JP4823570B2 - Conductive polymer solution and conductive coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrically conductive polymer solution capable of giving highly electrically conductive coating film, and to provide such a highly electrically conductive coating film. <P>SOLUTION: The electrically conductive polymer solution comprises a &pi;-conjugated electrically conductive polymer, a solubilizing polymer, an amide compound and a solvent. The electrically conductive coating film is such as to be formed by coating the above polymer solution. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a conductive polymer solution containing a π-conjugated conductive polymer and a conductive coating film.

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 electrolytic polymerization 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 π is placed on the support. A conjugated 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 form a π-conjugated conductive polymer film uniformly on the support surface.

Therefore, a method of introducing a functional group into a π-conjugated conductive polymer and solubilizing, a method of dispersing and solubilizing in a binder, and a method of solubilizing by adding an anionic group-containing polymer acid have been tried. .
For example, in order to improve the dispersibility in water, an oxidizing agent is used in the presence of polystyrenesulfonic acid, which is an anion group-containing polymer acid having a molecular weight in the range of 2,000 to 500,000, and 3, 4 -A method of producing a poly (3,4-dialkoxythiophene) aqueous solution by chemical oxidative polymerization of dialkoxythiophene has been proposed (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

  According to the methods described in Patent Documents 1 and 2, an aqueous dispersion containing a π-conjugated conductive polymer can be easily produced. However, in these methods, in order to ensure the dispersibility of the π-conjugated conductive polymer in water, it is necessary to contain a large amount of the anionic group-containing polymer acid. For this reason, the conductive coating film formed from the solution contains many compounds that do not contribute to conductivity, and there is a problem that high conductivity is difficult to obtain.

In the chemical oxidative polymerization method, an undesirable side reaction due to an oxidizing agent having a high oxidizing power occurs at the time of chemical oxidative polymerization. Since it was oxidized, it included a factor that lowers the conductivity of the obtained π-conjugated conductive polymer. In order to solve the problem, a method using a transition metal ion as a catalyst, a method of reacting at a low temperature for a long time, or the like may be employed. However, in these methods, the generated polymer causes a decrease in the structural regularity of the π-conjugated conductive polymer caused by protons generated by the dehydrogenation of the monomer, so that the decrease in conductivity is sufficiently prevented. I couldn't.
This invention is made | formed in view of the said subject, and it aims at providing the conductive polymer solution which can make the electroconductivity of a coating film high. Moreover, it aims at providing the electroconductive coating film with high electroconductivity.

The conductive polymer solution of the present invention contains a π-conjugated conductive polymer, a solubilized polymer, an aliphatic imide compound, and a solvent.
The conductive polymer solution of the present invention preferably further contains a binder.
The conductive coating film of the present invention is formed by applying the above-described conductive polymer solution.

The conductive polymer solution of the present invention can increase the conductivity of the coating film.
In the conductive polymer solution of the present invention, when the amide compound is a monomolecular compound containing an imide bond, the conductivity of the coating film can be further increased.
When the conductive polymer solution of the present invention further contains a binder, the scratch resistance and surface hardness of the coating film can be increased.
The conductive coating film of the present invention has high conductivity.

<Conductive polymer solution>
(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 carboxy group, a sulfo group, an alkoxy group, a hydroxy 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, compatibility with the binder, and dispersibility. 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 a relatively high thermal stability and a low degree of polymerization. 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 copolymers thereof, which are composed of a structural unit having an anionic group and a structural unit having no 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, benzophenone tetracarboxylic dianhydride, 2,2,3,3-tetracarboxydiphenyl ether dianhydride, 2,2- [4,4 Examples include polyimides from anhydrides such as' -di (dicarboxyphenyloxy) phenyl] propane dianhydride and diamines such as oxydianine, 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 hydroxy group, an amino group, a carboxy group, a cyano group, a phenyl group, a phenol group, an ester group, and an alkoxy group. In view of solubility in a solvent, heat resistance, compatibility with a resin, and the like, an alkyl group, a hydroxy 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, and hydroxy groups form hydrogen bonds with other hydrogen atoms. This makes it easy to increase solubility in organic solvents, compatibility with resins, dispersibility, and adhesion. 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 hydroxy group, an ester group, and a cyano group are preferable.

Examples of the alkyl group include chain alkyl groups such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl, and cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl. . In consideration of solubility in an organic solvent, dispersibility in a resin, steric hindrance, and the like, an alkyl group having 1 to 12 carbon atoms is more preferable.
Examples of the hydroxy group include a hydroxy group directly bonded to the main chain of the polyanion or a hydroxy group bonded via another functional group. Examples of other functional groups include an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an amide group, and an imide group. The hydroxy group is substituted at the end or in these functional groups. Among these, a hydroxy group bonded to the terminal of an alkyl group having 1 to 6 carbon atoms bonded to the main chain is more preferable from the viewpoint of compatibility with a resin and solubility in an organic solvent.
Examples of the amino group include an amino group directly bonded to the main chain of the polyanion or an amino group bonded via another functional group. Examples of other functional groups include an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an amide group, and an imide group. The amino group is substituted at the end or in these functional groups.
Examples of the phenol group include a phenol group directly bonded to the main chain of the polyanion or a phenol group bonded via another functional group. Examples of other functional groups include an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an amide group, and an imide group. The phenol group is substituted at the end or in these functional groups.
Examples of the ester group include an alkyl ester group directly bonded to the main chain of the polyanion, an aromatic ester group, and an alkyl ester group or an aromatic ester group having another functional group interposed therebetween.
The cyano group includes a cyano group directly bonded to the main chain of the polyanion, a cyano group bonded to the terminal of the alkyl group having 1 to 7 carbon atoms bonded to the main chain of the polyanion, and 2 to 2 carbon atoms bonded to the main chain of the polyanion. And a cyano group bonded to the terminal of 7 alkenyl group.

  The anion group of the polyanion may be a functional group capable of undergoing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate group, A monosubstituted phosphate group, a phosphate group, a carboxy 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 carboxy 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 carboxylic acid. Examples include 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 cyanoethylated hydroxyl group or amino group-containing resin. Examples thereof include resins (for example, cyanoethyl cellulose), polyvinyl pyrrolidone, alkylated polyvinyl pyrrolidone, and nitrocellulose.

  The solubilized polymer may be added with a synthetic rubber for improving impact resistance, an anti-aging agent, an antioxidant, or an ultraviolet absorber for improving environmental resistance. 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 dispersibility and solubility in the solvent are reduced, making it difficult to obtain a uniform dispersion. 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.

(Amide compound)
The amide compound is a general term for monomolecular compounds having an amide bond represented by —CO—NH— (the CO portion is a double bond) in the molecule. That is, examples of the amide compound include compounds having functional groups at both ends of the bond, compounds in which the bond forms part of a cyclic compound, urea and urea derivatives in which the functional groups at both ends are hydrogen, and the like. Can be mentioned.

Specific examples of the amide compound include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluamide, formamide, propionamide, propionamide, Butyramide, Isobutylamide, Methacrylamide, Palmitoamide, Stearylamide, Oleamide, Oxamide, Glutaramide, Adipamide, Cinnamamide, Glucolamide, Lactamide, Glyceramide, Tartaramide, Citrulamide, Glyoxylamide, Plubuamide, Acetoacetamide, Benzylamide, Anthranilamide , Ethylenediaminetetraacetamide, diacetamide, triacetoa And dibenzamide, tribenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1,3-diethylurea, and derivatives thereof. .
The molecular weight of the amide compound is preferably 46 to 5,000, more preferably 46 to 1,000, and particularly preferably 46 to 500.

[Imide compound]
Since the amide compound has higher conductivity, a monomolecular compound having an imide bond (hereinafter referred to as an imide compound) is preferable. Here, the imide compound is a compound having a bond structure represented by —CO—NH—CO— (wherein the CO portion is a double bond) in the molecule.

  Specific examples of the imide compound include 1,8-naphthylimide, phthalimide, 3-nitrophthalimide, 4-nitrophthalimide, 3-aminophthalimide, 4-aminophthalimide, cyclohexane-1,2-dicarboximide, allantoin and hydantoin. , Barbituric acid, alloxan, glutarimide, succinimide, 5-butylhydantoic acid, 5,5-dimethylhydantoin, 1-methylhydantoin, 1,5,5-trimethylhydantoin, 5-hydantoinacetic acid, N-hydroxy-5-norbornene -2,3-dicarboximide, glutarimide, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimidooxycarbonyloxy) ethyl] sulfone, α-methyl-α-propylsuccin Imide, cyclohexylimide, 1,3-dipropyleneurea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimidebutane, 1,6-bismaleimide hexane, 1,8- Examples thereof include bismaleimide octane and N-carboxyheptylmaleimide.

  Imide compounds are also classified as aliphatic imides, aromatic imides, etc., depending on the type of functional groups at both ends, but from the skeleton, phthalimide and phthalimide derivatives, succinimide and succinimide derivatives, benzimide and benzimide derivatives, maleimide and maleimide derivatives , Naphthalimide and naphthalimide derivatives. From the viewpoint of solubility, an aliphatic imide is preferred.

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, glutarimide, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimideoxy) Carbonyloxy) ethyl] sulfone, α-methyl-α-propylsuccinimide, cyclohexylimide and the like.
The 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 are 1,3-dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 1,8-bis. Maleimide octane, N-carboxyheptylmaleimide and the like can be mentioned.

  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 amide compound and the imide compound is preferably 0.1 to 100 molar equivalents relative to the anion and electron withdrawing group of the solubilized polymer that does not contribute to the dope of the π-conjugated polymer. It is more preferably 5 to 50 molar equivalents, and particularly preferably 1.0 to 20 molar equivalents. If the addition amount of the amide compound and the imide compound is less than the lower limit, the effect of the addition of the amide compound and the imide compound is lowered, which is not preferable. Moreover, when the said upper limit is exceeded, since the electroconductive fall resulting from the fall of (pi) conjugated system conductive polymer concentration will occur, it is unpreferable.

(solvent)
Examples of the solvent contained in the conductive polymer solution include water, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphortriamide, acetonitrile, benzoate. Polar solvents such as nitrile, 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 and acetic acid Carboxylic acids 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 reethylene glycol dialkyl ether and polypropylene glycol dialkyl ether, heterocyclic compounds such as 3-methyl-2-oxazolidinone, nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile, etc. Can be mentioned. These solvents may be used alone, as a mixture of two or more kinds, or as a mixture with other organic solvents.

(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 and the like containing one or more carboxy 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 Benzene disulfonic 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.

(Binder)
The conductive polymer solution preferably contains a binder because scratch resistance and surface hardness of the coating film are increased and adhesion to the substrate is improved.
The binder 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 binders 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 binders, 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 they have 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 and azidomethylmethyloxetane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolac polyglycidyl ether, N, N-diglycidyl-p-aminophenol Glycidyl ether compounds such as cidyl ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (ie, 2,2-bis (4-glycidyloxycyclohexyl) propane), N, N-diglycidylaniline, tetra Glycidylamine compounds such as glycidyldiaminodiphenylmethane, N, N, N, N-tetraglycidyl-m-xylylenediamine, triglycidyl isocyanurate, N, N-diglycidyl-5,5-dialkylhydantoin, diethylenetriamine, triethylenetetramine, Dimethylaminopropylamine, N-aminoethylpiperazine, benzyldimethylamine, tris (dimethylaminomethyl) phenol, DHP30-tri (2-ethylhexoate), Amine compounds such as taphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, boron trifluoride, monoethylamine, menthanediamine, xylenediamine, ethylmethylimidazole, etc. Among compounds containing two or more oxirane rings in one molecule And glycidyl compound of 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 ) 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, etc. can be mixed as a photosensitizer.

(Method for producing conductive polymer solution)
As a method for producing the conductive polymer solution, for example, first, a solubilized polymer is synthesized, and a precursor monomer of the π-conjugated conductive polymer is chemically oxidized in the presence of the solubilized polymer and a solvent. There is a method of polymerizing to obtain a solution of a π-conjugated conductive polymer and then adding an amide compound to the solution.

Examples of a method for synthesizing a polyanion that is a solubilized polymer include a method of directly introducing an anion group into a polymer having no anion group using an acid, and a polymer having no anion group is sulfonated with a sulfonating agent. Examples thereof include a method and a method of polymerizing an anionic group-containing polymerizable monomer.
Examples of the method for producing an anion group-containing polymerizable monomer by polymerization include a method for producing an anion group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.

Examples of the oxidizing agent and oxidation catalyst used in the polymerization of the anionic group-containing polymerizable monomer include ammonium peroxodisulfate (ammonium persulfate), sodium peroxodisulfate (sodium persulfate), and potassium peroxodisulfate (potassium persulfate). ), Etc., transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride, metal halide compounds such as boron trifluoride, silver oxide, cesium oxide, etc. Metal oxides, peroxides such as hydrogen peroxide and ozone, organic peroxides such as benzoyl peroxide, oxygen and the like.
Moreover, as a solvent, the solvent which comprises a conductive polymer solution can be used.

  When the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid. Examples of the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, and the like. Among these, the ultrafiltration method is preferable from the viewpoint of easy work.

The anionic group-containing polymerizable monomer is one in which a part of the monomer is substituted with a mono-substituted sulfate group, a carboxy group, a sulfo group, etc., for example, a substituted or unsubstituted ethylene sulfonic acid compound, a substituted or unsubstituted Styrene sulfonic acid compound, substituted or unsubstituted acrylate sulfonic acid compound, substituted or unsubstituted methacrylate sulfonic acid compound, substituted or unsubstituted acrylamide sulfonic acid compound, substituted or unsubstituted cyclovinylene sulfonic acid compound, substituted or unsubstituted And a substituted or unsubstituted vinyl aromatic sulfonic acid compound.
Specifically, vinyl sulfonic acid and salts thereof, allyl sulfonic acid and salts thereof, methallyl sulfonic acid and salts thereof, styrene sulfonic acid, methallyloxybenzene sulfonic acid and salts thereof, allyloxybenzene sulfonic acid and salts thereof, α-methylstyrenesulfonic acid and its salts, acrylamide-t-butylsulfonic acid and its salts, 2-acrylamido-2-methylpropanesulfonic acid and its salts, cyclobutene-3-sulfonic acid and its salts, isoprenesulfonic acid and its Salts, 1,3-butadiene-1-sulfonic acid and its salts, 1-methyl-1,3-butadiene-2-sulfonic acid and its salts, 1-methyl-1,3-butadiene-4-sulfonic acid and its salts, ethyl acrylate sulfonic acid _{(CH 2 CH-COO- (CH} 2 ₂ -SO ₃ H) and its salts, acrylic acid propyl sulfonic acid _{(CH 2 CH-COO- (CH} 2) 3 -SO 3 H) and its salts, acrylic acid -t- butyl sulfonic acid _(CH 2 _{CH-COO -C (CH 3) 2 CH 2} -SO 3 H) and its salts, acrylic acid -n- butyl sulfonic acid _{(CH 2 CH-COO- (CH} 2) 4 -SO 3 H) and salts thereof, ethyl allyl acid sulfonic acid _{(CH 2 CHCH 2 -COO- (CH} 2) 2 -SO 3 H) and its salts, allyl acid -t- butyl sulfonic acid _{(CH 2 CHCH 2 -COO-C} (CH 3) 2 CH 2 -SO ₃ H) and salts thereof, 4-pentenoic acid ethylsulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO— (CH ₂ ) ₂ —SO ₃ H) and salts thereof, 4-pentenoic acid propyl sulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO— (CH ₂ ) ₃ -SO ₃ H) and salts thereof, 4-pentenoic acid-n-butylsulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO— (CH ₂ ) ₄ —SO ₃ H) and salts thereof, 4-pentene Acid-t-butyl sulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO—C (CH ₃ ) ₂ CH ₂ —SO ₃ H) and its salts, 4-pentenoic acid phenylene sulfonic acid (CH ₂ CH (CH _{2 2} ) -COO—C ₆ H ₄ —SO ₃ H) and salts thereof, 4-pentenoic acid naphthalenesulfonic acid (CH ₂ CH (CH ₂ ) ₂ —COO—C ₁₀ H ₈ —SO ₃ H) and salts thereof, Ethyl methacrylate sulfonic acid (CH ₂ C (CH ₃ ) —COO— (CH ₂ ) ₂ —SO ₃ H) and salts thereof, propyl methacrylate methacrylate (CH ₂ C (CH ₃ ) —COO— (CH ₂ ) ₃ -SO ₃ H) and its salts,-t-methacrylic acid Buchirusu Acid _{(CH 2 C (CH 3)} -COO-C (CH 3) 2 CH 2 -SO 3 H) and its salts, methacrylic acid -n- butyl sulfonic acid _{(CH 2 C (CH 3)} -COO- ( CH ₂ ) ₄ —SO ₃ H) and salts thereof, phenylene sulfonic acid methacrylate (CH ₂ C (CH ₃ ) —COO—C ₆ H ₄ —SO ₃ H) and salts thereof, naphthalene sulfonic acid methacrylate (CH ₂₎ C (CH ₃ ) —COO—C ₁₀ H ₈ —SO ₃ H) and salts thereof, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamide— Examples include 2-methylpropanecarboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. Moreover, the copolymer containing 2 or more types of these may be sufficient.

Examples of the polymerizable monomer having no anionic group include ethylene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, styrene, p-methylstyrene, p. -Ethylstyrene, p-butylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, α-methylstyrene, 2-vinylnaphthalene, 6-methyl-2-vinylnaphthalene, 1-vinylimidazole, vinylpyridine, Vinyl acetate, acrylaldehyde, acrylonitrile, N-vinyl-2-pyrrolidone, N-vinylacetamide, N-vinylformamide, N-vinylimidazole, acrylamide, N, N-dimethylacrylamide, acrylic acid, methyl acrylate, Ethyl acrylate, propyl acrylate, acrylic acid -Butyl, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, isononyl butyl acrylate, lauryl acrylate, allyl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, benzyl acrylate, ethyl acrylate Carbitol, phenoxyethyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, methoxybutyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacryl T-butyl acid, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, methacrylic acid Benzyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acryloylmorpholine, vinylamine, N, N-dimethylvinylamine, N, N-diethylvinylamine, N, N-dibutylvinylamine, N, N-di -T-butylvinylamine, N, N-diphenylvinylamine, N-vinylcarbazole, vinyl alcohol, vinyl chloride, vinyl fluoride, methyl vinyl ether, ethyl vinyl ether, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 2-methylcyclohexene, vinylphenol, 1,3-butadiene, 1-methyl-1,3-butadiene, 2-methyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene, 1,2- Dimethyl , 3-butadiene, 1,3-dimethyl-1,3-butadiene, 1-octyl-1,3-butadiene, 2-octyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 2-phenyl -1,3-butadiene, 1-hydroxy-1,3-butadiene, 2-hydroxy-1,3-butadiene and the like.
By copolymerizing these polymerizable monomers having no anionic group, it is possible to control solvent solubility and binder compatibility.

The precursor monomer of the π-conjugated conductive polymer that undergoes chemical oxidative polymerization in the presence of the polyanion has a π-conjugated system in the molecule, and even when polymerized by the action of an appropriate oxidizing agent, A π-conjugated system is formed. Examples thereof include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.
Specific examples of the precursor monomer include pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 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, 3-ethylthiophene, -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-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxythiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butene Oxythiophene, 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, Examples include 3-isobutylaniline, 2-aniline sulfonic acid, and 3-aniline sulfonic acid.

Examples of the oxidizing agent and the oxidation catalyst used when the precursor monomer of the π-conjugated conductive polymer is chemically oxidatively polymerized are the same as those used for the synthesis of the polyanion.
The solvent may be any solvent that can dissolve or disperse the precursor monomer and can maintain the oxidizing power of the oxidizing agent and the oxidation catalyst. For example, the solvent contained in the conductive polymer solution The same thing is mentioned.

  In the conductive polymer solution described above, it is considered that the amide compound is present between or around the π-conjugated conductive polymers to reduce the hopping energy in the conductive mechanism. Therefore, although the π-conjugated conductive polymer is obtained by chemical oxidative polymerization, the conductivity of the coating film formed from the conductive polymer solution can be increased.

<Conductive coating film>
The conductive coating film of the present invention is formed by applying the above-described conductive polymer solution. Examples of the method for applying the conductive polymer solution include dipping, comma coating, spray coating, roll coating, and gravure printing.
After coating, it is preferable to cure the coating film by heat treatment or ultraviolet irradiation treatment. As the heat treatment, for example, a normal method such as hot air heating or infrared heating can be employed. As the ultraviolet irradiation treatment, for example, a method of irradiating ultraviolet rays from a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be employed.

When the amide compound contained in the conductive coating film is a saturated aliphatic imide compound, the conductivity increases according to the content of the saturated aliphatic imide compound, but in the region where the content of the saturated aliphatic imide is low. There is no significant improvement in conductivity. Therefore, the content of the saturated aliphatic imide compound in the conductive coating film is preferably 50 to 90% by mass.
Also, when the amide compound in the conductive coating is an unsaturated aliphatic imide compound, the conductivity is remarkably improved even in a region where the content of the unsaturated aliphatic imide compound is small, but if the content is too large, The effect according to the amount is not exhibited. Therefore, the content of the unsaturated aliphatic imide compound in the conductive coating film is preferably 40 to 80% by mass.

  Since the above conductive coating film is formed by applying the above conductive polymer solution, it is excellent in conductivity.

(Production Example 1) Synthesis of solubilized polymer 1.14 g of ammonium persulfate oxidizer solution in which 206 g of sodium styrenesulfonate was dissolved in 1000 ml of ion-exchanged water and was previously stirred in 10 ml of water while stirring at 80 ° C. 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 by ultrafiltration, and 2000 ml of ion-exchanged water was added to the remaining liquid. About 2000 ml of solution was removed by 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 the solution was removed by ultrafiltration. This ultrafiltration operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

(Production Example 2) Synthesis of a conductive polymer solution containing a π-conjugated conductive polymer 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid were dissolved in 2000 ml of ion-exchanged water. The solution was 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 obtained reaction solution, and about 2000 ml of solution was removed by ultrafiltration. 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, about 2000 ml of solution is removed by ultrafiltration, and 2000 ml of ion-exchanged water is added to this solution. About 2000 ml of solution was removed by external filtration. 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 by ultrafiltration. This operation was repeated 5 times to obtain about 1.5% by mass of blue polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PSS-PEDOT aqueous solution) as a conductive polymer solution.

Example 1
92 mg of succinimide was added to 5.0 g of an aqueous PSS-PEDOT solution and stirred to obtain a conductive polymer solution. Then, the conductive polymer solution was applied onto glass and dried to form a conductive coating film. The electric conductivity and surface resistance value of the conductive coating film were measured. The results are shown in Table 1.
In addition, the electrical conductivity (S / cm) and the surface resistance value (Ω) of the conductive coating film were measured using Loresta (manufactured by Mitsubishi Chemical).

(Example 2)
A conductive coating film was formed in the same manner as in Example 1 except that the amount of succinimide was 184 mg in Example 1, and the electrical conductivity and surface resistance value of the conductive coating film were measured. The results are shown in Table 1.

(Example 3)
A conductive coating film was formed in the same manner as in Example 1 except that 90 mg of maleimide was added instead of 92 mg of succinimide, and the electrical conductivity and surface resistance value of the conductive coating film were measured. The results are shown in Table 1.

Example 4
A conductive coating film was formed in the same manner as in Example 1 except that 180 mg of maleimide was added instead of 92 mg of succinimide, and the electrical conductivity and surface resistance value of the conductive coating film were measured. The results are shown in Table 1.

( Reference Example 5)
A conductive coating film was formed in the same manner as in Example 1 except that 113 mg of nicotinamide was added instead of 92 mg of succinimide, and the electrical conductivity and surface resistance value of the conductive coating film were measured. The results are shown in Table 1.

( Reference Example 6)
A conductive coating film was formed in the same manner as in Example 1 except that 227 mg of nicotinamide was added instead of 92 mg of succinimide, and the electrical conductivity and surface resistance value of the conductive coating film were measured. The results are shown in Table 1.

(Comparative Example 1)
Only the PSS-PEDOT aqueous solution was applied onto glass and dried to form a conductive coating, and the electrical conductivity and surface resistance of the conductive coating were measured. The results are shown in Table 2.

(Comparative Example 2)
184 mg of succinimide was added to 5.0 g of a 1.0% by weight aqueous solution of polystyrene sulfonic acid and stirred to prepare a solution. The solution was applied onto glass and dried to form a coating film, and the electrical conductivity and surface resistance value of the coating film were measured. The results are shown in Table 2.

(Comparative Example 3)
180 mg of maleimide was added to 5.0 g of a 1.0% by weight aqueous solution of polystyrene sulfonic acid and stirred to prepare a solution. The solution was applied onto glass and dried to form a coating film, and the electrical conductivity and surface resistance value of the coating film were measured. The results are shown in Table 2.

(Comparative Example 4)
113 mg of nicotinamide was added to 5.0 g of a 1.0% by weight aqueous solution of polystyrene sulfonic acid and stirred to prepare a solution. The solution was applied onto glass and dried to form a coating film, and the electrical conductivity and surface resistance value of the coating film were measured. The results are shown in Table 2.

The conductive coating films of Examples 1 to 4 formed from a conductive polymer solution containing a π-conjugated conductive polymer, a solubilized polymer, an amide compound, and a solvent had high conductivity.
In contrast, the conductive coating film of Comparative Example 1 formed from a conductive polymer solution containing a π-conjugated conductive polymer, a solubilized polymer, and a solvent and not containing an amide compound has low conductivity. It was.
Moreover, the coating films of Comparative Examples 2 to 4 formed from a solution containing a solubilized polymer, an amide compound, and a solvent and not containing a π-conjugated conductive polymer had extremely low conductivity.

Claims (3)

A conductive polymer solution comprising a π-conjugated conductive polymer, a solubilized polymer, an aliphatic imide compound, and a solvent. The conductive polymer solution according to claim 1, further comprising a binder. Conductive coating film which the conductive polymer solution according to claim 1 or 2, characterized in that it is formed by applying.