JP2022052252A - Conductive polymer powder and method for producing the same, conductive polymer composition, and electrode and method for producing the same - Google Patents

Abstract

To provide a conductive polymer powder useful as electrode materials for energy devices such as a battery and a method for producing the same, a conductive polymer composition, and an electrode and a method for producing the same.SOLUTION: A conductive polymer powder contains a π-conjugated conductive polymer and a polyanion. In the conductive polymer powder, the mass content ratio of the π-conjugated conductive polymer to the polyanion is (1:0.5) to (1:1). The conductive polymer powder 1 g and 99 g of ion exchanged water (20°C) were mixed, the resultant powder-containing water was agitated, and left to stand for 10 minutes, so that the sulfate ion content in the powder-containing water was 0.108 mass% or less relative to the total mass of the powder-containing water.SELECTED DRAWING: None

Description

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

A π-conjugated conductive polymer whose main chain is composed of a π-conjugated system is basically difficult to dissolve in water, but is water-dispersible by forming a complex with a polyanion having a hydrophilic anion group. A method of forming a conductive composite of the above is known. The formation of this conductive complex enhances conductivity. Further, there is known a method of dispersing an amine compound or an epoxy compound in an organic solvent by reacting the water-dispersible anionic group of the conductive composite with an epoxy compound (see Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2011-032382 International Publication No. 2014/125827

Patent Documents 1 and 2 aim to obtain a coating material in which a conductive composite is uniformly dispersed or dissolved at a molecular level with respect to a dispersion medium.
By the way, when a conductive polymer is used as an electrode material for an energy device such as a battery, it is not necessary for the conductive composites to be dispersed with each other at the molecular level, and the conductive composites are in the state of agglomerated powder. However, it may be easy to handle. Therefore, the present inventors have investigated a method for obtaining a powder of a conductive composite.

The present invention provides a conductive polymer powder and a method for producing the same, a conductive polymer composition, and an electrode and a method for producing the same, which are useful as an electrode material for an energy device such as a battery.

[1] A conductive polymer powder containing a π-conjugated conductive polymer and a polyanion, wherein the content ratio of the π-conjugated conductive polymer: the polyanion in the conductive polymer powder is based on mass. (1: 0.5) to (1: 1), 1 g of the conductive polymer powder and 99 g of ion-exchanged water (20 ° C.) were mixed, and the obtained powder-containing water was stirred. A conductive polymer powder in which the amount of sulfate ion in the powder-containing water after 10 minutes has passed is 0.108% by mass or less with respect to the total mass of the powder-containing water.
[2] The conductive polymer powder according to [1], wherein the conductive polymer powder contains at least one of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid.
[3] The conductive polymer powder according to [1] or [2], wherein some of the anion groups of the polyanion are modified by reacting with an amine compound.
[4] The conductive polymer powder according to [1] or [2], wherein some of the anion groups of the polyanion are modified by reacting with an epoxy compound.
[5] A conductive polymer composition comprising the conductive polymer powder according to any one of [1] to [4] and a binder component.
[6] An electrode containing the conductive polymer powder according to any one of [1] to [4].
[7] The monomer is oxidatively polymerized by adding a catalyst and an oxidizing agent to a reaction solution containing a monomer capable of forming a π-conjugated conductive polymer, a polyanion, and water, and the π-conjugated conductive polymer is obtained. It comprises a step of forming a conductive polymer powder containing a polymer and the polyanion, and a step of separating the conductive polymer powder from the reaction solution, and the monomer in the reaction solution: the said. The content ratio of the polyanomer is (1: 0.5) to (1: 1) on the basis of mass, and 1 g of the conductive polymer powder separated from the reaction solution and 99 g of ion-exchanged water (20 ° C.). , And the obtained powder-containing water is stirred, and the amount of sulfate ions in the powder-containing water after 10 minutes has passed is 0.108% by mass or less with respect to the total mass of the powder-containing water. A method for producing a conductive polymer powder.
[8] The monomer is oxidatively polymerized by adding a catalyst and an oxidizing agent to a reaction solution containing a monomer capable of forming a π-conjugated conductive polymer, a polyanion, and water, and the π-conjugated conductive polymer is obtained. By adding at least one of an amine compound and an epoxy compound to the step of forming the conductive polymer powder containing the polymer and the polyanion and the reaction solution containing the conductive polymer powder and reacting them. It has a step of precipitating the modified conductive polymer powder and a step of separating the conductive polymer powder from the reaction solution, and the monomer in the reaction solution: the polyanion. The content ratio is (1: 0.5) to (1: 1) on a mass basis, and 1 g of the conductive polymer powder separated from the reaction solution and 99 g of ion-exchanged water (20 ° C.) are mixed. Then, the obtained powder-containing water is stirred, and the amount of sulfate ion in the powder-containing water after 10 minutes has passed is 0.108% by mass or less with respect to the total mass of the powder-containing water. , Method for producing conductive polymer powder.
[9] The method for producing a conductive polymer powder according to [7] or [8], wherein sulfuric acid is added to the reaction solution and then oxidative polymerization of the monomer is carried out.
[10] The conductive polymer composition according to [5] is applied to at least a part of a base material, and the coating film formed on the base material is cured to form a conductive layer. A method for manufacturing an electrode, which obtains an electrode having the conductive layer on at least a part of the material.

The conductive molded body and the electrode produced by using the conductive polymer powder of the present invention have excellent conductivity, and are therefore useful as electrodes for batteries and the like.

The present invention is considered to contribute to SDGs Goal 12, "Responsibility to Create and Responsibility to Use".

In the present specification and claims, the lower limit value and the upper limit value of the numerical range indicated by "..." shall be included in the numerical range.

≪Conductive polymer powder≫
The first aspect of the present invention is a conductive polymer powder containing a π-conjugated conductive polymer and a polyanion, wherein the π-conjugated conductive polymer: the polyanion is contained in the conductive polymer powder. The ratio is (1: 0.5) to (1: 1) on a mass basis. Here, 1 g of the conductive polymer powder and 99 g of ion-exchanged water (20 ° C.) are mixed, the obtained powder-containing water is stirred, and after 10 minutes have passed, sulfuric acid in the powder-containing water is used. The amount of ions is 0.108% by mass or less with respect to the total mass of the powder-containing water.

The conductive polymer powder of this embodiment is an aggregate of conductive particles containing a π-conjugated conductive polymer and a conductive composite having a polyanion.

[Pi-conjugated conductive polymer]
The π-conjugated conductive polymer may be any conductive organic polymer whose main chain is composed of a π-conjugated system. For example, a polypyrrole-based conductive polymer, a polythiophene-based conductive polymer, or polyacetylene. Polyphenylene-based conductive polymer, polyphenylene-based conductive polymer, polyphenylene vinylene-based conductive polymer, polyaniline-based conductive polymer, polyacene-based conductive polymer, polythiophenine vinyl-based conductive polymer, and copolymers thereof, etc. Can be mentioned. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferable.

Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and 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-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene) , Poly (3,4-diheptyloxythiophene), Poly (3,4-dioctyloxythiophene), Poly (3,4-didecyloxythiophene), Poly (3,4-didodecyloxythiophene), Poly (3,4-didodecyloxythiophene) 3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butylenedioxythiophene), 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-carboxyphene) Butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and poly (3-butyl). Pyrrole), 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).
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).
Among these π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity, transparency and heat resistance.
The π-conjugated conductive polymer contained in the conductive polymer powder may be of one type or two or more types.

(Polyanion)
The polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anionic group of this polyanion functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer.
The anion group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ester having a sulfo group, and polymethacrylic acid ester having a sulfo group (for example, poly (4-sulfobutyl methacrylate). , Polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprenesulfonic acid and other polymers with sulfo groups, polyvinylcarboxylic acid, polystyrenecarboxylic acid, etc. Examples thereof include polymers having a carboxy group such as polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), and polyisoprenecarboxylic acid. The polyanion is a single monomer. It may be a homopolymer in which the above is polymerized, or it may be a copolymer in which two or more kinds of monomers are polymerized.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be made higher.
The polyanion may be used alone or in combination of two or more.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1 million or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight is a mass-based average molecular weight obtained in terms of polystyrene as measured by gel permeation chromatography.

The polyanion is doped with the π-conjugated conductive polymer to form a conductive composite having conductivity. When the content ratio of the π-conjugated conductive polymer and the polyanion in the conductive composite is as follows, the conductive composite can form a conductive polymer powder.

The content ratio of the π-conjugated conductive polymer: the polyanion in the conductive complex is (1: 0.5) to (1: 1) on a mass basis, and is (1: 0.5) to (1). 1: 0.90) is preferable, (1: 0.5) to (1: 0.80) are more preferable, and (1: 0.5) to (1: 0.70) are even more preferable.
When it is at least the lower limit of the above range, the doping effect of the polyanion is sufficiently exhibited, and the conductivity of the conductive polymer powder formed by the conductive composite is further improved.
When it is not more than the upper limit of the above range, it becomes a conductive polymer powder which has low dispersibility in water and can be easily precipitated in water while obtaining the doping effect by the polyanion.

In the polyanion of the conductive polymer powder of this embodiment, most or almost all of the anion groups are doped in the π-conjugated conductive polymer, and there are few or almost no surplus anion groups that are not involved in the doping. preferable. By setting the content ratio of the π-conjugated conductive polymer: polyanion to the above-mentioned preferable range, the excess anion group can be reduced or almost eliminated.
With few or few excess anionic groups, the conductive polymer powder is hydrophobic enough to easily precipitate in water. Further, the conductive powder containing the conductive polymer powder can form an electrode exhibiting excellent battery characteristics.

When some of the polyanions in the conductive polymer powder of this embodiment have surplus anion groups that do not participate in doping, these surplus anion groups react with at least one of the amine compound and the epoxy compound. It may be modified hydrophobically.

(Substituent A)
The substituent A that can be formed by reacting the excess anion group with the epoxy compound is represented by, for example, the following structural formula.
Although detailed analysis of the modified conductive complex is not always easy, it is presumed that the substituent (A) is a group represented by the following formula (A1) or a group represented by the following formula (A2). To.

［式（Ａ１）中、Ｒ^１１、Ｒ^１２、Ｒ^１３、及びＲ^１４はそれぞれ独立に、水素原子、又は任意の置換基である。］

[In the formula (A1), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or an arbitrary substituent. ]

［式（Ａ２）中、ｍは２以上の整数であり、複数のＲ^１５、複数のＲ^１６、複数のＲ^１７、及び複数のＲ^１８はそれぞれ独立に、水素原子、又は任意の置換基であり、複数のＲ^１５は同一でも異なっていてもよく、複数のＲ^１６は同一でも異なっていてもよく、複数のＲ^１７は同一でも異なっていてもよく、複数のＲ^１８は同一でも異なっていてもよい。］

[In formula (A2), m is an integer of 2 or more, and a plurality of R ¹⁵ , a plurality of R ¹⁶ , a plurality of R ¹⁷ , and a plurality of R ¹⁸ are independently each of a hydrogen atom or an arbitrary substituent. Yes, the plurality of R ^15s may be the same or different, the plurality of R ^16s may be the same or different, the plurality of R ^17s may be the same or different, and the plurality of R ^18s may be the same or different. You may. ]

In the formulas (A1) and (A2), the leftmost bond represents that the substituent (A) is substituted with the proton of the anion group. Examples of the anion group having a proton to be substituted include an anion group having an active proton bonded to an oxygen atom such as "-SO ₃ H".

In the formula (A1), as any substituent of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent may be used. Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be possessed. R ¹¹ and R ¹³ may be bonded to form a ring which may have a substituent. For example, R ¹¹ and R ¹³ are the hydrocarbon groups, a divalent hydrocarbon group excluding any one hydrogen atom of the monovalent hydrocarbon group of R ¹¹ and a monovalent hydrocarbon of R ¹³ . Examples thereof include a case where a divalent hydrocarbon group excluding any one hydrogen atom of a hydrogen group is bonded to each other by carbon atoms from which the hydrogen atom has been removed to form a ring.
Among them, in the formula (A1), R ¹¹ is a hydrogen atom or an alkoxyalkyl group having 10 to 16 carbon atoms, R ¹² is a hydrogen atom, and R ¹³ is a hydrogen atom or an alkoxyalkyl group having 10 to 16 carbon atoms. It is preferable that R ¹⁴ is a hydrogen atom.

In the formula (A2), as any substituent of R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ , an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent may be used. Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be possessed. R ¹⁵ and R ¹⁷ may be bonded to form a ring which may have a substituent. The example of forming a ring is the same as above.
Among them, in the formula (A2), R ¹⁵ is a hydrogen atom or an alkoxyalkyl group having 10 to 16 carbon atoms, R ¹⁶ is a hydrogen atom, and R ¹⁷ is a hydrogen atom or an alkoxyalkyl group having 10 to 16 carbon atoms. It is preferable that R ¹⁸ is a hydrogen atom.

In the present specification, "may have a substituent" means that the hydrogen atom (-H) is substituted with a monovalent group and the methylene group ( _-CH2- ) is substituted with a divalent group. Includes both cases of replacement.
The monovalent group as a substituent includes an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), and a trialkoxysilyl group. (Trimethoxysilyl group, etc.), etc. may be mentioned.
Examples of the divalent group as a substituent include an oxygen atom (-O-), -C (= O)-, -C (= O) -O- and the like. However, this does not apply when two oxygen atoms are adjacent to each other.

In the formula (A2), m is an integer of 2 or more, preferably 2 to 100, more preferably 2 to 50, and even more preferably 2 to 25. When m is at least the above lower limit value, the hydrophobicity of the conductive complex becomes sufficiently high. When m is not more than the upper limit value, it is possible to suppress that the hydrophobicity becomes too high or the conductivity decreases.

The epoxy group-containing compound (epoxy compound) is a compound having one or more epoxy groups in one molecule. The epoxy compound is preferably a compound having one epoxy group in one molecule from the viewpoint of preventing aggregation or gelation when modifying the conductive complex.
One type of epoxy compound may be used alone, or two or more types may be used in combination.

Examples of the monofunctional epoxy compound having one epoxy group in one molecule include ethylene oxide, propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, and 1 , 2-Epoxide heptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monooxide, 1,2-epoxytetradecane, glycidylmethyl ether, 1,2- Epoxide octadecane, 1,2-epoxyhexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeikosan, 2- (chloromethyl) -1,2-epoxypropane, glycidol, epichlorohydrin, Epibromohydrin, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2- (chloromethyl) -1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2- Epoxy-1H, 1H, 2H, 2H, 3H, 3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidylmethacrylate, 1,2-epoxycyclododecane, 1-Methyl-1,2-epoxide cyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxide-1H, 1H, 2H, 2H, 3H, 3H-Heptadecafluorobutane, 3,4-epoxytetralate, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxysuccinic acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, Benzyl glycidyl ether, diethoxy (3-glycidyloxypropyl) methylsilane, 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxide propane, 1,1,1,3,5,5,5-heptamethyl- 3- (3-glycidyloxypropyl) trisiloxane, 9,10-epoxy-1,5-cyclododecadien, 4-tert-butyl glycidyl benzoate, 2,2-bis (4-glycidyloxyphenyl) propane, 2 -Tert-Butyl-2- [2- (4-chlorophenyl) )] Ethyloxylan, styrene oxide, glycidyltrityl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α, 6α-epoxide, stillbenoxide, glycidyl p-toluenesulfonate , 3-Methyl-3-phenylglycidate ethyl, N-propyl-N- (2,3-epoxypropyl) perfluoro-n-octylsulfonic acid, (2S, 3S) -1,2-epoxy-3-( tert-Butoxycarbonylamino) -4-phenylbutane, 3-nitrobenzene sulfonic acid (R) -glycidyl, 3-nitrobenzene sulfonic acid-glycidyl, parthenolide, N-glycidyl phthalimide, endolin, dirdoline, 4-glycidyl oxycarbazole, 7, Examples thereof include 7-dimethyloctanoic acid [oxylanylmethyl], 1,2-epoxy-4-vinylcyclohexane, and higher alcohol glycidyl ether having 10 to 16 carbon atoms.

As the higher alcohol glycidyl ether, one or more higher alcohol glycidyl ethers having 10 to 16 carbon atoms are preferable, and one or more higher alcohol glycidyl ethers having 12 to 14 carbon atoms are more preferable, and C12 (12 carbon atoms) higher grade. At least one of the alcohol glycidyl ether and the C13 (13 carbon atoms) higher alcohol glycidyl ether is more preferable, and the C12 and C13 mixed higher alcohol glycidyl ether is particularly preferable.

Examples of the polyfunctional epoxy compound having two or more epoxy groups in one molecule include 1,6-hexanediol diglycidyl ether, 1,7-octadiendiepoxide, neopentyl glycol diglycidyl ether, and 4-butanediol. Diglycidyl ether, 1,2: 3,4-diepoxybutane, 1,2-cyclohexanedicarboxylate diglycidyl, triglycidyl isocyanurate, neopentyl glycol diglycidyl ether, 1,2: 3,4-diepoxybutane, polyethylene Glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, Trimethylol propane triglycidyl ether, trimethylol propane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycidyl polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol-based poly Examples thereof include diglycidyl ether and ethylene oxide lauryl alcohol diglycidyl ether.

The epoxy compound preferably has a molecular weight of 50 or more and 2000 or less because it has good reactivity with excess anionic groups. From the same viewpoint, the epoxy compound preferably has 2 or more and 100 or less carbon atoms, more preferably 5 or more and 80 or less, and further preferably 10 or more and 50 or less.

(Substituent B)
The substituent B that can be formed by reacting the excess anion group with the amine compound is represented by, for example, the following structural formula.
Although detailed analysis of the conductive complex is not always easy, it is presumed that the substituent (B) is a group represented by the following formula (B).

-HN ⁺ R ²¹ R ²² R ²³ ... (B)
[In the formula (B), R ²¹ to R ²³ are each independently a hydrocarbon group which may have a hydrogen atom or a substituent, except that at least one of R ²¹ to R ²³ is a substituent. It is a hydrocarbon group which may have. ]

In the substituent (B), the leftmost bond indicates that the negative charge of the anion group and the positive charge of the amine compound are bonded. Examples of the anion group that can be negatively charged include an anion group having an oxygen atom to which an active proton can be bonded ^, such as "-SO _3- ".

R ²¹ to R ²³ in the formula (B) are hydrogen atoms or hydrocarbon groups which may have a substituent. R ²¹ to R ²³ in the formula (B) are substituents derived from the amine compound.
The hydrocarbon group in the formula (B) is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and an aromatic hydrocarbon having 6 to 20 carbon atoms which may have a substituent. The group is mentioned.
Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.
Examples of the substituent which may replace the hydrogen of the aliphatic hydrocarbon group include a phenyl group and a hydroxyl group.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
Examples of the substituent which may replace the hydrogen of the aromatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group and the like.

The amine compound is at least one selected from the group consisting of primary amines (primary amines), secondary amines (secondary amines) and tertiary amines (tertiary amines). One type of amine compound may be used alone, or two or more types may be used in combination.
Examples of the primary amine include aniline, toluidine, benzylamine, ethanolamine and the like.
Examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine and the like.
Examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, trinaphthylamine and the like.
Of the amine compounds, tertiary amines are preferable, and at least one of trioctylamine and tributylamine is more preferable, because the conductive complex can be easily hydrophobized.

The amine compound preferably has a substituent having 4 or more carbon atoms on the nitrogen atom, and more preferably has a substituent having 6 or more carbon atoms on the nitrogen atom.

(Substituent C)
When the amine compound reacted with the surplus anionic group is a heterocyclic aromatic amine, the substituent C formed by the reaction with the heterocyclic aromatic amine is represented by, for example, the following structural formula.

-HN ⁺ R ²⁴ ... (C)
[In the formula (C), N ⁺ R ²⁴ represents a heterocyclic aromatic amine containing a nitrogen atom positively charged by the addition of a proton. ]
Here, the heterocyclic aromatic amine means a cyclic amine compound containing a nitrogen atom constituting the aromatic ring, and the hydrogen atom bonded to the amine compound may be arbitrarily substituted.

In the formula (C), the leftmost bond represents that the negative charge of the anion group and the positive charge of the heterocyclic aromatic amine are bonded. Examples of the anion group that can be negatively charged include an anion group having an oxygen atom to which an active proton can be bonded ^, such as "-SO _3- ".

If the basicity of the heterocyclic aromatic amine is too strong, the conductivity of the modified conductive complex may decrease. Therefore, among the heterocyclic aromatic amines, the imidazole amine having a weak basicity is used. preferable. Here, the imidazole-based amine means a compound having an imidazole ring, and a hydrogen atom bonded to the imidazole ring may be arbitrarily substituted.

Examples of the substituent which may arbitrarily substitute the hydrogen atom of the imidazole ring include a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Be done. The hydrogen atoms constituting these substituents may be substituted with a hydroxyl group or a cyano group. Further, the divalent or trivalent group constituting these substituents may be substituted with —C (= O) −, —C (= O) —O−, —N =, or the like. Further, when it has two or more substituents that substitute hydrogen atoms in the imidazole ring, these substituents may be bonded to each other to form a ring.

Examples of the imidazole-based amine include imidazole, 2-methylimidazole, 2-propyl imidazole, N-methylimidazole, 1- (2-hydroxyethyl) imidazole, 2-ethyl-4-methylimidazole, 1,2-dimethyl. Imidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, Examples thereof include 2-aminobenzimidazole, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole, 2- (2-pyridyl) benzimidazole and the like.
Of these, imidazole is preferable because it has good reactivity with the anionic group of the conductive complex and is inexpensive.

The electrical conductivity (unit: S / cm) of the conductive polymer powder of this embodiment is preferably 0.1 or more and 100 or less, more preferably 0.3 or more and 100 or less, still more preferably 1 or more and 100 or less, and 2 More than 100 or less is particularly preferable, and 3 or more and 100 or less is most preferable.
The higher the electrical conductivity, the higher the conductivity of the conductive polymer powder, which is preferable.
The upper limit of the electric conductivity is not particularly limited, and a value of 100 or less in the above range is a guide.
The electric conductivity of the conductive polymer powder of this embodiment is measured by using a molded product obtained by compacting the conductive polymer powder as a sample.

The number average particle size of the conductive polymer powder of this embodiment is preferably 0.1 μm or more and 100 μm or less, more preferably 0.5 μm or more and 50 μm or less, and further preferably 1 μm or more and 10 μm or less.
When it is at least the lower limit of the above range, it becomes easier to handle as a powder.
When it is not more than the upper limit of the above range, the dispersibility of the conductive polymer powder with respect to the binder component is further improved.
The number average particle size of the conductive polymer powder of this embodiment is a number-based average particle size measured by using a dynamic light scattering particle size distribution measuring device.

(Sulfate ion content)
The content of sulfate ion contained in the conductive polymer powder of this embodiment is obtained by mixing 1 g of the conductive polymer powder and 99 g of ion-exchanged water (20 ° C.) to obtain the powder-containing water. The amount of sulfate ions in the powder-containing water after stirring for 10 minutes is 0.108% by mass or less with respect to the total mass of the powder-containing water.

Here, when 1 g of the conductive polymer powder is weighed, the amount of water contained in the conductive polymer powder in advance is 10% by mass or less with respect to the total mass of the conductive polymer powder. do.
It is preferable to reduce the water content to 5% by mass or less by drying the conductive polymer powder before weighing. The method of drying is not particularly limited, and conventional methods such as freeze-drying, heat-drying, air-drying, and natural drying can be applied. Since the conductive polymer powder has hygroscopicity, it is difficult to reduce the water content to 0% by mass in a normal laboratory atmosphere.
The water content is a value measured by the Karl Fischer method.

The content of sulfate ion in the powder-containing water is a value measured by a known ion chromatography method. Specifically, the measurement sample is introduced into an anion exchange column that adsorbs sulfate ions, the sulfate ions in the measurement sample are adsorbed, and then the amount of sulfate ions is eluted with a known elution agent. At this time, a method is known in which a change in the electric conductivity meter of the eluate is measured and the amount of sulfate ion is calculated from the change amount.
From the viewpoint of improving the accuracy of the measured value, it is preferable to use a column manufactured by Thermo Fisher Scientific Co., Ltd., model number: Dionex IonPac AS-19-4 μm, as the anion exchange column. Further, it is preferable to use an aqueous potassium hydroxide solution as the eluent.

The preferred range of the sulfate ion content varies depending on the ratio of the π-conjugated conductive polymer constituting the conductive polymer powder to the polyanion.
When the ratio is based on mass and the π-conjugated conductive polymer: polyanion = (1: 0.5) to (1: 0.75) (however, the case where it is 1: 0.75 is excluded). The content of the sulfate ion is preferably 0.010% by mass or more and 0.090% by mass or less, more preferably 0.015% by mass or more and 0.070% by mass or less, and 0.020% by mass or more and 0.060% by mass or less. % Or less is more preferable, 0.025% by mass or more and 0.055% by mass or less is particularly preferable, and 0.030% by mass or more and 0.050% by mass or less is most preferable.
When the ratio is based on mass and the π-conjugated conductive polymer: polyanion = (1: 0.75) to (1: 1), the iron content is 0.040% by mass or more and 0.100. It is preferably 0.045% by mass or more, more preferably 0.095% by mass or less, further preferably 0.050% by mass or more and 0.090% by mass or less, and 0.055% by mass or more and 0.085% by mass or less. Is particularly preferable, and 0.060% by mass or more and 0.080% by mass or less is most preferable.
Within the above-mentioned suitable range, the conductivity of the conductive molded body or the electrode containing the conductive polymer powder of this embodiment can be further enhanced.

The conductive polymer powder of this embodiment may contain water, but it is preferable that the content of water is small. The content of water with respect to the total mass of the conductive polymer powder is, for example, preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less. Most preferably, the water content is substantially 0% by mass. However, the water content exemplified here is not a preferable water content when measuring the sulfate ion content.
When it is not more than the upper limit of the above range, aggregation of the conductive polymer powder can be suppressed when mixed with a non-aqueous material, for example, a binder component.
The content of water contained in the conductive polymer powder is a value measured by the Karl Fischer method.

[Conductive aid]
The conductive polymer powder of this embodiment may contain a conductive auxiliary agent other than the above-mentioned conductive polymer powder.
Examples of the conductive auxiliary agent include a conductive auxiliary agent added to the electrode active material of a known lithium ion secondary battery. Specific examples thereof include carbon materials and metal particles.
Examples of the carbon material include carbon black, graphite, vapor-grown carbon fiber, carbon nanofiber, carbon nanotube, and graphene.
Examples of the metal particles include silver particles, copper particles, gold particles, aluminum particles and the like.
The conductive auxiliary agent contained in this embodiment may be one kind or two or more kinds.

The content of the conductive auxiliary agent with respect to the total mass of the conductive polymer powder of this embodiment can be, for example, 0% by mass or more and 10% by mass or less.

(Other optional ingredients)
The conductive polymer powder of this embodiment may contain an arbitrary component other than the above-mentioned conductive auxiliary agent. Specific examples thereof include inorganic compounds (excluding carbon materials and metal particles).
Examples of the inorganic compound include silica, silica-alumina, glass, calcium carbonate, calcium hydroxide, talc, alumina, titania, zirconia, magnesium hydroxide, aluminum hydroxide, hydrotalcite, mica and the like.

The content of the other optional component with respect to the total mass of the conductive polymer powder of this embodiment can be, for example, 0% by mass or more and 10% by mass or less.

<< Conductive polymer composition >>
The second aspect of the present invention is a conductive polymer composition containing the conductive powder of the first aspect and a binder component. The form of this embodiment may be liquid, gel-like, or solid-like.

(Binder component)
The binder component is a resin other than the π-conjugated conductive polymer and the polyanion or a precursor thereof, and is a thermoplastic resin or a curable monomer or oligomer that cures when the conductive layer is formed. The thermoplastic resin becomes a binder resin as it is, and the curable monomer or oligomer is a resin formed by curing as a binder resin.
The binder component contained in the conductive polymer composition of this embodiment may be one kind or two or more kinds.

Specific examples of the binder resin derived from the binder component include epoxy resin, acrylic resin (acrylic compound), polyester resin, polyurethane resin, polyimide resin, polyether resin, melamine resin, silicone and the like.

The curable monomer or oligomer may be a thermosetting monomer or oligomer, or may be a photocurable monomer or oligomer. Here, the oligomer is a polymer having a mass average molecular weight of less than 10,000.
Examples of the curable monomer include an acrylic monomer (acrylic compound), an epoxy monomer, an organosiloxane, and the like. Examples of the curable oligomer include an acrylic oligomer (acrylic compound), an epoxy oligomer, and a silicone oligomer (curable silicone).
When an acrylic monomer or an acrylic oligomer is used as the binder component, it can be easily cured by heating or light irradiation.

When a curable monomer or oligomer is contained, it is preferable to further contain a curing catalyst. For example, when a thermosetting monomer or oligomer is contained, it is preferable to contain a thermopolymerization initiator that generates a radical by heating, and when a photocurable monomer or oligomer is contained, a radical is generated by light irradiation. It is preferable to include a photopolymerization initiator to cause the reaction.

The content ratio of the binder component in the conductive polymer composition of this embodiment can be, for example, 10 parts by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of the conductive polymer powder, and 100 parts by mass or more. It is preferably 5000 parts by mass or less, more preferably 200 parts by mass or more and 3000 parts by mass or less, and further preferably 300 parts by mass or more and 1500 parts by mass or less.
When it is at least the lower limit of the above range, the film-forming property and the film strength when the coating material made of the conductive polymer composition of this embodiment is applied to a film substrate or the like can be improved.
When it is not more than the upper limit of the above range, the decrease in conductivity due to the decrease in the content ratio of the conductive polymer powder can be suppressed.

The content of the conductive polymer powder in the conductive polymer composition of this embodiment is preferably, for example, 0.1% by mass or more and 30% by mass, more preferably 0.5% by mass or more and 20% by mass or less. It is more preferably 1% by mass or more and 10% by mass or less.
When it is at least the lower limit of the above range, a conductive layer having excellent conductivity can be formed.
When it is not more than the upper limit of the above range, a relatively large amount of the binder component can be contained, and a conductive layer having excellent mechanical strength can be formed.

The conductive polymer composition of this embodiment may contain a dispersion medium for dilution. The dispersion medium may be water, an organic solvent, or a mixed solution of water and an organic solvent.

Examples of the organic solvent include alcohol-based solvents (alcohols), ether-based solvents, ketone-based solvents, nitrogen atom-containing solvents and the like.
Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, and the like. Examples thereof include ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether.
Examples of the ether solvent include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, diethylene glycol diethyl ether and the like.
Examples of the ketone solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like.
Examples of the nitrogen atom-containing solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.
The organic solvent contained in the conductive polymer composition of this embodiment may be one kind or two or more kinds.

(Other additives)
The conductive polymer composition of this embodiment may contain other additives other than the binder component and the dispersion medium.
Examples of the additive include a surfactant, an inorganic conductive agent, a defoaming agent, an antioxidant, an ultraviolet absorber and the like.
However, the additive is other than the above-mentioned π-conjugated conductive polymer, polyanion, and conductive auxiliary agent.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferable from the viewpoint of storage stability. Further, a polymer-based surfactant such as polyvinylpyrrolidone may be added.
Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and the like.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, saccharides and the like.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, etc. Can be mentioned.

When the conductive polymer composition of this embodiment contains the other additives, the content ratio thereof is appropriately determined depending on the type of the additive, and is, for example, with respect to 100 parts by mass of the conductive polymer powder. The range can be 0.001 part by mass or more and 5 parts by mass or less.

≪Conductive molded body≫
Another aspect related to the present invention is a conductive molded product containing the conductive polymer powder of the first aspect. The conductive molded body of this embodiment is preferably a conductive molded body obtained by compacting the conductive polymer powder of the first aspect.
The shape of the conductive molded body is not particularly limited, and examples thereof include a plate shape, a sheet shape, a film shape, a rod shape, and a columnar shape.
The average thickness of the plate-shaped, sheet-shaped, and film-shaped conductive molded bodies is preferably, for example, 0.01 μm or more and 1000 μm or less, from the viewpoint of reducing electrical resistance and reducing the thickness of the conductive molded bodies. More preferably, it is 1 μm or more and 100 μm or less.
The average thickness of the plate-shaped, sheet-shaped, and film-shaped conductive molded bodies is 10 or more randomly selected by observing the cross section of the conductive molded body using a magnifying observation means such as a measuring microscope. It is the average value of the measured value of the thickness.
The conductive molded product of this embodiment may be supported by a base material such as a film or a substrate, or may be an independent conductive molded product.

<Manufacturing method of conductive molded product>
As a method for producing the conductive molded body of the present embodiment, for example, a method of molding the conductive polymer powder of the first aspect into a desired shape by a known method of molding a known powder, and a method of forming the conductive molded body of the second aspect. A method of applying a coating material made of a conductive polymer composition to a desired substrate and drying the substrate to form a conductive molded product (for example, a conductive layer) containing the conductive powder of the first aspect on the surface of the substrate. Can be mentioned.
As a method for molding the conductive polymer powder of the first aspect, for example, the shape of the mold is reflected by filling the mold with the conductive polymer powder of the first aspect and compacting the mold. Examples thereof include a method of obtaining a conductive molded body having a shape.
The base material to which the coating material made of the conductive polymer composition of the second aspect is applied is not particularly limited, and examples thereof include a base material made of any material such as plastic, glass, and metal. The coating method is not particularly limited, and a conventional method may be applied.

≪Electrodes≫
The third aspect of the present invention is an electrode containing the conductive polymer powder of the first aspect.
The shape of the electrode is not particularly limited, and examples thereof include known electrode shapes such as a plate shape, a sheet shape, a film shape, a rod shape, and a columnar shape.
The average thickness of the plate-shaped, sheet-shaped, and film-shaped electrodes is preferably, for example, 0.01 μm or more and 1000 μm or less, and 0.1 μm or more and 100 μm or less, from the viewpoint of achieving both reduction of electrical resistance and thinning of the electrodes. preferable.
The average thickness of the plate-shaped, sheet-shaped, and film-shaped electrodes is a value obtained by observing the cross section of the electrode using a magnifying observation means such as a measuring microscope and measuring the thickness of 10 or more randomly selected points. Is the average value of.
The electrode of this embodiment may be supported by a base material such as a film or a substrate, or may be an independent electrode.
When the electrode of this embodiment is used as an electrode of a lithium ion secondary battery, it may be a positive electrode or a negative electrode.

As a measure of good conductivity, the electrode preferably has a surface resistance value of less than 10 Ω / □, and more preferably a surface resistance value of 0.5 Ω / □ or more and 9 Ω / □ or less.

<Method of manufacturing electrodes>
As a method for producing an electrode according to the present embodiment, for example, a method for molding the conductive polymer powder of the first aspect into an electrode having a desired shape, and a coating material comprising the conductive polymer composition of the second aspect are desired. Examples thereof include a method of applying to a material and drying to form an electrode layer (conductive layer) containing the conductive polymer powder of the first aspect on the surface of the base material.
The method for forming the conductive polymer powder of the first aspect is not particularly limited, and for example, a binder and the like contained in the electrode active material of a known lithium ion secondary battery and the conductive polymer powder of the first aspect are used. May be kneaded to obtain pellets, and the pellets may be used for molding with a molding die or the like, or may be extruded. Alternatively, the mold may be filled with the conductive polymer powder and compacted to form a three-dimensional electrode that reflects the shape of the mold.
As the base material to which the coating material made of the conductive polymer composition of the second aspect is applied, a base material that supports the electrode active material layer of a known battery can be applied, and for example, a metal material such as a metal foil or a metal plate can be used. Can be mentioned. For example, copper foil, aluminum foil, stainless steel plate and the like can be mentioned. Further, a known resin film or resin plate may be used as a base material. The coating method is not particularly limited, and a conventional method may be applied.

<Battery>
Batteries and capacitors provided with the electrodes of this embodiment can also be manufactured.
The battery may be a primary battery or a secondary battery. The form of the battery is not particularly limited, and examples thereof include known battery forms such as a dry battery, an electrode laminated laminated battery, and a button battery.
The battery usually has a positive electrode, a negative electrode, and an electrolyte. The electrode of this embodiment may be a positive electrode or a negative electrode. It is preferable that the positive electrode and the negative electrode of the battery are insulated by a separator such as a non-woven fabric.
The battery is preferably a lithium ion secondary battery.

<Manufacturing method of conductive film>
In another aspect related to the present invention, the coating material comprising the conductive polymer composition of the second aspect is applied to at least one surface of the film substrate to cure the coating film formed on the film substrate. This is a method for producing a conductive film, which obtains a conductive film having the conductive layer formed on at least a part of the base material by forming the conductive layer.
The conductive layer may be an electrode layer, and the conductive film may be an electrode supported by a film substrate.

(Film base material)
Examples of the film base material include a plastic film.
Examples of the resin for the film base material constituting the plastic film include ethylene-methylmethacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, and polybutylene terephthalate. , Polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene-based elastomer, polyester-based elastomer, polyether sulfone, polyetherimide, polyether ether ketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio Examples include Nate. Among these resins for film substrates, polyethylene terephthalate is preferable because it is inexpensive and has excellent mechanical strength.

The resin for the film substrate may be amorphous or crystalline.
The film substrate may be unstretched or stretched.
The film substrate may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, etc. in order to further improve the adhesion of the conductive layer formed from the conductive polymer-containing liquid.

The average thickness of the film substrate is preferably 5 μm or more and 500 μm or less, and more preferably 20 μm or more and 200 μm or less. When the average thickness of the film substrate is at least the lower limit value, it is difficult to break, and when it is at least the upper limit value, sufficient flexibility as a film can be ensured.
The thickness of the film substrate is a value obtained by measuring the thickness at any 10 points and averaging the measured values.

Examples of the method of applying (applying) the paint to the film substrate include a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a kiss coater, a fountain coater, a rod coater, and an air doctor coater. A method using a coater such as a knife coater, a blade coater, a cast coater, a screen coater, a method using an atomizer such as an air spray, an airless spray, or a rotor dampening, a dipping method such as a dip, or the like can be applied.

A conductive film having a conductive layer formed can be obtained by drying and curing a coating film made of the paint coated on a film substrate.
Examples of the method for drying the coating film include heat drying and vacuum drying. As the heat drying, for example, a usual method such as hot air heating or infrared heating can be adopted.
When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium used, but is usually in the range of 50 ° C. or higher and 150 ° C. or lower. Here, the heating temperature is a set temperature of the drying device.

When the coating material contains a thermosetting monomer or oligomer as a binder component, the coating film is heated to cure the binder component, whereby a conductive film having a conductive layer formed can be obtained.
When the coating material contains a photocurable monomer or oligomer as a binder component, the coating film is irradiated with ultraviolet rays or electron beams to cure the binder component, thereby forming a conductive film having a conductive layer. Obtainable.

<Conductive film>
Another aspect related to the present invention is a conductive film having a film base material and a conductive layer provided on at least one surface of the film base material, and the conductive layer has the high conductivity of the first aspect. A conductive film containing molecular powder. The conductive film of this embodiment can be manufactured by the above-mentioned manufacturing method.
The conductive layer may be an electrode layer, and the conductive film may be an electrode supported by a film substrate.

(Conductive layer)
The average thickness of the conductive layer provided on at least one surface of the film substrate is, for example, preferably 1 μm or more and 50 μm or less, and more preferably 2 μm or more and 10 μm or less.
When the average thickness of the conductive layer is not less than the lower limit value, sufficiently high conductivity can be exhibited, and when it is not more than the upper limit value, the conductive layer can be easily formed.

As a measure of good conductivity, the conductive layer preferably has a surface resistance value of 1 Ω / □ or more and 1 × 10 ¹⁰ Ω / □ or less, and is preferably 10 Ω / □ or more and 1 × 10 ⁹ Ω / □ or less. It is more preferable to have a surface resistance value, and it is further preferable to have a surface resistance value of 100 Ω / □ or more and 1 × 10 ⁸ Ω / □ or less.

<< Manufacturing method of conductive polymer powder (1) >>
A fourth aspect of the present invention is to oxidatively polymerize the monomer by adding a catalyst and an oxidizing agent to a reaction solution containing a monomer capable of forming a π-conjugated conductive polymer, a polyanion, and water. A step of forming a conductive polymer powder containing a π-conjugated conductive polymer and the polyanion (polymerization step), and a step of separating the conductive polymer powder from the reaction solution (separation step). It is a method for producing a conductive polymer powder having the above.
The content ratio of the monomer: the polyanion in the reaction solution is (1: 0.5) to (1: 1) on a mass basis.
1 g of the conductive polymer powder separated from the reaction solution and 99 g of ion-exchanged water (20 ° C.) were mixed, and the obtained powder-containing water was stirred, and the powder after 10 minutes had passed. The amount of sulfate ion in the contained water is 0.108% by mass or less with respect to the total mass of the powder-containing water.

(Polymerization process)
In this step, an aqueous solution (reaction solution) containing the monomer and the polyanion in a specific content ratio is prepared, and the monomer is polymerized to form a π-conjugated conductive polymer. In the reaction solution, the polyanion is naturally doped into the π-conjugated conductive polymer to form a conductive polymer powder containing a conductive composite composed of the π-conjugated conductive polymer and the polyanion. The content ratio (mass basis) of the π-conjugated conductive polymer: polyanion contained in the formed conductive composite is the content of the monomer contained in the aqueous solution immediately before the start of polymerization and the polyanion. It is the same as the content ratio of. That is, the content ratio of the monomer and the polyanion blended in the reaction solution is reflected in the content ratio of the π-conjugated conductive polymer and the polyanion in the formed conductive composite and the conductive polymer powder.

The content ratio of the monomer: the polyanion contained in the reaction solution immediately before the start of polymerization is (1: 0.5) to (1: 1) on a mass basis, and is (1: 0.5) to (1: 1). 0.90) is preferable, (1: 0.5) to (1: 0.80) are more preferable, and (1: 0.5) to (1: 0.70) are even more preferable.
When it is at least the lower limit of the above range, the doping effect of the polyanion is sufficiently exhibited, and a conductive polymer powder having more excellent conductivity can be obtained.
When it is not more than the upper limit of the above range, it is possible to form a conductive polymer powder having low dispersibility in water and easily precipitating while obtaining the doping effect by the polyanion.

In this step, the catalyst contained in the reaction solution is not particularly limited as long as it polymerizes the monomer, and for example, ferric chloride, ferric sulfate, ferric nitrate, ferric chloride and the like can be used. Examples include transition metal compounds.
It is preferable to contain an oxidizing agent together with the catalyst. The oxidant can restore the reduced catalyst to its original oxidized state. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.
When a catalyst containing Fe (iron) is used as the catalyst, Fe derived from the catalyst may be contained in the conductive polymer powder.

In this step, sulfuric acid may be added to the reaction solution. By adding sulfuric acid, the sulfate ion contained in the produced conductive polymer powder can be increased.

The content of the monomer contained in the reaction solution immediately before the start of polymerization is, for example, preferably 0.1% by mass or more and 20% by mass or less, and 0.3% by mass or more and 10% by mass with respect to the total mass of the reaction solution. % Or less is more preferable, and 0.5% by mass or more and 5% by mass or less is further preferable.
When it is at least the lower limit of the above range, the formed conductive polymer powder can be easily separated.
When it is not more than the upper limit of the above range, the polymerization reaction can proceed stably, so that the complexing with the polyanion existing in the reaction system proceeds stably, and a high-quality conductive polymer powder having high conductivity can be easily obtained. be able to.

The content of the polyanion contained in the reaction solution immediately before the start of polymerization is preferably set based on the content ratio with respect to the monomer.

The content of the catalyst contained in the reaction solution immediately before the start of polymerization is, for example, preferably 0.01% by mass or more and 3% by mass or less, and 0.1% by mass or more and 2% by mass with respect to the total mass of the reaction solution. % Or less is more preferable, and 0.3% by mass or more and 1% by mass or less is further preferable.
When it is at least the lower limit of the above range, the conductive polymer powder can be easily formed.
When it is not more than the upper limit of the above range, the polymerization reaction can proceed stably, so that the complexing with the polyanion existing in the reaction system proceeds stably, and a high-quality conductive polymer powder having high conductivity can be easily obtained. be able to.

From the viewpoint of accelerating the polymerization reaction, the reaction solution may be heated and reacted while stirring. The heating temperature of the reaction solution can be, for example, 60 to 100 ° C.
When it is at least the lower limit of the above range, the polymerization reaction can be sufficiently promoted.
When it is not more than the upper limit of the above range, deterioration due to heat of the π-conjugated conductive polymer can be suppressed.
The reaction time performed at the heating temperature in the above range can be, for example, about 1 to 10 hours.

(Precipitation process)
A precipitation step may be provided between the polymerization step and the recovery step. In this step, the method of precipitating the conductive polymer powder in the reaction liquid after the polymerization reaction of the monomer is not particularly limited, and for example, a method of allowing the reaction liquid after the reaction to stand still, or a reaction liquid after the reaction. A method of slowly stirring the reaction solution, a method of cooling the reaction solution after the reaction to about −20 ° C. to 4 ° C., a method of adding at least one of an amine compound and an epoxy compound to the reaction solution, and the like can be mentioned. In either method, the conductive polymer powder can be naturally precipitated due to its insoluble property in water.

By adding at least one of the amine compound and the epoxy compound to the reaction solution after the polymerization reaction, at least one of the amine compound and the epoxy compound is added to the surplus anionic group of the conductive composite formed after the polymerization reaction. By reacting with the above and modifying the excess anionic group, the hydrophobicity of the conductive composite is enhanced, and it becomes easier to precipitate the conductive polymer powder in the reaction solution.

Since the description of the amine compound and the epoxy compound added to the reaction solution is the same as the description of the first aspect, duplicated description will be omitted. The type of the amine compound or the epoxy compound added to the reaction solution may be one type or two or more types.

The amount of the amine compound added to the reaction solution is preferably 100 parts by mass or more and 10,000 parts by mass or less, preferably 200 parts by mass, with respect to 100 parts by mass of the conductive composite constituting the conductive polymer powder. It is more preferably 6000 parts by mass or less, and further preferably 300 parts by mass or more and 3000 parts by mass or less. When it is at least the lower limit of the above range, the hydrophobicity of the conductive composite is sufficiently improved, and the precipitated conductive composite floats on the upper layer of the reaction solution, so that the yield is good as a conductive polymer powder. It can be recovered. When it is not more than the upper limit of the above range, the decrease in conductivity due to the modification of the conductive composite can be suppressed.

The amount of the epoxy compound added to the reaction solution is preferably 100 parts by mass or more and 10,000 parts by mass or less, preferably 200 parts by mass, with respect to 100 parts by mass of the conductive composite constituting the conductive polymer powder. It is more preferably 6000 parts by mass or less, and further preferably 300 parts by mass or more and 3000 parts by mass or less. When it is at least the lower limit of the above range, the hydrophobicity of the conductive composite is sufficiently improved, and the precipitated conductive composite is settled in the lower layer of the reaction solution, so that the yield is good as a conductive polymer powder. It can be recovered. When it is not more than the upper limit of the above range, the decrease in conductivity due to the modification of the conductive composite can be suppressed.

An organic solvent may be added before, at the same time as, or after the addition of the amine compound or the epoxy compound to the reaction solution. As the organic solvent, a water-soluble organic solvent is preferable. Examples of the water-soluble organic solvent include alcohol-based solvents, ketone-based solvents, and ester-based solvents. The water-soluble organic solvent to be added may be one kind or two or more kinds.

(Preparation process)
The preparative step is a step of separating and recovering the conductive polymer powder containing the conductive composite formed in the reaction liquid from the reaction liquid. Examples of the preparative method include a method of naturally precipitating the conductive polymer powder on the bottom of the container containing the reaction solution to remove the supernatant liquid, and a method of removing the supernatant liquid, and the conductive polymer suspended in the upper layer of the reaction solution. A method of sucking and collecting the powder, a method of filtering the reaction solution to obtain a conductive polymer powder on a filter, and a method of centrifuging the conductive polymer powder on the bottom of the container containing the reaction solution. Examples thereof include a method of forming pellets, a method of spraying the reaction solution into a gas and drying it to obtain a dried conductive polymer powder, and the like.
Among these recovery methods, the method of naturally precipitating or suspending and recovering is preferable because it has few impurities, is excellent in conductivity, and can easily obtain a conductive polymer powder having excellent fluidity.

Since the conductive polymer powder immediately after being recovered from the reaction solution has a reaction solution containing a catalyst, an oxidizing agent, or the like attached to the conductive polymer powder, the conductive polymer powder may be washed with water or an organic solvent.
Specifically, for example, a method of recovering the conductive polymer powder from the cleaning liquid by adding a conductive polymer powder to a cleaning liquid consisting of water or an organic solvent, stirring the mixture, and then precipitating again. Can be mentioned.
As the organic solvent, for example, at least one selected from isopropyl alcohol, methanol, and acetone is preferable because it is difficult to dissolve the conductive polymer powder and has excellent detergency.

The conductive polymer powder obtained in this step can be dried to obtain a dry powder that is easy to handle. The drying method is not particularly limited, and a known method for drying the powder is applied.

The conductive polymer powder obtained in this step may be pulverized so as to have a desired particle size. The crushing method is not particularly limited, and examples thereof include a method of grinding and crushing using a mortar, a method of crushing using a crusher, and the like. Examples of the crusher include a homogenizer, a ball mill, a bead mill, a roller mill, a jet mill, a hammer mill and the like.

The method of pulverizing the conductive polymer powder may be a wet method of pulverizing in a dispersion medium or a dry method of pulverizing in a state containing no dispersion medium. A wet type is preferable in that a conductive polymer powder having a number average particle diameter of 0.1 μm or more and 100 μm or less can be easily produced. When the wet type is applied, the conductive polymer powder is obtained in a state of being dispersed in the dispersion medium. The dispersion medium used for wet pulverization preferably contains, for example, one or more selected from isopropyl alcohol, methanol, and acetone. When these preferable dispersion media are used, it is possible to more easily produce a conductive polymer powder having a number average particle diameter in the range of 0.1 μm or more and 100 μm or less without impairing the conductivity of the conductive polymer powder.

By each of the steps described above, the conductive polymer powder of the first aspect can be easily produced.
The content of sulfate ion contained in the produced conductive polymer powder can be adjusted by the amount of sulfate added as a catalyst in the polymerization step. Further, when increasing the content of sulfate ion, an appropriate amount of sulfuric acid may be added to the reaction solution in the oxidative polymerization step. On the contrary, when it is desired to reduce the content of sulfate ions, the conductive polymer powder may be washed by the above-mentioned method.

(Production Example 1) Production of polystyrene sulfonic acid 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water was added by dissolving 206 g of sodium styrene sulfonate in 1000 ml of ion-exchanged water and stirring at 80 ° C. The solution was added dropwise for 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 sodium polystyrene sulfonate-containing solution, and 1000 ml of the solvent of the obtained polystyrene sulfonate-containing solution was removed by an ultrafiltration method. Then, 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by an ultrafiltration method, and the polystyrene sulfonic acid was washed with water. This washing operation was repeated 3 times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.

(Example 1)
A solution of 5.0 g of 3,4-ethylenedioxythiophene and 2.5 g of polystyrene sulfonic acid in 997.5 ml of ion-exchanged water was mixed at 20 ° C.
An oxidation catalyst of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. The solution was added slowly and stirred for 24 hours for reaction.
The obtained reaction solution was filtered to obtain 7.5 g (PEDOT: PSS = 5 g: 2.5 g) of a polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS) powder.

1 g of the powder from which water was removed by drying was added to 99 g of ion-exchanged water (20 ° C.) to obtain powder-containing water, which was lightly stirred to obtain a supernatant liquid after 10 minutes. Using ion chromatography (column manufactured by Thermo Fisher Scientific Co., Ltd., model number: Dionex IonPac AS-19-4 μm), the sulfate ion concentration (unit: mass%) with respect to the total mass of the powder-containing water was measured. The results are shown in Table 1.

Next, a PET film (manufactured by Toray Industries, Inc., Lumirror, T60, thickness 188 μm) cut out at a 15 mm square was placed on an iron plate, and the obtained powder was put on the PET film (on the cut out film portion) to 0. .1 g was placed, another iron plate was placed, and the mixture was pressed at a pressure of 5N / 225 mm ² for 3 minutes. Table 1 shows the results of taking out a 15 mm square plate-shaped conductive molded body made of powder solidified between iron plates and measuring the surface resistance value thereof.

(Example 2)
A solution of 5.0 g of 3,4-ethylenedioxythiophene, 2.5 g of polystyrene sulfonic acid and 0.5 g of sulfuric acid in 997.0 ml of ion-exchanged water was mixed at 20 ° C.
An oxidation catalyst of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. The solution was added slowly and stirred for 24 hours for reaction.
The obtained reaction solution was filtered to obtain 7.5 g (PEDOT: PSS = 5 g: 2.5 g) of PEDOT-PSS powder. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
7.5 g of PEDOT-PSS powder was obtained in the same manner as in Example 2 except that sulfuric acid was changed to 1.0 g and ion-exchanged water was changed to 996.5 ml in Example 2. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 4)
7.5 g of PEDOT-PSS powder was obtained in the same manner as in Example 2 except that sulfuric acid was changed to 2.5 g and ion-exchanged water was changed to 995.0 ml in Example 2. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
7.5 g of PEDOT-PSS powder was obtained in the same manner as in Example 2 except that sulfuric acid was changed to 5.0 g and ion-exchanged water was changed to 992.5 ml in Example 2. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 6)
7.5 g of PEDOT-PSS powder was obtained in the same manner as in Example 2 except that sulfuric acid was changed to 7.5 g and ion-exchanged water was changed to 990.0 ml in Example 2. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 7)
7.5 g of PEDOT-PSS powder was obtained in the same manner as in Example 2 except that sulfuric acid was changed to 10.0 g and ion-exchanged water was changed to 987.5 ml in Example 2. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 8)
7.5 g of PEDOT-PSS powder was obtained in the same manner as in Example 2 except that sulfuric acid was changed to 12.5 g and ion-exchanged water was changed to 985.0 ml in Example 2. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 9)
7.5 g of PEDOT-PSS powder was obtained in the same manner as in Example 2 except that sulfuric acid was changed to 15.0 g and ion-exchanged water was changed to 982.5 ml in Example 2. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 10)
7.5 g of PEDOT-PSS powder was obtained in the same manner as in Example 2 except that sulfuric acid was changed to 17.5 g and ion-exchanged water was changed to 980.0 ml in Example 2. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
7.5 g of PEDOT-PSS powder was obtained in the same manner as in Example 2 except that sulfuric acid was changed to 20.0 g and ion-exchanged water was changed to 977.5 ml in Example 2. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 11)
5.0 g of 3,4-ethylenedioxythiophene and a solution of 5.0 g of polystyrene sulfonic acid in 995.0 ml of ion-exchanged water were mixed at 20 ° C.
An oxidation catalyst of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. The solution was added slowly and stirred for 24 hours for reaction.
The obtained reaction solution was filtered to obtain 10.0 g (PEDOT: PSS = 5 g: 5 g) of PEDOT-PSS powder. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 12)
A solution of 5.0 g of 3,4-ethylenedioxythiophene, 5.0 g of polystyrene sulfonic acid and 0.5 g of sulfuric acid in 994.5 ml of ion-exchanged water was mixed at 20 ° C.
An oxidation catalyst of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. The solution was added slowly and stirred for 24 hours for reaction.
The obtained reaction solution was filtered to obtain 10.0 g (PEDOT: PSS = 5 g: 5 g) of PEDOT-PSS powder. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 13)
10.0 g of PEDOT-PSS powder was obtained in the same manner as in Example 12 except that sulfuric acid was changed to 1.0 g and ion-exchanged water was changed to 994.0 ml in Example 12. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 14)
10.0 g of PEDOT-PSS powder was obtained in the same manner as in Example 12 except that sulfuric acid was changed to 2.5 g and ion-exchanged water was changed to 992.5 ml in Example 12. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 15)
10.0 g of PEDOT-PSS powder was obtained in the same manner as in Example 12 except that sulfuric acid was changed to 5.0 g and ion-exchanged water was changed to 990.0 ml in Example 12. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 16)
10.0 g of PEDOT-PSS powder was obtained in the same manner as in Example 12 except that sulfuric acid was changed to 7.5 g and ion-exchanged water was changed to 987.5 ml in Example 12. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 17)
10.0 g of PEDOT-PSS powder was obtained in the same manner as in Example 12, except that sulfuric acid was changed to 10.0 g and ion-exchanged water was changed to 985.0 ml in Example 12. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 18)
10.0 g of PEDOT-PSS powder was obtained in the same manner as in Example 12 except that sulfuric acid was changed to 12.5 g and ion-exchanged water was changed to 982.5 ml in Example 12. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
10.0 g of PEDOT-PSS powder was obtained in the same manner as in Example 12 except that sulfuric acid was changed to 15.0 g and ion-exchanged water was changed to 980.0 ml in Example 12. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
10.0 g of PEDOT-PSS powder was obtained in the same manner as in Example 12 except that sulfuric acid was changed to 17.5 g and ion-exchanged water was changed to 977.5 ml in Example 12. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 4)
10.0 g of PEDOT-PSS powder was obtained in the same manner as in Example 12 except that sulfuric acid was changed to 20.0 g and ion-exchanged water was changed to 975.0 ml in Example 12. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 19)
A solution of 5.0 g of 3,4-ethylenedioxythiophene and 2.5 g of polystyrene sulfonic acid in 997.5 ml of ion-exchanged water was mixed at 20 ° C.
An oxidation catalyst of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. The solution was added slowly and stirred for 24 hours for reaction.
Next, 500 g of isopropanol and 100 g of trioctylamine were added, and the mixture was stirred for 1 hour. Here, it was confirmed that all the reacted products of the precipitated π-conjugated conductive polymer, polyanion and trioctylamine were suspended in the upper layer of the solution. The obtained reaction solution was filtered to obtain 7.7 g (PEDOT: PSS = 5 g: 2.5 g) of a powder of the reaction product of PEDOT-PSS and trioctylamine. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 20)
A solution of 5.0 g of 3,4-ethylenedioxythiophene, 2.5 g of polystyrene sulfonic acid and 10.0 g of sulfuric acid in 997.5 ml of ion-exchanged water was mixed at 20 ° C.
An oxidation catalyst of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. The solution was added slowly and stirred for 24 hours for reaction.
Next, 500 g of isopropanol and 100 g of trioctylamine were added, and the mixture was stirred for 1 hour. Here, it was confirmed that all the reacted products of the precipitated π-conjugated conductive polymer, polyanion and trioctylamine were suspended in the upper layer of the solution. The obtained reaction solution was filtered to obtain 7.7 g (PEDOT: PSS = 5 g: 2.5 g) of a powder of the reaction product of PEDOT-PSS and trioctylamine. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 21)
A solution of 5.0 g of 3,4-ethylenedioxythiophene and 2.5 g of polystyrene sulfonic acid in 997.5 ml of ion-exchanged water was mixed at 20 ° C.
An oxidation catalyst of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. The solution was added slowly and stirred for 24 hours for reaction.
Next, 100 g of butyl glycidyl ether was added, and the mixture was stirred for 1 hour. Here, it was confirmed that all of the precipitated π-conjugated conductive polymer, polyanion, and butyl glycidyl ether reaction product had settled in the lower layer of the solution. The obtained reaction solution was filtered to obtain 7.8 g (PEDOT: PSS = 5 g: 2.5 g) of a reaction product of PEDOT-PSS and butyl glycidyl ether. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 22)
A solution of 5.0 g of 3,4-ethylenedioxythiophene, 2.5 g of polystyrene sulfonic acid and 10.0 g of sulfuric acid in 997.5 ml of ion-exchanged water was mixed at 20 ° C. An oxidation catalyst of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. The solution was added slowly and stirred for 24 hours for reaction.
Next, 100 g of butyl glycidyl ether was added, and the mixture was stirred for 1 hour. Here, it was confirmed that all of the precipitated π-conjugated conductive polymer, polyanion, and butyl glycidyl ether reaction product had settled in the lower layer of the solution. The obtained reaction solution was filtered to obtain 7.8 g (PEDOT: PSS = 5 g: 2.5 g) of a reaction product of PEDOT-PSS and butyl glycidyl ether. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 23)
A solution of 5.0 g of 3,4-ethylenedioxythiophene and 2.5 g of polystyrene sulfonic acid in 997.5 ml of ion-exchanged water was mixed at 20 ° C.
An oxidation catalyst of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. The solution was added slowly and stirred for 24 hours for reaction.
Next, 100 g of butyl glycidyl ether was added and stirred for 1 hour. Subsequently, 500 g of isopropanol and 100 g of trioctylamine were added, and the mixture was stirred for 1 hour. Here, it was confirmed that all of the precipitated π-conjugated conductive polymer, polyanion, butyl glycidyl ether, and trioctylamine reaction product had settled in the lower layer of the solution. The obtained reaction solution was filtered to obtain 8.0 g (PEDOT: PSS = 5 g: 2.5 g) of a reaction product of PEDOT-PSS, butyl glycidyl ether and trioctylamine. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 24)
A solution of 5.0 g of 3,4-ethylenedioxythiophene, 2.5 g of polystyrene sulfonic acid and 10.0 g of sulfuric acid in 997.5 ml of ion-exchanged water was mixed at 20 ° C. An oxidation catalyst of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. The solution was added slowly and stirred for 24 hours for reaction.
Next, 100 g of butyl glycidyl ether was added and stirred for 1 hour. Subsequently, 500 g of isopropanol and 100 g of trioctylamine were added, and the mixture was stirred for 1 hour. Here, it was confirmed that all of the precipitated π-conjugated conductive polymer, polyanion, butyl glycidyl ether, and trioctylamine reaction product had settled in the lower layer of the solution. The obtained reaction solution was filtered to obtain 8.0 g (PEDOT: PSS = 5 g: 2.5 g) of a reaction product of PEDOT-PSS, butyl glycidyl ether and trioctylamine. Next, the sulfate ion content and the surface resistance value were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 5)
A solution of 5.0 g of 3,4-ethylenedioxythiophene in 1000 ml of ion-exchanged water was mixed at 20 ° C.
An oxidation catalyst of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. The solution was added slowly and stirred for 24 hours for reaction.
The obtained reaction solution was filtered to obtain 5.0 g (PEDOT: PSS = 5 g: 0 g) of a poly (3,4-ethylenedioxythiophene) powder.

(Comparative Example 6)
A solution of 5.0 g of 3,4-ethylenedioxythiophene and 10.0 g of polystyrene sulfonic acid in 990.0 ml of ion-exchanged water was mixed at 20 ° C.
An oxidation catalyst solution of 11 g of ammonium persulfate dissolved in 89 ml of ion-exchanged water and 0.3 g of ferric sulfate dissolved in 49.7 ml of ion-exchanged water while keeping the obtained mixed solution at 20 ° C. and stirring. And slowly added and stirred for 24 hours to react.
No precipitates were formed in the obtained reaction solution, and when filtered, all the reactants passed through the filter paper, so the study was discontinued.

<Evaluation method>
[Surface resistance value]
The surface resistance value of the conductive molded body of each example was measured using a resistivity meter (High Restor manufactured by Nittoseiko Analytech Co., Ltd.) with an applied voltage of 10 V. The measurement results are shown in Table 1. In addition, "Ω / □" in the table means ohmper square, and the smaller the surface resistance value, the higher the conductivity.

<Result>
In each example according to the present invention, a conductive polymer powder having a mass ratio of PEDOT: PSS of (1: 0.5) to (1: 1) was obtained. Since the sulfate ion content of this conductive polymer powder measured under predetermined conditions is 0.108% by mass or less, the conductivity of the conductive molded body obtained by pressing this powder is excellent. When the conductive composite constituting the conductive polymer powder reacts with at least one of the amine compound and the epoxy compound, it floats or precipitates in the reaction solution, so that it is easier to separate from the reaction solution. ..
Since the sulfate ion content of the conductive polymer powders of Comparative Examples 1 to 4 exceeded 0.108% by mass, the conductivity was inferior.
Since the PEDOT powder obtained in Comparative Example 5 did not contain PSS, it was inferior in conductivity.
Since the PEDOT-PSS obtained in Comparative Example 6 had a larger ratio of PSS than PEDOT, it had excellent dispersibility in water and did not form a powder.

Claims (10)

A conductive polymer powder containing a π-conjugated conductive polymer and a polyanion.
The content ratio of the π-conjugated conductive polymer: the polyanion in the conductive polymer powder is (1: 0.5) to (1: 1) on a mass basis.
1 g of the conductive polymer powder and 99 g of ion-exchanged water (20 ° C.) are mixed, the obtained powder-containing water is stirred, and the amount of sulfate ion in the powder-containing water after 10 minutes has passed is increased. , 0.108 mass% or less with respect to the total mass of the powder-containing water, a conductive polymer powder. The conductive polymer powder according to claim 1, wherein the conductive polymer powder contains at least one of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid. The conductive polymer powder according to claim 1 or 2, wherein some of the anionic groups of the polyanion are modified by reacting with an amine compound. The conductive polymer powder according to claim 1 or 2, wherein some of the anionic groups of the polyanion are modified by reacting with an epoxy compound. A conductive polymer composition comprising the conductive polymer powder according to any one of claims 1 to 4 and a binder component. An electrode comprising the conductive polymer powder according to any one of claims 1 to 4. By adding a catalyst and an oxidizing agent to a reaction solution containing a monomer capable of forming a π-conjugated conductive polymer, a polyanion, and water, the monomer is oxidatively polymerized to form the π-conjugated conductive polymer and the π-conjugated conductive polymer. The step of forming the conductive polymer powder containing the polyanion, and
It has a step of separating the conductive polymer powder from the reaction liquid.
The content ratio of the monomer: the polyanion in the reaction solution is (1: 0.5) to (1: 1) on a mass basis.
1 g of the conductive polymer powder separated from the reaction solution and 99 g of ion-exchanged water (20 ° C.) were mixed, and the obtained powder-containing water was stirred, and the powder after 10 minutes had passed. A method for producing a conductive polymer powder, wherein the amount of sulfate ions in the contained water is 0.108% by mass or less with respect to the total mass of the powder-containing water. By adding a catalyst and an oxidizing agent to a reaction solution containing a monomer capable of forming a π-conjugated conductive polymer, a polyanion, and water, the monomer is oxidatively polymerized to form the π-conjugated conductive polymer and the π-conjugated conductive polymer. The step of forming the conductive polymer powder containing the polyanion, and
A step of precipitating the modified conductive polymer powder by adding at least one of an amine compound and an epoxy compound to the reaction solution containing the conductive polymer powder and causing the reaction.
It has a step of separating the conductive polymer powder from the reaction liquid.
The content ratio of the monomer: the polyanion in the reaction solution is (1: 0.5) to (1: 1) on a mass basis.
1 g of the conductive polymer powder separated from the reaction solution and 99 g of ion-exchanged water (20 ° C.) were mixed, and the obtained powder-containing water was stirred, and the powder after 10 minutes had passed. A method for producing a conductive polymer powder, wherein the amount of sulfate ions in the contained water is 0.108% by mass or less with respect to the total mass of the powder-containing water. The method for producing a conductive polymer powder according to claim 7 or 8, wherein sulfuric acid is added to the reaction solution and then oxidative polymerization of the monomer is carried out. At least a part of the base material is coated with the conductive polymer composition according to claim 5, and the coating film formed on the base material is cured to form a conductive layer. A method for manufacturing an electrode, which obtains an electrode partially provided with the conductive layer.