lost. Yes. Therefore, this conductive solid can be dissolved in an organic solvent at a high concentration.

<Method for producing conductive solid>
The method for producing a conductive solid of the present invention comprises preparing a conductive polymer aqueous solution by polymerizing a π-conjugated conductive polymer precursor monomer in water in the presence of a solubilized polymer. In this method, an amine compound is added to the molecular aqueous solution.

  Specific examples of the precursor monomer of the π-conjugated conductive polymer include pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, and 3-octylpyrrole. 3-decylpyrrole, 3-dodecylpyrrole, 3,4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3 -Methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, 3-methyl-4 -Hexyloxypyrrole, thiophene, 3-methylthiophene, -Ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3 -Chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3- Butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3-octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4 -Dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxy Thiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxythiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4- Butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl -4-carboxybutylthiophene, aniline 2-methylaniline, 3-isobutyl aniline, 2-aniline sulfonic acid, and 3-aniline sulfonic acid.

  Examples of the oxidizing agent and oxidation catalyst used in the polymerization of the precursor monomer include ammonium peroxodisulfate (ammonium persulfate), sodium peroxodisulfate (sodium persulfate), potassium peroxodisulfate (potassium persulfate), and the like. Peroxodisulfate, transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, cupric chloride, metal halides such as boron trifluoride, metals such as silver oxide and cesium oxide Examples thereof include oxides, peroxides such as hydrogen peroxide and ozone, organic peroxides such as benzoyl peroxide, and oxygen.

  The amount of the amine compound added when the amine compound is added to the aqueous conductive polymer solution is the same as the amount of the amine compound in the conductive solid.

By adding an amine compound to the aqueous conductive polymer solution, the amine compound is coordinated or bonded to the anion group or electron withdrawing group of the solubilized polymer to convert hydrophilicity to lipophilicity. And the π-conjugated conductive polymer coordinated therewith do not dissolve in water, and a conductive solid can be obtained. Since this manufacturing method does not require complicated operations, a conductive solid that can be dissolved in an organic solvent at a high concentration can be easily obtained.
Usually, the obtained conductive solid is recovered from water. Examples of the method for recovering the conductive solid include a method of removing water and solvent using an evaporator, and a method of removing water and solvent by heating.

<Conductive polymer solution>
The conductive polymer solution of the present invention is a solution in which the above-described conductive solid is dissolved in an organic solvent.

(Organic solvent)
Examples of the organic solvent contained in the conductive polymer solution include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylenephosphonium triamide, acetonitrile, and benzonitrile. Polar solvents such as cresol, phenols such as cresol, phenol and xylenol, alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, hydrocarbons such as hexane, benzene and toluene, formic acid, acetic acid, etc. Carboxylic acids, carbonate compounds such as ethylene carbonate and propylene carbonate, ether compounds such as dioxane and diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether , Chain ethers such as polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether, heterocyclic compounds such as 3-methyl-2-oxazolidinone, nitrile compounds such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, etc. Is mentioned. These organic solvents may be used alone, as a mixture of two or more kinds, or as a mixture with other organic solvents.

(Binder resin)
The conductive polymer solution preferably contains a binder resin because scratch resistance and surface hardness of the resulting conductive coating film are increased and adhesion with the substrate is improved.
The binder resin may be a thermosetting resin or a thermoplastic resin. For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyimides; polyamide imides; polyamides such as polyamide 6, polyamide 6, 6, polyamide 12, and polyamide 11; polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene Fluoropolymers such as ethylene tetrafluoroethylene copolymer and polychlorotrifluoroethylene; vinyl resins such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, and polyvinyl chloride; epoxy resins; xylene resins; aramid resins; Polyurea; polyurea; melamine resin; phenol resin; polyether; acrylic resin and copolymers thereof.
These binder resins may be dissolved in an organic solvent, may be provided with a functional group such as a sulfonic acid group or a carboxylic acid group, may be formed into an aqueous solution, or may be dispersed in water such as emulsification. .

  Among the binder resins, one or more of polyurethane, polyester, acrylic resin, polyamide, polyimide, epoxy resin, and polyimide silicone are preferable because they can be easily mixed. Acrylic resins are suitable for applications such as optical filters because of their high hardness and excellent transparency.

The acrylic resin preferably contains a liquid polymer that is cured by heat 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.
The reactive polymer is a polymer in which a monomer having a substituent is polymerized, and examples of the substituent include a carboxyl group, an acid anhydride, an oxetane group, a glycidyl group, and an amino group. Specific monomers include malonic acid, succinic acid, glutamic acid, pimelic acid, ascorbic acid, phthalic acid, acetylsalicylic acid, adipic acid, isophthalic acid, benzoic acid, m-toluic acid and other carboxylic acid compounds, anhydrous Maleic acid, phthalic anhydride, dodecyl succinic anhydride, dichloromaleic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, acid anhydrides such as pimelic anhydride, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane Oxetane compounds such as 3-methyl-3-hydroxymethyloxetane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolac polyglycidyl ether, N, N-diglycidyl-p-aminophenol glycidyl ether, tetrabromo Glycidyl ether compounds such as spunol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (ie, 2,2-bis (4-glycidyloxycyclohexyl) propane), N, N-diglycidylaniline, tetraglycidyldiaminodiphenylmethane, N, N, N, N-tetraglycidyl-m-xylylenediamine, triglycidyl isocyanurate, glycidylamine compounds such as N, N-diglycidyl-5,5-dialkylhydantoin, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine N-aminoethylpiperazine, benzyldimethylamine, tris (dimethylaminomethyl) phenol, DHP30-tri (2-ethylhexoate), metaphenylenediamine, diamy Amine compounds such as diphenylmethane, diaminodiphenylsulfone, dicyandiamide, boron trifluoride, monoethylamine, menthanediamine, xylenediamine, and ethylmethylimidazole. Among compounds containing two or more oxirane rings in one molecule, bisphenol A epi The glycidyl compound by chlorohydrin, or its analog is mentioned.

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 ) ₂ , ZrO (OCH ₃ ), Mg (OOC · CH _3). ), Ca (OH) ₂ , Ba (OH) _{3 and the} like can be used as appropriate.

  The self-crosslinking polymer is self-crosslinking between functional groups by heating, and examples thereof include those containing a glycidyl group and a carboxyl group, and those containing both an N-methylol and a carboxyl 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 Relates, acrylates such as 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 , Dimethylaminopropylmethacrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylformamide, N-methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N-phenyl Acrylics such as acrylamide, acryloylpiperidine, 2-hydroxyethylacrylamide ( Methacryl) amides, 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, vinyl ethers such as triethylene glycol vinyl ether, carboxylic acid vinyl esters such as vinyl butyrate, vinyl monochloroacetate and vinyl pivalate And monofunctional monomers as well as polyfunctional monomers.

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.

(Dopant)
In order to further improve the conductivity, other dopants may be added to the conductive polymer solution in addition to the polyanion. Other dopants may be donor or acceptor as long as the π-conjugated conductive polymer can be oxidized and reduced.

[Donor dopant]
Examples of the donor dopant include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, dimethyldiethylammonium, and the like. A quaternary amine compound etc. are mentioned.

[Acceptor dopant]
As the acceptor dopant, for example, a halogen compound, Lewis acid, proton acid, organic cyano compound, organometallic compound, fullerene, hydrogenated fullerene, hydroxylated fullerene, carboxylated fullerene, sulfonated fullerene, or the like can be used.
Furthermore, examples of the halogen compound include chlorine (Cl ₂ ), bromine (Br ₂ ), iodine (I ₂ ), iodine chloride (ICl), iodine bromide (IBr), and iodine fluoride (IF). .
Examples of the Lewis acid include PF ₅ , AsF ₅ , SbF ₅ , BF ₅ , BCl ₅ , BBr ₅ , SO _{3 and the} like.
As the organic cyano compound, a compound containing two or more cyano groups in a conjugated bond can be used. Examples include tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, dichlorodicyanobenzoquinone (DDQ), tetracyanoquinodimethane, and tetracyanoazanaphthalene.

  Examples of the protonic acid include inorganic acids and organic acids. Furthermore, examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, borohydrofluoric acid, hydrofluoric acid, and perchloric acid. Examples of organic acids include organic carboxylic acids, phenols, and organic sulfonic acids.

  As the organic carboxylic acid, aliphatic, aromatic, cycloaliphatic or the like containing one or more carboxyl groups can be used. For example, formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, nitroacetic acid, And triphenylacetic acid.

As the organic sulfonic acid, aliphatic, aromatic, cycloaliphatic or the like containing one or more sulfo groups, or a polymer containing sulfo groups can be used.
As one containing one sulfo group, for example, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1 -Nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfone Acid, trifluoroethanesulfonic acid, colistin methanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-5-naphthol- 7-sulfonic acid, 3-aminopropanesulfone N-cyclohexyl-3-aminopropanesulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hex Tylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, 2, 4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid 4-amino-2-chlorotoluene-5-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-amino-5-methoxy-2-methylbenzenesulfonic acid, 2-amino-5-methyl Benzene-1-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4 -Acetamide-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, 4 -Amino-1-naphthalenesulfonic acid, 8-chloronaphthalene-1- Examples include sulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, anthraquinone sulfonic acid, and pyrene sulfonic acid. These metal salts can also be used.

  Examples of those containing two or more sulfo groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, o-benzenedisulfonic acid, m-benzenedisulfonic acid, p-benzenedisulfonic acid, and toluenedisulfonic acid. Xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 3,4-dihydroxy-1,3 -Benzenedisulfonic acid, naphthalene disulfonic acid, methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, pentadecyl naphthalene disulfonic acid, 3-amino-5-hydroxy-2,7-naphthalene disulfonic acid, 1- Cetamide-8-hydroxy-3,6-naphthalenedisulfonic acid, 2-amino-1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalenedisulfonic acid, 3-amino-1,5-naphthalenedisulfonic acid, 8-Amino-1-naphthol-3,6-disulfonic acid, 4-amino-5-naphthol-2,7-disulfonic acid, 4-acetamido-4'-isothio-cyanotostilbene-2,2'-disulfonic acid 4-acetamido-4′-isothiocyanatostilbene-2,2′-disulfonic acid, 4-acetamido-4′-maleimidylstilbene-2,2′-disulfonic acid, naphthalenetrisulfonic acid, dinaphthylmethanedisulfone An acid, anthraquinone disulfonic acid, anthracene sulfonic acid, etc. are mentioned. These metal salts can also be used.

Since the conductive polymer solution described above is an organic solvent solution of the conductive solid described above, the drying time for forming the coating film can be shortened by selecting an organic solvent having a low boiling point. Therefore, the productivity of the conductive coating film can be increased.
In addition, since the π-conjugated conductive polymer contained in the conductive polymer solution is not hydrophilic but is oleophilic, it is easily compatible with the hydrophobic resin.
And the electroconductive coating film formed from this electroconductive polymer solution has high electroconductivity.

<Method for producing conductive solid>
(Production Example 1) Production of polystyrene sulfonic acid 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water was stirred at 80 ° C. The solution was added dropwise for 20 minutes, and the solution was stirred for 12 hours.
To the obtained sodium styrenesulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, about 1000 ml of the polystyrenesulfonic acid-containing solution was removed using an ultrafiltration method, and 2000 ml of ion-exchanged water was added to the remaining liquid. And about 2000 ml solution was removed using ultrafiltration. The above ultrafiltration operation was repeated three times.
Further, about 2000 ml of ion-exchanged water was added to the obtained filtrate, and about 2000 ml of solution was removed using an ultrafiltration method. This ultrafiltration operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid.

(Production Example 2) Production of aqueous solution of PEDOT-PSS 14.2 g of 3,4-ethylenedioxythiophene and a solution of 36.7 g of polystyrene sulfonic acid dissolved in 2000 ml of ion-exchanged water were mixed at 20 ° C. .
While maintaining the mixed solution thus obtained at 20 ° C. and stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added, The reaction was stirred for 3 hours.
2000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2000 ml of solution was removed using an ultrafiltration method. This operation was repeated three times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water are added to the resulting solution, and about 2000 ml of solution is removed using an ultrafiltration method, and 2000 ml of ion-exchanged water is added thereto. About 2000 ml of liquid was removed using an ultrafiltration method. This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain an aqueous solution of about 1.2% by mass of blue PEDOT-PSS.

(Example 1)
To 100 mL of the PEDOT-PSS aqueous solution, 100 mL of methyl ethyl ketone in which 1.05 g of trioctylamine was dissolved was added to coordinate the trioctylamine to the sulfo group of polystyrene sulfonic acid. Thereby, a trioctylammonium salt solution of PEDOT-PSS was obtained. Then, water and methyl ethyl ketone were removed from the solution by an evaporator to obtain a powdered PEDOT-PSS trioctylammonium salt.

(Example 2)
A powdery PEDOT-PSS didecylammonium salt was obtained in the same manner as in Example 1 except that 0.89 g of didecylamine was used instead of 1.05 g of trioctylamine.

(Example 3)
A powdery PEDOT-PSS stearyl ammonium salt was obtained in the same manner as in Example 1 except that 0.81 g of stearylamine was used instead of 1.05 g of trioctylamine.

Example 4
A powdery PEDOT-PSS imidazole salt was obtained in the same manner as in Example 1 except that 0.20 g of imidazole was used instead of 1.05 g of trioctylamine.

(Example 5)
In the same manner as in Example 1, except that 0.62 g of 2,6-di-t-butyl-4-methylpyridine was used instead of 1.05 g of trioctylamine, 6-di-t-butyl-4-methylpyridine salt was obtained.

<Conductive polymer solution>
(Example 6)
200 mL of isopropanol was added to the trioctylammonium salt of PEDOT-PSS obtained in Example 1, and the mixture was stirred for 1 hour using a stirrer. Then, the nanomizer process was performed and the 0.6 mass% isopropanol solution of the trioctyl ammonium salt of PEDOT-PSS was obtained.
This solution was applied onto a polyethylene terephthalate film (T680E manufactured by Mitsubishi Polyester Co., Ltd.) using a # 8 bar coater and formed at 100 ° C. for 1 minute to form a conductive coating film. The surface resistance value of the conductive coating film was measured by Hiresta (Mitsubishi Chemical). The results are shown in Table 1.

(Example 7)
A 0.6 mass% methyl ethyl ketone solution of PEDOT-PSS trioctyl ammonium salt was obtained in the same manner as in Example 6 except that 200 mL of methyl ethyl ketone was used instead of 200 mL of isopropanol. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Example 8)
A 0.6 mass% ethyl acetate solution of PEDOT-PSS trioctylammonium salt was obtained in the same manner as in Example 6 except that 200 mL of ethyl acetate was used instead of 200 mL of isopropanol. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

Example 9
A 0.6 mass% butyl acetate solution of PEDOT-PSS trioctylammonium salt was obtained in the same manner as in Example 6 except that 200 mL of butyl acetate was used instead of 200 mL of isopropanol. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Example 10)
A 0.6 mass% toluene solution of PEDOT-PSS trioctylammonium salt was obtained in the same manner as in Example 6 except that 200 mL of toluene was used instead of 200 mL of isopropanol. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Example 11)
A 0.6 mass% methyl ethyl ketone / butyl acetate solution of trioctylammonium salt of PEDOT-PSS was obtained in the same manner as in Example 6 except that a mixed solvent of 100 mL of methyl ethyl ketone and 200 mL of butyl acetate was used instead of 200 mL of isopropanol. . And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

Example 12
A 0.6 mass% methyl ethyl ketone / ethyl acetate solution of PEDOT-PSS trioctylammonium salt was obtained in the same manner as in Example 6 except that a mixed solvent of 100 mL of methyl ethyl ketone and 100 mL of ethyl acetate was used instead of 200 mL of isopropanol. . And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Example 13)
To the PEDOT-PSS didecylammonium salt obtained in Example 2, 200 mL of methyl ethyl ketone was added and stirred for 1 hour using a stirrer. Then, the nanomizer process was performed and the 0.6 mass% methyl ethyl ketone solution of the didecyl ammonium salt of PEDOT-PSS was obtained. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Example 14)
200 mL of isopropanol was added to the stearyl ammonium salt of PEDOT-PSS obtained in Example 3, and the mixture was stirred for 1 hour using a stirrer. Then, the nanomizer process was performed and the 0.6 mass% isopropanol solution of the stearyl ammonium salt of PEDOT-PSS was obtained. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Example 15)
Ethanol 200mL was added to the imidazole salt of PEDOT-PSS obtained in Example 4, and it stirred for 1 hour using the stirrer. Then, the nanomizer process was performed and the 0.6 mass% ethanol solution of the imidazole salt of PEDOT-PSS was obtained. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Example 16)
200 mL of isopropanol was added to 2,6-di-t-butyl-4-methylpyridine salt of PEDOT-PSS obtained in Example 5, and the mixture was stirred for 1 hour using a stirrer. Thereafter, nanomizer treatment was performed to obtain a 0.6 mass% isopropanol solution of 2,6-di-t-butyl-4-methylpyridine salt of PEDOT-PSS. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Example 17)
2 g of isopropanol was further added to 2 g of a 0.6 mass% isopropanol solution of 2,6-di-t-butyl-4-methylpyridine salt of PEDOT-PSS obtained in Example 16, and PEDOT-PSS 2 A 0.3 mass% isopropanol solution of 6-di-t-butyl-4-methylpyridine salt was obtained. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Example 18)
2 g of methyl ethyl ketone was further added to 2 g of a 0.6 mass% isopropanol solution of 2,6-di-t-butyl-4-methylpyridine salt of PEDOT-PSS obtained in Example 16, and 2 of PEDOT-PSS A 0.3 mass% isopropanol / methyl ethyl ketone solution of 6-di-t-butyl-4-methylpyridine salt was obtained. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Example 19)
2 g of acetone was added to 2 g of a 0.6 mass% isopropanol solution of 2,6-di-t-butyl-4-methylpyridine salt of PEDOT-PSS obtained in Example 16 to obtain 2,6 of PEDOT-PSS. A 0.3 mass% isopropanol / acetone solution of -di-t-butyl-4-methylpyridine salt was obtained. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Example 20)
2 g of n-butanol was added to 2 g of a 0.6 mass% isopropanol solution of 2,6-di-t-butyl-4-methylpyridine salt of PEDOT-PSS obtained in Example 16 to obtain 2 of PEDOT-PSS. , 6-Di-t-butyl-4-methylpyridine salt 0.3 mass% isopropanol butanol solution was obtained. And it carried out similarly to Example 6, the conductive coating film was formed, and the surface resistance value was measured. The results are shown in Table 1.

(Comparative Example 1)
When 100 mL of methyl ethyl ketone was added to 100 mL of the aqueous PEDOT-PSS solution obtained in Production Example 2 and the solvent was removed using an evaporator, the PEDOT-PSS became a film. 200 mL of methyl ethyl ketone was added to this film-like PEDOT-PSS, stirred for 1 hour using a stirrer, and then nanomized. As a result, all PEDOT-PSS precipitated and a solution was not obtained.

Examples 6 to 20 in which the π-conjugated conductive polymer was dissolved in an organic solvent at a high concentration by using the conductive solids of Examples 1 to 5 in which an amine compound was coordinated to the sulfo group of polystyrene sulfonic acid. As a result, a conductive polymer solution was obtained. The conductive coating film formed from these conductive polymer solutions was excellent in conductivity. Moreover, in the conductive polymer solutions of Examples 6 to 20, the drying time for coating film formation could be shortened. Moreover, since the π-conjugated conductive polymer contained in the conductive polymer solutions of Examples 6 to 20 is lipophilic, it is likely to be compatible with the hydrophobic resin.
On the other hand, in Comparative Example 1 in which no amine compound was added, an organic solvent of a π-conjugated conductive polymer was not obtained.

Claims (4)

containing a π-conjugated conductive polymer and a solubilized polymer having an anion group or an electron-withdrawing group,
A conductive solid, wherein an amine compound is coordinated or bonded to an anion group or electron withdrawing group of a solubilized polymer.   In the presence of a solubilized polymer, a precursor monomer of a π-conjugated conductive polymer is polymerized in water to prepare a conductive polymer aqueous solution, and an amine compound is added to the conductive polymer aqueous solution. A method for producing a conductive solid.   A conductive polymer solution, wherein the conductive solid according to claim 1 is dissolved in an organic solvent.   The conductive polymer solution according to claim 3, comprising a binder resin.