JP5283818B2 - Conductive composition and method for producing the same - Google Patents

Description

  The present invention relates to a conductive composition containing a π-conjugated conductive polymer and a method for producing the same.

  As an organic conductive material, a π-conjugated conductive polymer is known. The π-conjugated conductive polymer generally refers to an organic polymer whose main chain is composed of π-conjugated system. For example, polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes. , Polyanilines, polyacenes, polythiophene vinylenes and copolymers thereof. Such a π-conjugated conductive polymer is usually 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. In addition, the π-conjugated conductive polymer tends to be an indeterminate shape, and there is a problem that the conductive composition containing the π-conjugated conductive polymer has low conductivity.

Therefore, there are 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 (polyanion). Has been tried.
For example, in order to improve the dispersibility in water, 3,4-dialkoxythiophene is chemically oxidatively polymerized using an oxidizing agent in the presence of polystyrene sulfonic acid, which is a polyanion having a molecular weight in the range of 2000 to 500,000. A method for producing an aqueous poly (3,4-dialkoxythiophene) solution 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, a large amount of polyanion is contained in order to ensure the dispersibility of the π-conjugated conductive polymer in water. Therefore, the obtained conductive composition contains a large number of compounds that do not contribute to conductivity, and there is a problem that high conductivity is difficult to obtain.
In chemical oxidative polymerization, unfavorable side reactions due to oxidants with high oxidizing power occur during chemical oxidative polymerization with a high probability, resulting in the formation of polymer structures with low conjugation, excessive oxidation, and impurity ions. Etc. remained, the conductivity and long-term stability of the resulting π-conjugated conductive polymer were low. Moreover, because π-conjugated conductive polymers are in a highly oxidized state, they are said to be partially oxidized and deteriorated by an external environment such as heat to generate radicals, which are said to progress through the radical chain. Yes.
This invention solves the said subject, and aims at providing the electroconductive composition excellent in electroconductivity and stability, and its manufacturing method.

The conductive composition of the present invention includes a π-conjugated conductive polymer composed of polypyrrole or poly (3,4-ethylenedioxythiophene) , a polyanion, a compound represented by the following formula (1), or 1,2 , characterized in that it comprises a heat Dorokishi group-containing aromatic compound consisting of 3-trihydroxybenzene.

(In the formula (1), R represents a linear or branched alkyl group having 1 to 15 carbon atoms, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or an aralkyl group.)
The electrically conductive composition of the present invention preferably further contains a binder resin.
The method for producing a conductive composition of the present invention includes a polymerization step in which a precursor monomer composed of pyrrole or 3,4-ethylenedioxythiophene is dispersed or dissolved in a solvent in the presence of a polyanion, and chemical oxidative polymerization is performed.
And having an additive step of adding the above following formula (1) compounds represented by or 1,2,3 consisting trihydroxybenzene hydroxy group-containing aromatic compound.
It is preferable that the manufacturing method of the electrically conductive composition of this invention has a filtration process which removes a part of free ions further by the ultrafiltration method.

The conductive composition of the present invention is excellent in conductivity and stability.
In the conductive composition of the present invention, if the hydroxy group-containing aromatic compound has a sulfo group and / or a carboxy group, the conductivity becomes higher.
If the conductive composition of the present invention further contains a binder resin, the film formability and film strength of the coating film of the conductive composition can be adjusted.
According to the method for producing a conductive composition of the present invention, a conductive composition having excellent conductivity and stability can be easily obtained.
If the manufacturing method of the electroconductive composition of this invention has the filtration process which removes a part of free ion by an ultrafiltration method, the operation | work from an anion acid salt to an anionic acid is also simple.

The conductive composition of the present invention will be described.
The conductive composition of the present invention includes a π-conjugated conductive polymer, a polyanion, and an aromatic compound having two or more hydroxy groups.
Below, each component of the electrically conductive composition of this invention is demonstrated.

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer contained in the conductive composition of the present invention can be used as long as it is an organic polymer having a π-conjugated main chain. 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 resin can be obtained, but in order to further improve conductivity and dispersibility or solubility in the binder resin. It is preferable to introduce a functional group such as an alkyl 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 (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and 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-dibutylthiophene), poly (3 -Hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3 -Octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4-dimethoxy) Thiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3 , 4-diheptyloxythiophene), poly (3,4-dioctyloxythio) Phen), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene) , 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.

The π-conjugated conductive polymer can be easily produced by chemical oxidative polymerization of a precursor monomer that forms a π-conjugated conductive polymer in a solvent in the presence of an appropriate oxidizing agent and an oxidation catalyst.
(Precursor monomer)
The precursor monomer has a π-conjugated system in the molecule, and a π-conjugated system is formed in the main chain even when polymerized by the action of an appropriate oxidizing agent. 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, 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, 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-dimeth Cithiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxy Thiophene, 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-isobutylanily , 2-aniline sulfonic acid, 3-aniline sulfonic acid and the like.

(solvent)
The solvent used in the production of the π-conjugated conductive polymer is not particularly limited, and is a solvent that can dissolve or disperse the precursor monomer, and can maintain the oxidizing power of the oxidizing agent and the oxidation catalyst. I just need it. For example, polar solvents such as water, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphortriamide, acetonitrile, benzonitrile, cresol, phenol, xylenol, etc. Phenols, 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, etc. Carbonate compounds, ether compounds such as dioxane, diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether Chain ethers such as polypropylene glycol dialkyl ether, 3-methyl-2-oxazolidinone heterocyclic compounds such as, acetonitrile, glutarodinitrile, methoxy acetonitrile, propionitrile, nitrile compounds such as benzonitrile and the like. These solvents may be used alone, as a mixture of two or more kinds, or as a mixture with other organic solvents.

(Oxidant)
Any oxidizing agent may be used as long as it can oxidize the precursor monomer to obtain a π-conjugated conductive polymer. Examples thereof include ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate. Peroxodisulfate, transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, cupric chloride, metal oxides such as silver oxide and cesium oxide, hydrogen peroxide, ozone, etc. Examples thereof include organic peroxides such as peroxide and benzoyl peroxide, oxygen, and the like.

(Polyanion)
The polyanion is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a copolymer thereof. It consists of a structural unit having a group and a structural unit having no anionic group.
The anion group of this polyanion functions as a dopant for the π-conjugated conductive polymer.

  Polyalkylene is a polymer composed of repeating methylene. Examples of the substituted or unsubstituted polyalkylene include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly3,3,3-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-propyl-2-pentenylene, 4- Tyl-2-pentenylene, 4-hexyl-2-pentenylene, 4-cyano-2-pentenylene, 3-methyl-2-pentenylene, 4-ethyl-2-pentenylene, 3-phenyl-2-pentenylene, 4-hydroxy- Examples thereof include polymers containing one or more structural units selected from 2-pentenylene, hexenylene and the like.

As polyimide, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2- [4,4'-di (dicarboxyphenyloxy) phenyl] propane dianhydride And the like and polyimides such as oxydianine, paraphenylenediamine, metaphenylenediamine, benzophenonediamine and the like.
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 carboxyl 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.
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. .
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.
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 ester group directly bonded to the main chain of the polyanion and an ester group bonded via another functional group.

Examples of the anion group of the _{^{polyanion, -O-SO 3 - X +}} , -SO 3 - X +, -COO - X + (. X + is the hydrogen ion in each of the formulas, represents an alkali metal ion), and the like.
That is, the polyanion is a polymer acid containing a sulfo group and / or a carboxy group. Among these, from the viewpoint of doping effects on the π-conjugated conductive _{^{polymer, -SO 3 - X +, -COO}} - X + are preferable.
Moreover, it is preferable that this anion group is arrange | positioned in the principal chain of a polyanion adjacently or at fixed intervals.

Examples of methods for producing polyanions include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, and anionic group-containing polymerization. And a method of production by polymerization of a functional 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. For example, a predetermined amount of an 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 solution and reacted for a predetermined time. Let 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.
The oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the π-conjugated conductive polymer.
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 one or more functional groups such as a monosubstituted sulfate group, a carboxy group, and a sulfo group. For example, a substituted or unsubstituted ethylenesulfonic acid Compound, 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 sulfone Acid compounds, substituted or unsubstituted butadiene sulfonic acid compounds, substituted or unsubstituted vinyl aromatic sulfonic acid compounds. For example, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, methallyl sulfonic acid and its salts, styrene sulfonic acid, methallyloxybenzene sulfonic acid and its salts, allyloxybenzene sulfonic acid and its salts, α-methyl Styrenesulfonic 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, , 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, acrylic Acid ethyl sulfonic acid (CH ₂ CH—COO— (CH ₂ ) ₂ — SO ₃ H) and its salts, propyl sulfonic acid acrylate (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 salts thereof, acrylic acid-n-butylsulfonic acid (CH ₂ CH—COO— (CH ₂ ) ₄ —SO ₃ H) and salts thereof, ethyl allylate _{(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 propylsulfonic acid (CH ₂ CH ( _{CH 2) 2 -COO- (CH 2} ) 3 -SO ₃ H) and salts thereof, 4-pentenoic acid -n- butyl sulfonic acid _{(CH 2 CH (CH 2)} 2 -COO- (CH 2) 4 -SO 3 H) and salts thereof, 4-pentenoic 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 its salts, methacrylic acid Ethyl sulfonic acid (CH ₂ C (CH ₃ ) —COO— (CH ₂ ) ₂ —SO ₃ H) and its salts, propyl sulfonic acid methacrylate (CH ₂ C (CH ₃ ) —COO— (CH ₂ ) ₃ — SO ₃ H) and its salts, methacrylic acid -t- butyl sulfone 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.

  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 n-butyl, isobutyl acrylate, tert-butyl acrylate, isooctyl acrylate, isononyl butyl acrylate, lauryl acrylate, allyl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, benzyl acrylate, acrylic Ethyl carbitol, phenoxyethyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, methoxybutyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-butyl, methacrylic acid Isobutyl, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, meta Benzyl crylate, 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, cyclo Octene, 2-methylcyclohexene, vinylphenol, 1,3-butadiene, 1-methyl-1,3-butadiene, 2-methyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene, 1, 2-di Chill-1,3-butadiene, 1,3-dimethyl-1,3-butadiene, 1-octyl-1,3-butadiene, 2-octyl-1,3-butadiene, 1-phenyl-1,3-butadiene, Examples include 2-phenyl-1,3-butadiene, 1-hydroxy-1,3-butadiene, 2-hydroxy-1,3-butadiene and the like.

  Among polyanions, in terms of solvent solubility and conductivity, polyisoprene sulfonic acid, copolymer containing polyisoprene sulfonic acid, polymethallyl sulfonic acid, copolymer containing polymethallyl sulfonic acid, polysulfoethyl methacrylate Copolymer containing polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), copolymer containing poly (4-sulfobutyl methacrylate), polymethallyloxybenzenesulfonic acid, polymethallyloxybenzenesulfonic acid Preferred are a copolymer containing, polystyrene sulfonic acid, a copolymer containing polystyrene sulfonic acid, and the like.

  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.

  The content of the polyanion in the conductive composition is preferably in the range of 0.1 to 10 mol, and in the range of 1 to 7 mol, with respect to 1 mol of the π-conjugated conductive polymer. Is more preferable. When the polyanion content 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 polyanion content exceeds 10 mol, the content of the π-conjugated conductive polymer in the conductive composition decreases, and it is difficult to obtain sufficient conductivity.

(Dopant)
In the conductive composition of the present invention, other dopants may be added in addition to the polyanion in order to adjust electrical conductivity (conductivity). 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, a Lewis acid, a proton acid, an organic cyano compound, an organometallic compound, 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. For example, tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, tetracyanoquinodimethane, tetracyanoazanaphthalene, and the like can be given.

  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, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid , Heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, 2,4-dimethylbenzene Sulfonic 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-methylbenzene-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-acetamido-3-chlorobenzenesulfone Acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, 4-amino-1-naphthalenesulfone Acid, 8-chloronaphthalene-1-sulfonic acid, and the like.

  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, and the like.

(Hydroxy group-containing aromatic compound)
In the hydroxy group-containing aromatic compound, two or more hydroxy groups are substituted on the aromatic ring. For example, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 2,3-dihydroxy-1-pentadecylbenzene, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,4-dihydroxybenzophenone, 2 , 6-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 2,4′-dihydroxydiphenyl sulfone, 2,2 ′, 5,5′-tetrahydroxydiphenyl sulfone, 3,3 ′, 5 , 5′-tetramethyl-4,4′-dihydroxydiphenylsulfone, hydroxyquinonecarboxylic acid and its salts, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2, 6-dihydroxybenzoic acid, 3 5-dihydroxybenzoic acid, 1,4-hydroquinonesulfonic acid and its salts, 4,5-hydroxybenzene-1,3-disulfonic acid and its salts, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene-2,6-dicarboxylic acid, 1,6-dihydroxynaphthalene-2,5-dicarboxylic acid, 1,5 -Dihydroxynaphthoic acid, 1,4-dihydroxy-2-naphthoic acid phenyl ester, 4,5-dihydroxynaphthalene-2,7-disulfonic acid and its salts, 1,8-dihydroxy-3,6-naphthalenedisulfonic acid and its Salts, 6,7-dihydroxy-2-naphthalenesulfonic acid And salts thereof, 1,2,3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene, 5-methyl-1,2,3-trihydroxybenzene, 5-ethyl-1,2,3- Trihydroxybenzene, 5-propyl-1,2,3-trihydroxybenzene, trihydroxybenzoic acid, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, Examples thereof include tetrahydroxy-p-benzoquinone and tetrahydroxyanthraquinone.
Among the hydroxy group-containing aromatic compounds, from the viewpoint of the conductivity of the conductive composition, compounds having a sulfo group and / or a carboxy group, which are anionic groups, can be doped into the π-conjugated conductive polymer. preferable.

In addition, among the hydroxy group-containing aromatic compounds, the compound represented by the above formula (1) is preferable because of higher conductivity and stability.
Specific examples of R in the formula (1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, isohexyl group, t- Hexyl group, alkyl group such as sec-hexyl group, alkenyl group such as vinyl group, propenyl group and butenyl group, cycloalkyl group such as cyclohexyl group and cyclopentyl group, cycloalkenyl group such as cyclohexenyl group, phenyl group, Examples thereof include aryl groups such as naphthyl group, aralkyl groups such as benzyl group and phenethyl group.

  The content of the hydroxy group-substituted aromatic compound is preferably in the range of 0.05 to 10 mol, more preferably in the range of 0.3 to 5 mol, with respect to 1 mol of the anion group unit of the polyanion. . If the polyanion content is less than 0.05 mol, conductivity and heat resistance may be insufficient. If the polyanion content is more than 10 mol, the content of the π-conjugated conductive polymer in the conductive composition decreases, and it is difficult to obtain sufficient conductivity, and the physical properties of the conductive composition are reduced. May change.

The conductive composition of the present invention may be composed of the three components described above, but a binder resin is included to adjust the film formability, film strength, etc. of the coating film formed from the conductive composition. It may be.
The binder resin is not particularly limited as long as it is compatible or mixed and dispersible with each component in the conductive composition, and may be a thermosetting resin or a thermoplastic resin. For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyimides such as polyimide and polyamideimide, polyamides such as polyamide 6, polyamide 6,6, polyamide 12 and polyamide 11, polyvinylidene fluoride, polyvinyl fluoride, poly Fluorine resin such as tetrafluoroethylene, ethylenetetrafluoroethylene copolymer, polychlorotrifluoroethylene, polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, vinyl resin such as polyvinyl chloride, epoxy resin, xylene resin, aramid resin, Examples include polyurethane, polyurea, melamine resin, phenolic resin, polyether, acrylic resin, and copolymers thereof.

  Further, instead of the binder resin, a precursor compound or monomer that forms the binder resin may be included in the conductive composition. This is because the binder resin can be formed by polymerizing the precursor compound or the monomer.

The conductive composition of the present invention may contain an additive for the same reason as the binder resin. Any additive can be used as long as it can be mixed with each component of the conductive composition. Examples thereof include surfactants, antifoaming agents, coupling agents, neutralizing agents, and antioxidants.
Further, as surfactants, anionic surfactants such as carboxylate, sulfonate, sulfate ester salt, phosphate ester salt; cationic surfactants such as amine salt, quaternary ammonium salt; carboxybetaine, aminocarboxyl Examples include amphoteric surfactants such as acid salts and imidazolium betaines; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, ethylene glycol fatty acid esters, and polyoxyethylene fatty acid amides.
Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone resin.
Examples of the coupling agent include silane coupling agents having a vinyl group, an amino group, an epoxy group, and the like.
Examples of the neutralizing agent include alkali compounds such as ammonia and sodium hydroxide; nitrogen-containing compounds such as primary amines, secondary amines, and tertiary amines.
Examples of the antioxidant include phenolic antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, sugars, and vitamins.

Since the conductive composition of the present invention described above contains a hydroxy group-containing aromatic compound, the conductivity and heat resistance are high. This is considered to be due to the following reason. Since the π-conjugated conductive polymer in the conductive composition is in a highly oxidized state, a part of the π-conjugated conductive polymer is oxidized and deteriorated by an external environment such as heat to generate radicals, and the deterioration proceeds due to the chain reaction of the radicals. It is speculated that it will. However, the hydroxy group-containing aromatic compound has a property that the interaction between the hydroxy group and the aromatic ring is strong, and hydrogen in the compound is easily released. Therefore, radicals generated by oxidative degradation of the π-conjugated conductive polymer can be deactivated by hydrogen released from the hydroxy group-containing aromatic compound. Thereby, the chain reaction of radicals can be blocked and the progress of deterioration can be suppressed, so that heat resistance and stability are considered to be improved. This action is exhibited when the aromatic compound has two or more hydroxy groups.
Further, the hydroxy group-containing aromatic compound is likely to interact with the anion group in the polyanion, and it is considered that the polyanion can be brought close to each other by this interaction. Therefore, π-conjugated conductive polymers adsorbed on the polyanion by doping can also be brought close to each other. As a result, it is considered that the energy required for hopping, which is an electrical conduction phenomenon between π-conjugated conductive polymers, is reduced, and the overall electrical resistance is reduced (conductivity is increased).

Next, an example of the manufacturing method of the electrically conductive composition of this invention is demonstrated.
In the method for producing a conductive composition of this example, first, in the polymerization step, a precursor monomer that forms a π-conjugated conductive polymer is dispersed or dissolved in a solvent in the presence of a polyanion, and chemical oxidative polymerization is performed. . Specifically, an oxidant and / or an oxidative polymerization catalyst for chemically oxidatively polymerizing the polyanion, the precursor monomer, and the precursor monomer are prepared. Then, a precursor monomer, an oxidizing agent and / or an oxidation polymerization catalyst are added to the polyanion kept at a constant temperature, and the precursor monomer is reacted for a predetermined time with stirring to chemically oxidize and polymerize the precursor monomer. The operation method, operation order, reaction conditions, etc. in the polymerization step are not particularly limited.
A solvent may be added in advance to the polyanion, precursor monomer, oxidizing agent and / or oxidative polymerization catalyst to form a mixed solution having a predetermined concentration.

  During chemical oxidative polymerization of π-conjugated conductive polymer, the main chain of π-conjugated conductive polymer grows along the polyanion main chain, and the π-conjugated conductive polymer is in a highly oxidized state. To form a bipolaron structure. Thereby, it is considered that the anion group of the polyanion is doped into the π-conjugated conductive polymer to form a salt of the polyanion and the π-conjugated conductive polymer. In particular, when the polyanion is a sulfo group, a salt having a strong bond between the polyanion and the π-conjugated conductive polymer can be formed. Accordingly, since the π-conjugated conductive polymer is strongly attracted to the main chain of the polyanion, a π-conjugated conductive polymer that is grown along the main chain of the polyanion and regularly arranged can be easily obtained.

By this polymerization step, a mixed solution containing a polyanion and a π-conjugated conductive polymer can be obtained.
After the polymerization step, a reaction terminator for stopping the polymerization reaction may be added as necessary. Further, after the polymerization step is completed, excess oxidant and / or oxidative polymerization catalyst, reaction by-products may be removed and ion exchange may be performed.

Next, in the addition step, a predetermined amount of the hydroxy group-containing aromatic compound is added to the mixed solution obtained in the polymerization step and mixed uniformly.
As a method of adding a hydroxy group-containing aromatic compound, a method of directly adding a hydroxy group-containing aromatic compound as it is, a method of adding a hydroxy group-containing aromatic compound in a solution state in which the hydroxy group-containing aromatic compound is dissolved or dispersed in a solvent Is mentioned. From the viewpoint of miscibility with the mixed solution, a method of adding in a solution state dissolved or dispersed in a solvent is preferable. The solvent for dissolving or dispersing the hydroxy group-containing aromatic compound is not particularly limited, and the solvents described above can be used. The solvent may be of a different type from the mixed solution.

Thereafter, in the filtration step, a part of free ions is removed by ultrafiltration to obtain a conductive composition. In addition, in the manufacturing method of the electroconductive composition of this invention, a filtration process is an arbitrary process and may be abbreviate | omitted.
In the ultrafiltration method, a polymer membrane (ultrafiltration membrane) formed with a constant diameter is disposed on a porous material, and the solution is circulated. At that time, a pressure difference occurs between the circulating solution side and the permeated solution side across the ultrafiltration membrane, so that part of the solution on the circulating solution side permeates the permeated solution side and relieves the pressure on the circulating solution side. . Due to this phenomenon, a part of particles, dissolved ions, etc. smaller than the diameter of the ultrafiltration membrane contained in the circulating solution are moved to the permeate solution side and removed. This method is a dilution method, and impurities can be easily removed by increasing the number of dilutions.
The ultrafiltration membrane to be used is appropriately selected depending on the particle diameter to be removed and the ionic species, and among them, those having a fractional molecular weight of 1,000 to 1,000,000 are preferable.

  Many of the thus obtained π-conjugated conductive polymers exhibit insoluble and infusible characteristics because they have a π-conjugated system developed in the main chain. Also in a π-conjugated conductive polymer solution that is dissolved or dispersed, self-coordination of the π-conjugated conductive polymer occurs due to removal of the solvent, heating, doping, etc. during film formation, and becomes insoluble in the solvent. Sometimes. Therefore, it is preferable to select an appropriate solvent.

  In the method for producing a conductive composition described above, in the presence of a polyanion, a polymerization step of chemically oxidizing polymerization of a precursor monomer that forms a π-conjugated conductive polymer, and addition of adding a hydroxy group-containing aromatic compound Therefore, a conductive composition including a π-conjugated conductive polymer, a polyanion, and a hydroxy group-containing aromatic compound can be obtained. Since this conductive composition contains a hydroxy group-containing aromatic compound, it is excellent in conductivity and stability.

Examples of the present invention will be described below, but the present invention is not limited to the examples.
(Production Example 1) Synthesis of poly (ethyl methacrylate sulfonate) (PMAS) 216 g of sodium ethyl sulfonate was dissolved in 1000 ml of ion-exchanged water and dissolved in 10 ml of water in advance while stirring at 80 ° C. 14 g of ammonium persulfate oxidant solution was added dropwise over 20 minutes and the solution was stirred for 12 hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the obtained polyethyl methacrylate sodium sulfonate-containing solution, and about 1000 ml of the polyethyl methacrylate sulfonate-containing solution was removed using an ultrafiltration method. 2000 ml of ion-exchanged water was added to the solution, and about 2000 ml of solution was removed using an ultrafiltration method. The above ultrafiltration operation was repeated three times.
Furthermore, 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.
The ultrafiltration conditions were as follows (the same applies to other examples).
Ultrafiltration membrane molecular weight cut-off: 30,000
Cross flow type Supply liquid flow rate: 3000 ml / min Membrane partial pressure: 0.12 Pa Water in the obtained solution was removed under reduced pressure to obtain a colorless solid.

(Production Example 2) Synthesis 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 the 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.

( Reference Example 1)
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 solution was removed using ultrafiltration. 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 about 1.5% by mass of blue polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PSS-PEDOT). This was designated as a π-conjugated conductive polymer solution A.
To 100 g of the obtained π-conjugated conductive polymer solution A, 1.0 g of potassium hydroquinonesulfonate was added and dispersed uniformly to obtain a conductive composition solution.
The conductive composition solution was applied onto glass and dried in an oven at 150 ° C. to obtain a coating film of the conductive composition. The electrical characteristics of the obtained coating film were evaluated by the following evaluation methods. The results are shown in Table 1.

(Evaluation method) Electrical conductivity (S / cm):
The electrical conductivity of the coating film was measured using a Loresta (manufactured by Mitsubishi Chemical). The higher the electrical conductivity, the higher the conductivity.
-Electrical conductivity heat retention rate (%):
The electrical conductivity R _25B of the coating film at a temperature of 25 ° C. was measured using a Loresta (manufactured by Mitsubishi Chemical), and the coating film after measurement was left in an environment at a temperature of 125 ° C. for 300 hours. The temperature was returned to ° C., the electric conductivity R _25A was measured, and the measured values were substituted into the following formula to calculate the electric conductivity heat retention rate. In addition, this electrical conductivity heat maintenance factor becomes a stability parameter | index with respect to a heat | fever.
Electrical conductivity heat retention rate (%) = 100 × R _25A / R _25B
-Electric conductivity humidity change rate (%):
The electrical conductivity R _25B of the coating film in an environment of temperature 25 ° C. and humidity 60% RH is measured, and the coating film after measurement is left in an environment of temperature 80 ° C. and humidity 90% RH for 200 hours, and then the coating is applied. The membrane was returned to the environment of temperature 25 ° C. and humidity 60% RH, and the electric conductivity R _25A was measured. The measured value was substituted into the following equation to calculate the electric conductivity humidity change rate. This rate of change in electrical conductivity and humidity is an indicator of stability against humidity.
Electric conductivity humidity change rate (%) = 100 × (R _25B −R _25A ) / R _25B

( Reference Example 2)
The conductive composition was prepared in the same manner as in Reference Example 1 except that 0.48 g of hydroquinone was added in place of potassium hydroquinonesulfonate to 100 g of the π-conjugated conductive polymer solution A obtained in Reference Example 1. A coating film was obtained and evaluated. The results are shown in Table 1.
( Reference Examples 3-4)
Using the π-conjugated conductive polymer solution A obtained in Reference Example 1, the amount of potassium hydroquinonesulfonate added in Reference Example 1 was changed from 1.0 g to 2.0 g ( Reference Example 3) or 6.0 g ( Reference Example). A coating film of the conductive composition was obtained and evaluated in the same manner as in Reference Example 1 except that it was changed to 4). The results are shown in Table 1.
(Example 5)
The π-conjugated conductive polymer solution A of 100g obtained in Reference Example 1, except for adding 1,2,3-trihydroxybenzene of 1.5g instead of hydroquinone potassium sulfonate in Reference Example 1 Similarly, a coating film of the conductive composition was obtained and evaluated. The results are shown in Table 1.

( Reference Example 6)
14.2 g of 3,4-ethylenedioxythiophene and a solution of 38.8 g of polyethyl methacrylate sulfonic acid dissolved in 2000 ml of ion exchange 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, Stir for 3 hours.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the 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 obtained 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 solution was removed using ultrafiltration. 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 about 1.5% by mass of blue poly (ethyl methacrylate sulfonate) doped poly (3,4-ethylenedioxythiophene) (PMAS-PEDOT). This was designated as π-conjugated conductive polymer solution B.
To 100 ml of the obtained π-conjugated conductive polymer solution B, 2.0 g of an aqueous potassium hydroquinone sulfonate solution previously dissolved in 5 ml of water was added and dispersed uniformly to obtain a conductive composition solution.
The conductive composition solution was applied onto glass and dried in an oven at 150 ° C. to obtain a coating film of the conductive composition. The electrical characteristics of the obtained coating film were evaluated by the following evaluation methods. The results are shown in Table 1.

(Example 7)
The π conjugated conductive polymer solution B of 100g obtained in Reference Example 6, except for adding 1,2,3-trihydroxybenzene of 1.5g instead of hydroquinone potassium sulfonate in Reference Example 6 Similarly, a coating film of the conductive composition was obtained and evaluated. The results are shown in Table 1.

( Reference Example 8)
A solution of 6.8 g of pyrrole and 38.8 g of polyethyl methacrylate sulfonic acid dissolved in 2000 ml of ion exchange water was mixed and cooled to 0 ° C.
While maintaining the mixed solution thus obtained at 0 ° 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, Stir for 3 hours.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the 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 obtained 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 solution was removed using ultrafiltration. 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 about 1.5% by mass of blue poly (ethyl methacrylate sulfonate) doped polypyrrole (PMAS-PPY). This was designated as a π-conjugated conductive polymer solution C.
To 100 g of the obtained π-conjugated conductive polymer solution C, 2.0 g of potassium hydroquinonesulfonate was added and dispersed uniformly to obtain a conductive composition solution.
The conductive composition solution was applied onto glass and dried in an oven at 150 ° C. to obtain a coating film of the conductive composition. The electrical characteristics of the obtained coating film were evaluated by the following evaluation methods. The results are shown in Table 1.

Example 9
The π-conjugated conductive polymer solution C obtained 100g in Reference Example 8, except that the addition of 1,2,3-trihydroxybenzene of 1.5g instead of hydroquinone potassium sulfonate in Reference Example 8 Similarly, a coating film of the conductive composition was obtained and evaluated. The results are shown in Table 1.

(Example 10)
Instead of potassium hydroquinonesulfonate, 1.5 g of 1,2,3-trihydroxybenzene was added to 100 g of the π-conjugated conductive polymer solution obtained in Reference Example 1. Furthermore, 9 g of water-soluble polyester (trade name: Plus Coat Z-448D, manufactured by Kyoyo Chemical Industry Co., Ltd.) having a solid content of 25% by mass was added to this solution and dispersed uniformly to obtain a solution of a conductive composition. .
The conductive composition solution was applied onto glass and dried in an oven at 150 ° C. to obtain a coating film of the conductive composition. The electrical characteristics of the obtained coating film were evaluated by the following evaluation methods. The results are shown in Table 1.

(Comparative Example 1)
6.8 g of pyrrole and a solution of 10.8 g of polyacrylic acid dissolved in 1000 ml of ion-exchanged water were mixed and cooled to 0 ° C.
While maintaining the mixed solution thus obtained at 0 ° 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, Stir for 3 hours.
The obtained reaction solution was adjusted to pH 10 with aqueous ammonia (25% by mass), solids were precipitated with isopropyl alcohol, filtered, and the filtrate was washed three times with ion-exchanged water. The filtrate was redispersed with 1000 ml of ion exchange water to obtain a polyacrylic acid-polypyrrole colloid aqueous solution.
And the obtained polyacrylic acid-polypyrrole colloid aqueous solution was apply | coated on glass, and the coating film was dried in 150 degreeC oven, and the coating film of the electroconductive composition was obtained. The electrical properties of the coating film were evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

(Comparative Examples 2 to 4)
Π-conjugated conductive polymer solution A obtained in Reference Example 1 (Comparative Example 2), π-conjugated conductive polymer solution B obtained in Reference Example 6 (Comparative Example 3), obtained in Reference Example 8 The π-conjugated conductive polymer solution C (Comparative Example 4) was directly coated on glass, and the coating film was dried in an oven at 150 ° C. to obtain a coating film of a conductive composition. The electrical properties of the coating film were evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

The conductive compositions of Examples 5 , 7 , 9, and 10 and Reference Examples 1 to 4 , 6, and 8 containing the hydroxy group-containing aromatic compound have high conductivity, and also have excellent thermal stability and humidity stability. It was excellent.
On the other hand, the conductive compositions of Comparative Examples 1 to 4 that did not contain a hydroxy group-containing aromatic compound had low conductivity and were inferior in thermal stability and humidity stability.

(Example 11)
Except that 100 g of the π-conjugated conductive polymer solution A obtained in Reference Example 1 was added with methyl 3,4,5-trihydroxybenzoate in the amount shown in Table 2 instead of potassium hydroquinonesulfonate. In the same manner as in Reference Example 1, a coating film of the conductive composition was obtained and evaluated. The results are shown in Table 2.

(Example 12)
Except that 100 g of π-conjugated conductive polymer solution A obtained in Reference Example 1 was added with propyl 3,4,5-trihydroxybenzoate in the amount shown in Table 2 instead of potassium hydroquinonesulfonate. In the same manner as in Reference Example 1, a coating film of the conductive composition was obtained and evaluated. The results are shown in Table 2.

  The conductive compositions of Example 11 and Example 12 in which the hydroxy group-containing aromatic compound is a compound represented by the formula (1) had higher electrical conductivity (conductivity).

(Examples 13 and 14)
The coating film added with 0.3 mol of methyl 3,4,5-trihydroxybenzoate in Example 11 was left in a dryer at 150 ° C. for 550 hours (Example 13). The coating film of Example 5 was left in a dryer at 150 ° C. for 550 hours (Example 14). The electric conductivity of the coating film after heating and the electric conductivity heat retention rate were evaluated. The results are shown in Table 3.

  The conductive compositions of Example 13 and Example 14 containing a hydroxy group-containing aromatic compound had high electrical conductivity and electrical conductivity and heat retention rate. Moreover, it was found from these comparisons that Example 13 in which the hydroxy group-containing aromatic compound is a compound represented by the formula (1) has excellent electrical conductivity and high electrical conductivity and heat retention. .

  The present invention relates to conductive paint, antistatic agent, electromagnetic wave shielding material, conductive material requiring transparency, battery material, capacitor material, conductive adhesive material, sensor, electronic device material, semiconductive material, electrostatic copying It is expected to be used in various fields requiring members, photosensitive members such as printers, electrophotographic materials, and conductivity.

Claims (4)

A π-conjugated conductive polymer composed of polypyrrole or poly (3,4-ethylenedioxythiophene) , a polyanion, a compound represented by the following formula (1), or a polymer composed of 1,2,3-trihydroxybenzene A conductive composition comprising a droxy group-containing aromatic compound.
(In the formula (1), R represents a linear or branched alkyl group having 1 to 15 carbon atoms, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or an aralkyl group.)

Further, the conductive composition according to claim 1, characterized in that it contains a binder resin. A polymerization step in which a precursor monomer composed of pyrrole or 3,4-ethylenedioxythiophene is dispersed or dissolved in a solvent in the presence of a polyanion, and subjected to chemical oxidative polymerization;
And an addition step of adding a hydroxy group-containing aromatic compound composed of a compound represented by the following formula (1) or 1,2,3-trihydroxybenzene.

(In the formula (1), R represents a linear or branched alkyl group having 1 to 15 carbon atoms, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or an aralkyl group.) Furthermore, it has the filtration process which removes a part of free ion by an ultrafiltration method, The manufacturing method of the electrically conductive composition of Claim 3 characterized by the above-mentioned.