JP5026054B2 - Method for producing conductive polymer paint, method for producing conductive coating film - Google Patents

Description

  The present invention relates to a conductive polymer paint in which a π-conjugated conductive polymer is dissolved in an organic compound and a method for producing the same. The present invention also relates to a conductive coating film containing a π-conjugated conductive polymer.

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, it is conceivable to prepare an organic solvent solution of the conductive polymer by adding a highly volatile organic solvent such as alcohol to the conductive polymer aqueous solution and removing water and the organic solvent with an evaporator or the like. However, if the π-conjugated conductive polymer concentration is increased to a practical level in the organic solvent solution of the conductive polymer, the π-conjugated conductive polymer tends to separate and precipitate or gel. there were. With such an organic solvent solution of a conductive polymer, it is difficult to form a coating film, and even if a coating film is forcibly formed, it is difficult to ensure sufficient conductivity.
Further, when an organic solvent solution is used, the environment may be polluted because the organic solvent is released into the atmosphere during drying.
The present invention has been made in view of the circumstances described above, and is a conductive polymer that can increase the productivity of coating film formation, has high dispersibility of the π-conjugated conductive polymer, and can prevent environmental pollution. The object is to provide a paint. Moreover, it aims at providing the manufacturing method of the conductive polymer coating which can manufacture such a conductive polymer coating easily. Furthermore, it aims at providing the electroconductive coating film with which high electroconductivity was ensured.

The present invention includes the following inventions .
[1 ] A step of polymerizing a precursor monomer of a π-conjugated conductive polymer in water in the presence of a solubilized polymer to prepare a conductive polymer aqueous solution;
Adding an amine compound to the conductive polymer aqueous solution;
A step of concentrating an aqueous conductive polymer solution to which an amine compound has been added by ultrafiltration, adding an organic solvent, and preparing an organic solvent solution of the conductive polymer;
Adding a liquid acrylic compound to the organic solvent solution of the conductive polymer;
And a step of removing the organic solvent from the organic solvent solution of the conductive polymer to which the liquid acrylic compound has been added.
[2] A step of polymerizing a precursor monomer of a π-conjugated conductive polymer in water in the presence of a solubilized polymer to prepare a conductive polymer aqueous solution;
Adding an amine compound to the conductive polymer aqueous solution;
A step of concentrating an aqueous conductive polymer solution to which an amine compound has been added by ultrafiltration, adding an organic solvent, and preparing an organic solvent solution of the conductive polymer;
Adding a liquid acrylic compound to the organic solvent solution of the conductive polymer;
Removing the organic solvent from the organic solvent solution of the conductive polymer to which the liquid acrylic compound is added to obtain a conductive polymer paint;
Applying the conductive polymer coating and polymerizing the liquid acrylic compound.

The conductive polymer paint of the present invention can increase the productivity of coating film formation, has a high dispersibility of the π-conjugated conductive polymer, and can prevent environmental pollution.
According to the method for producing a conductive polymer paint of the present invention, the conductive polymer paint can be easily produced.
The conductive coating film of the present invention has high conductivity.

<Conductive polymer paint>
The conductive polymer coating of the present invention contains a π-conjugated conductive polymer, a solubilized polymer, an amine compound coordinated or bonded to the solubilized polymer, and a liquid acrylic compound. .

(Π-conjugated conductive polymer)
Specific examples of the π-conjugated conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), 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-hexyl) Ruoxypyrrole), 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-dibutylthio) Phen), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxy) Thiophene), 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-dihexyloxy) Thiophene), poly (3,4-diheptyloxythiophene), poly (3,4- Octyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxy) Thiophene), 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-isobutyl Aniline), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid) and the like. That.

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 ′-[ Examples include polyimides from anhydrides such as 4,4′-di (dicarboxyphenyloxy) phenyl] propane dianhydride and diamines 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 amount 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 obtained. When the amount of the solubilized polymer with respect to 1 mol of the obtained π-conjugated conductive polymer is less than 0.1 mol, the doping effect on the π-conjugated conductive polymer tends to be weak, and the conductivity is insufficient. Sometimes. In addition, the solubility in a solvent becomes low, and it becomes difficult to obtain a uniform conductive polymer paint. Further, when the amount of the solubilized polymer with respect to 1 mol of the π-conjugated conductive polymer is more than 10 mol, the content ratio of the π-conjugated conductive polymer is decreased, and it is difficult to obtain sufficient conductivity.

  The solubilized polymer is coordinated to the π-conjugated conductive polymer via an anion group or electron withdrawing group, and as a result, the π-conjugated conductive polymer and the solubilized polymer form a complex. is doing. When the solubilized polymer is a polyanion in the composite, it functions as a dopant for the π-conjugated conductive polymer.

(Amine compound)
The amine compound is not 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 molar equivalent, and it is especially preferable that it is 0.85-1.25 molar equivalent.
If the amount of the amine compound is equal to or greater than the lower limit, the amine compound coordinates to almost all of the anion group and electron withdrawing group of the solubilized polymer, so that the solubility of the π-conjugated conductive polymer in an organic solvent is increased. Becomes higher. Moreover, if it is below the said upper limit, since an excess amine compound is not contained in a conductive polymer coating material, the fall of the electroconductivity of a conductive film obtained and a mechanical physical property can be prevented.

(Liquid acrylic compound)
Examples of liquid acrylic compounds include bisphenol A / ethylene oxide-modified diacrylate, dipentaerythritol hexa (penta) acrylate, dipentaerythritol monohydroxypentaacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, and glycerin propoxytriacrylate. 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, trimethylol Propane triacrylate, tripropylene glycol dia Acrylates such as relate, tetraethylene glycol dimethacrylate, alkyl methacrylate, allyl methacrylate, 1,3-butylene glycol dimethacrylate, n-butyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol dimethacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 1,6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, t-butyl methacrylate, tetrahydrofurfuryl methacrylate, methacrylates such as trimethylolpropane trimethacrylate, allyl glycidyl ether , Butyl Glyci Glycidyl ethers such as ether, higher alcohol glycidyl edel, 1,6-hexanediol glycidyl ether, phenyl glycidyl ether, stearyl glycidyl ether, diacetone acrylamide, N, N-dimethylacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide , Methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylformamide, N-methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N-phenylacrylamide, acryloylpiperidine, 2 -Acrylic (methacrylic) amides such as hydroxyethyl acrylamide, 2-chloroethyl vinyl Monofunctional and polyfunctional monomers such as vinyl ethers such as nyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, and vinyl carboxylates such as vinyl butyrate, vinyl monochloroacetate and vinyl pivalate Can be mentioned.
The liquid acrylic compound is polymerized after application and becomes a part of the obtained conductive coating film.

  The amount of the π-conjugated conductive polymer with respect to 100% by mass of the liquid acrylic compound is preferably 0.01 to 3.0% by mass. If the amount of the π-conjugated conductive polymer relative to the liquid acrylic compound is 0.01% by mass or more, the dispersibility of the π-conjugated conductive polymer in the conductive polymer coating can be further increased, and 3.0 mass. If it is% or less, the π-conjugated conductive polymer content in the conductive coating can be sufficiently ensured, so that the conductivity can be increased.

(Photopolymerization initiator)
The conductive polymer paint preferably contains a photopolymerization initiator for accelerating the polymerization of the liquid acrylic compound. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoylbenzoate, tetramethylthiuram monosulfide, and thioxanthones. 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)
The conductive polymer paint may contain a dopant.
The dopant may be donor-type or acceptor-type as long as the π-conjugated conductive polymer can be oxidized and reduced.
When a dopant is added, the conductivity can be further improved.

[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 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.

In the conductive polymer coating material described above, the amine compound is coordinated or bonded to the solubilized polymer, so that the solubilized polymer is oil-soluble. As a result, the complex of the π-conjugated conductive polymer and the solubilized polymer is also oil-soluble and dissolved in the liquid acrylic compound that is a liquid organic compound. Therefore, the conductive polymer paint has a high dispersibility of the π-conjugated conductive polymer.
The liquid acrylic compound can be polymerized and cured by heating, ultraviolet irradiation and electron beam irradiation. Therefore, by heating the conductive polymer paint applied to the substrate, etc., or by irradiating the conductive polymer paint with ultraviolet rays and electron beams, the liquid acrylic compound is cured to form a conductive coating film. it can. Therefore, the conductive polymer coating does not require drying of the solvent when forming the conductive coating film, so that the coating film formation time can be shortened and the productivity is excellent. Release is prevented.

<Method for producing conductive polymer paint>
The method for producing a conductive polymer paint according to the present invention includes a step of preparing a conductive polymer aqueous solution (hereinafter referred to as a first step), and a step of adding an amine compound to the conductive polymer aqueous solution (hereinafter referred to as the following step). And a step of concentrating the aqueous conductive polymer solution to which the amine compound is added and adding an organic solvent to prepare an organic solvent solution of the conductive polymer (hereinafter referred to as a third step). ), A step of adding a liquid acrylic compound to the organic solvent solution of the conductive polymer (hereinafter referred to as the fourth step), and an organic solvent from the organic solvent solution of the conductive polymer to which the liquid acrylic compound is added. And a step of removing (hereinafter referred to as a fifth step).

(First step)
In the first step, in order to prepare an aqueous conductive polymer solution, a precursor monomer of a π-conjugated conductive polymer is polymerized in water in the presence of a solubilized polymer.
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.

(Second step)
The addition amount of the amine compound in the second step is the same as the amine compound content in the conductive polymer paint.

(Third step)
In the third step, ultrafiltration is applied when the aqueous conductive polymer solution to which the amine compound is added is concentrated.
Ultrafiltration is one type of membrane separation, and is a method of separating components using, for example, an ultrafiltration membrane having a polymer membrane having pores smaller than that on a porous support substrate.
As an ultrafiltration membrane used for ultrafiltration, those having a fractional molecular weight of 10,000 to 500,000 are preferable. If the molecular weight cut-off is less than 10,000, the solvent will not easily permeate the ultrafiltration membrane and tend to be difficult to concentrate. Therefore, it tends to be difficult to concentrate.

  It is preferable to repeat the concentration of the aqueous conductive polymer solution by ultrafiltration and the addition of the organic solvent a plurality of times. If the concentration of the conductive polymer aqueous solution and the addition of the organic solvent are repeated a plurality of times, the amount of water in the organic solvent solution of the obtained conductive polymer can be reduced, specifically, 5% by mass or less.

In the third step, the organic solvent may be added before the concentration of the aqueous conductive polymer solution or may be added after the concentration.
Examples of the organic solvent include polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphortriamide, acetonitrile, benzonitrile, cresol, phenol , Phenols such as xylenol, alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, hydrocarbons such as hexane, benzene and toluene, carboxylic acids such as formic acid and acetic acid, ethylene carbonate, propylene Carbonate compounds such as carbonate, ether compounds such as dioxane and diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dia Use chain ethers such as kill ether and polypropylene glycol dialkyl ether, heterocyclic compounds such as 3-methyl-2-oxazolidinone, nitrile compounds such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, and benzonitrile. . These organic solvents may be used alone, as a mixture of two or more kinds, or as a mixture with other organic solvents.

(Fourth process)
The addition amount of the liquid acrylic compound in the fourth step is the same as the content of the liquid acrylic compound in the conductive polymer paint.

(Fifth step)
Examples of the method for removing the organic solvent in the fifth step include a method for removing the organic solvent using an evaporator.

  According to the method for producing a conductive polymer paint described above, the solubilized polymer in which the amine compound is coordinated or bonded and the π-conjugated conductive polymer coordinated in the solubilized polymer are organic compounds. The conductive polymer paint dissolved in the liquid acrylic compound can be easily produced.

<Conductive coating film>
The conductive coating film of the present invention is formed by applying the above-described conductive polymer coating and polymerizing a liquid acrylic compound. That is, the conductive coating film contains a polymer of a π-conjugated conductive polymer, a solubilized polymer, an amine compound, and a liquid acrylic compound.

Examples of the method for applying the conductive polymer coating include immersion, comma coating, spray coating, roll coating, and gravure printing.
As the polymerization method, polymerization by heating, polymerization by ultraviolet irradiation, or the like can be applied.
As a heating method, for example, a normal method such as hot air heating or infrared heating can be employed. As heating temperature, 50-200 degreeC is preferable. If the heating temperature is 50 ° C. or higher, the liquid acrylic compound can be polymerized quickly, and if it is 200 ° C. or lower, excessive heating can be suppressed.
As the ultraviolet irradiation method, 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.
According to the method for forming a conductive coating film that polymerizes a liquid acrylic compound, drying of the solvent is not required, so the coating film formation time can be shortened, the productivity is excellent, and the release of organic solvents to the atmosphere is prevented. Is done.

The conductive coating film described above is formed using a conductive polymer coating material having high dispersibility of the π-conjugated conductive polymer, and the dispersion of the π-conjugated conductive polymer in the conductive coating film. Therefore, sufficient conductivity is ensured.
Furthermore, since the conductive coating film contains a polymer of a liquid acrylic compound, the scratch resistance and surface hardness are high, and the adhesion to the substrate is also high.

(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
400 mL of isopropanol in which 1.70 g of tripropylamine is dissolved is added to 400 mL of the aqueous solution of PEDOT-PSS, and 300 mL of water and isopropanol are obtained using an ultrafilter (FB02-CC-FUS1582 manufactured by Daisen Membrane Systems Co., Ltd.). And concentrated. To 500 mL of the resulting concentrated solution, 3000 mL of isopropanol was added, and 3000 mL of water and isopropanol were removed using an ultrafilter, and the mixture was concentrated. Then, nanomizer treatment was performed to obtain a 0.6 mass% isopropanol solution (water content 1.6 mass%) of 800 mL of PEDOT-PSS tripropylammonium salt.
After adding 50 g of dipentaerythritol hexaacrylate to 50 g of this solution, isopropanol was removed by an evaporator, and a conductive polymer comprising a 0.6 mass% dipentaerythritol hexaacrylate solution of tripropylammonium salt of PEDOT-PSS. 50 g of paint was obtained.
1 g of Irgacure 754 (manufactured by Ciba Spatialty Chemicals) was added to this conductive polymer paint, and this was applied onto a polyethylene terephthalate film (T680E manufactured by Mitsubishi Polyester) using a # 16 bar coater and irradiated with ultraviolet rays. . Thus, dipentaerythritol hexaacrylate was cured with ultraviolet rays 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 2)
A conductive polymer coating comprising a 0.6 mass% pentaerythritol triacrylate solution of trioctylammonium salt of PEDOT-PSS in the same manner as in Example 1 except that dipentaerythritol hexaacrylate is replaced with pentaerythritol triacrylate. 50 g was obtained.
Using this conductive polymer paint, a conductive coating film was formed in the same manner as in Example 1, and the surface resistance value of the conductive coating film was measured with Hiresta (manufactured by Mitsubishi Chemical). The results are shown in Table 1.

(Example 3)
In the same manner as in Example 1 except that dipentaerythritol hexaacrylate was replaced with hydroxyethyl acrylate, 50 g of a conductive polymer paint comprising a 0.6 mass% hydroxyethyl acrylate solution of PEDOT-PSS trioctylammonium salt was prepared. Obtained.
Using this conductive polymer paint, a conductive coating film was formed in the same manner as in Example 1, and the surface resistance value of the conductive coating film was measured with Hiresta (manufactured by Mitsubishi Chemical). The results are shown in Table 1.

(Comparative Example 1)
To 400 mL of the aqueous PEDOT-PSS solution, 400 mL of isopropanol was added, and 300 mL of water and isopropanol were removed by an ultrafilter and concentrated. To 500 mL of the obtained concentrated solution, 3000 mL of isopropanol was added, and 2700 mL of water and isopropanol were removed with an ultrafilter to concentrate. Then, nanomizer treatment was performed to obtain 800 mL of 0.6 mass% isopropanol solution of PEDOT-PSS (water content 1.6 mass%).
When 50 g of pentaerythritol triacrylate was added to 50 g of this solution and isopropanol was removed by an evaporator, PEDOT-PSS aggregated. Therefore, a conductive polymer paint could not be obtained.

  The conductive polymer paints of Examples 1 to 3 containing an amine compound and a liquid acrylic compound in a conductive polymer aqueous solution were excellent in dispersibility of the π-conjugated conductive polymer. Moreover, according to these conductive polymer coatings, the liquid acrylic compound can be cured to form a conductive coating film, so that the productivity of the coating film was excellent and the release of organic solvents into the atmosphere was prevented. It had been. And the obtained electroconductive coating film was excellent in electroconductivity.

Claims (2)

A step of polymerizing a precursor monomer of a π-conjugated conductive polymer in water in the presence of a solubilized polymer to prepare a conductive polymer aqueous solution;
Adding an amine compound to the conductive polymer aqueous solution;
A step of concentrating an aqueous conductive polymer solution to which an amine compound has been added by ultrafiltration, adding an organic solvent, and preparing an organic solvent solution of the conductive polymer;
Adding a liquid acrylic compound to the organic solvent solution of the conductive polymer;
And a step of removing the organic solvent from the organic solvent solution of the conductive polymer to which the liquid acrylic compound has been added. A step of polymerizing a precursor monomer of a π-conjugated conductive polymer in water in the presence of a solubilized polymer to prepare a conductive polymer aqueous solution;
Adding an amine compound to the conductive polymer aqueous solution;
A step of concentrating an aqueous conductive polymer solution to which an amine compound has been added by ultrafiltration, adding an organic solvent, and preparing an organic solvent solution of the conductive polymer;
Adding a liquid acrylic compound to the organic solvent solution of the conductive polymer;
Removing the organic solvent from the organic solvent solution of the conductive polymer to which the liquid acrylic compound is added to obtain a conductive polymer paint;
Applying the conductive polymer coating and polymerizing the liquid acrylic compound.