JP2018002777A - Conductive polymer dispersion and manufacturing method therefor, and manufacturing method of conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive polymer dispersion high in conductivity of the resulting conductive layer and capable of suppressing conductivity reduction with time in air regardless using an organic solvent as a dispersant, and a manufacturing method therefor.SOLUTION: A conductive polymer dispersion contains a conductive composite body containing π conjugated conductive polymer and polyanion, an epoxy isocyanurate compound having an epoxy group and an isocyanurate ring, and an organic solvent. The manufacturing method of the conductive polymer dispersion has a deposit recovery process for adding the epoxy isocyanurate compound having the epoxy group and the isocyanurate ring to an aqueous dispersion containing the conductive composite body containing the π conjugated conductive polymer and the polyanion in an aqueous dispersant and depositing the conductive composite body to obtain a deposit, and then recovering the deposit, and an organic solvent adding process for adding an organic solvent to the recovered deposit.SELECTED DRAWING: None

Description

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

As a paint for forming the conductive layer, a conductive polymer aqueous dispersion in which poly (3,4-ethylenedioxythiophene) is doped with polystyrene sulfonic acid may be used.
Usually, the film substrate to which the conductive layer is applied is made of a hydrophobic plastic film. Therefore, the conductive polymer aqueous dispersion which is a water-based paint tends to have low adhesion to the film substrate. In addition, since the conductive polymer aqueous dispersion has a long drying time, the productivity of forming the conductive layer tends to be low.
Therefore, a conductive polymer organic solvent dispersion in which water, which is a dispersion medium of the conductive polymer aqueous dispersion, is replaced with an organic solvent may be used.
As the conductive polymer organic solvent dispersion liquid, a conductive polymer aqueous dispersion containing a conductive complex composed of a π-conjugated conductive polymer and a polyanion is freeze-dried to obtain a dried product, and then the dried product is obtained. A product obtained by adding an organic solvent and an amine compound to is known (Patent Document 1).
However, a conductive layer formed from a conductive polymer organic solvent dispersion containing an amine compound has a lower conductivity or a change in color tone than a conductive layer formed from a conductive polymer aqueous dispersion. May occur. In addition, when an addition curable silicone is blended in the conductive polymer organic solvent dispersion in order to make the conductive layer exhibit releasability, the addition curable silicone may inhibit the curing due to the presence of the amine compound. Therefore, in the conductive polymer organic solvent dispersion using the amine compound, the release property could not be expressed in the conductive layer.

  Therefore, in Patent Document 2, a cyclic ether compound having at least one of an oxirane group and an oxetane group is added to a conductive polymer aqueous dispersion containing a conductive complex composed of a π-conjugated conductive polymer and a polyanion. It is known to obtain a conductive polymer organic solvent dispersion (Patent Document 2). In the method described in Patent Document 2, an anionic group not doped in a π-conjugated conductive polymer is reacted with an oxirane group or an oxetane group of a cyclic ether compound to make it hydrophobic, thereby forming a conductive composite organically. Make solvent dispersible.

JP 2011-032382 A International Publication No. 2014/125827

However, when the conductive layer formed from the conductive polymer organic solvent dispersion described in Patent Document 2 is left in the air, the conductivity tends to decrease with time.
Therefore, the present invention provides a conductive polymer dispersion liquid in which the conductive layer obtained has a high conductivity and can suppress a decrease in conductivity over time in the air, even though an organic solvent is used as a dispersion medium. It aims at providing the manufacturing method. Also, there is provided a method for producing a conductive film that can easily produce a conductive film having a high adhesion of the conductive layer to the substrate, a high conductivity of the conductive layer, and a reduction in conductivity over time in air. The purpose is to provide.

The present invention has the following aspects.
[1] A conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an epoxy isocyanurate compound having an epoxy group and an isocyanurate ring, and an organic solvent.
[2] The conductive polymer dispersion according to [1], wherein the epoxy isocyanurate compound is a compound represented by the following formula (1).
(In Formula (1), R ¹ and R ² are each independently a hydrogen atom or an arbitrary substituent.)
[3] The conductive polymer dispersion according to [1] or [2], wherein the epoxy isocyanurate compound is a compound represented by the following formula (2).

[4] The conductive polymer dispersion according to any one of [1] to [3], which contains a reaction product of the epoxy isocyanurate compound and the polyanion.
[5] The conductive polymer dispersion according to any one of [1] to [4], wherein the organic solvent is at least one of methyl ethyl ketone and toluene.
[6] The conductive polymer dispersion according to any one of [1] to [5], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[7] The conductive polymer dispersion according to any one of [1] to [6], wherein the polyanion is polystyrene sulfonic acid.
[8] The conductive polymer dispersion according to any one of [1] to [7], further containing a binder component.
[9] The conductive polymer dispersion according to [8], wherein the binder component is a polyester resin.
[10] The conductive polymer dispersion according to [8], wherein the binder component is an acrylic compound.
[11] The conductive polymer dispersion according to [8], wherein the binder component is a silicone compound.
[12] The conductive polymer dispersion according to [11], wherein the silicone compound is an addition-curable silicone compound.
[13] The conductive polymer dispersion according to any one of [1] to [12], further containing triallyl isocyanurate.
[14] An epoxy isocyanurate compound having an epoxy group and an isocyanurate ring is added to an aqueous dispersion in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium. A conductive polymer dispersion having a precipitation recovery step of recovering the precipitate after depositing the complex and an organic solvent addition step of adding an organic solvent to the recovered precipitate Production method.
[15] The method for producing a conductive polymer dispersion according to [14], wherein the epoxy isocyanurate compound is a compound represented by the above formula (1).
[16] The method for producing a conductive polymer dispersion according to [14] or [15], wherein the epoxy isocyanurate compound is a compound represented by the above formula (2).
[17] A coating step of coating the conductive polymer dispersion according to any one of [1] to [13] on at least one surface of the film substrate, and the coated conductive polymer dispersion The manufacturing method of an electroconductive film which has a drying process which dries a liquid.

According to the conductive polymer dispersion of the present invention, the conductivity of the obtained conductive layer is high and it is possible to suppress a decrease in conductivity over time in the air, even though an organic solvent is used as a dispersion medium. .
According to the method for producing a conductive polymer dispersion of the present invention, even though an organic solvent is used as a dispersion medium, the conductivity is high and the conductivity is prevented from decreasing over time in air. Layers can be easily formed.
According to the method for producing a conductive film of the present invention, a conductive film having high adhesion of the conductive layer to the film substrate, high conductivity of the conductive layer, and suppression of decrease in conductivity over time in air. Can be easily manufactured.

<Conductive polymer dispersion>
The conductive polymer dispersion in one embodiment of the present invention contains a conductive complex including a π-conjugated conductive polymer and a polyanion, an epoxy isocyanurate compound, and an organic solvent.

  The π-conjugated conductive polymer is not particularly limited as long as it has the effect of the present invention as long as the main chain is an organic polymer composed of π-conjugated system. For example, polypyrrole-based conductive polymer, polythiophene-based Conductive polymer, polyacetylene conductive polymer, polyphenylene conductive polymer, polyphenylene vinylene conductive polymer, polyaniline conductive polymer, polyacene conductive polymer, polythiophene vinylene conductive polymer, and These copolymers are exemplified. 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 ( -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-dioctyl) Oxythiophene), poly (3,4-didecyloxythiophene), poly (3, -Didodecyloxythiophene), poly (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-carboxybutylthiophene) is mentioned.
Examples of the polypyrrole conductive polymer 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-hexyl) Oxy pyrrole), poly (3-methyl-4-hexyloxy-pyrrole) and the like.
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), and poly (3-anilinesulfonic acid).
Among the 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 may be used alone or in combination of two or more.

The polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anion group of the 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, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene sulfone. Polymers having a sulfonic acid group such as acid, polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethacryloxybenzenesulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid , Polymers having a carboxylic acid group such as polymethacrylcarboxylic acid, poly (2-acrylamido-2-methylpropanecarboxylic acid), polyisoprene carboxylic acid, polyacrylic acid and the like. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
Among these polyanions, a polymer having a sulfonic acid group is preferable, and polystyrene sulfonic acid is more preferable because conductivity can be further increased.
The said polyanion may be used individually by 1 type, and may use 2 or more types together.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, and more preferably 100,000 or more and 500,000 or less.
The mass average molecular weight in the present specification is a value obtained by measuring with gel permeation chromatography and obtaining the standard substance as polystyrene.

  The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass to 1000 parts by mass with respect to 100 parts by mass of the π-conjugated conductive polymer, and 10 parts by mass to 700 parts by mass. It is more preferable that it is the range of 100 mass parts or more and 500 mass parts or less. If the polyanion content is less than the lower limit, the doping effect on the π-conjugated conductive polymer tends to be weak, the conductivity may be insufficient, and the conductivity in the conductive polymer dispersion may be insufficient. The dispersibility of the sex complex decreases. On the other hand, when the content of the polyanion exceeds the upper limit, the content of the π-conjugated conductive polymer is decreased, and it is difficult to obtain sufficient conductivity.

The polyanion is coordinated and doped to the π-conjugated conductive polymer to form a conductive composite.
However, in the polyanion in this embodiment, not all anion groups are doped into the π-conjugated conductive polymer, but have excess anion groups that do not contribute to doping.

The epoxy isocyanurate compound used in this embodiment has an epoxy group and an isocyanurate ring, and the compound represented by the formula (1) is preferable because it is easily available.
In the formula (1), R ¹ and R ² are each independently a hydrogen atom or an arbitrary substituent.
Here, as an arbitrary substituent, for example, an alkenyl group (for example, propenyl group, butynyl group, etc.), an alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, etc.), an alkoxy group (for example, methoxy group) Group, ethoxy group, propoxy group, butoxy group and the like), aryl group (for example, phenyl group and the like), and the like. These substituents may further have a substituent (for example, (meth) acryloyloxy group, carboxy group, hydroxy group, epoxy group, amino group, trialkoxysilyl group, etc.).
Among the compounds represented by the formula (1), it can react with a reactive acrylic resin having a vinyl group or an addition-type silicone to form a tough coating film. Therefore, both R ¹ and R ² are propenyl groups (allyl groups). ), That is, a compound represented by the formula (2) is preferable.
Epoxy isocyanurate compounds can form reactants with polyanions. Therefore, the conductive polymer dispersion of this embodiment may contain a reaction product of an epoxy isocyanurate compound and a polyanion. The reaction product is highly dispersible in an organic solvent.

  The content of the epoxy isocyanurate compound is preferably from 0.1 times to 1000 times the conductive complex, more preferably from 0.5 times to 500 times, It is more preferable that the amount be 1 to 100 times. If the content of the epoxy isocyanurate compound is equal to or higher than the lower limit, it is possible to further suppress the decrease in conductivity in air, and if the content is equal to or lower than the upper limit, the decrease in conductivity due to the decrease in the concentration of the π-conjugated conductive polymer. Can be prevented.

Examples of the organic solvent used in this embodiment include alcohol solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, and the like. An organic solvent may be used individually by 1 type, and may use 2 or more types together.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, and allyl alcohol.
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 ester solvent include ethyl acetate, propyl acetate, butyl acetate and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, and the like.
Examples of the amide solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.
Among organic solvents, at least one of methyl ethyl ketone and toluene is preferable because it is versatile.

  As a dispersion medium, water may be included together with an organic solvent. However, when the total amount of the organic solvent and water is 100% by mass, the content ratio of water is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 1% by mass or less. The content is preferably 0% by mass or less. If the water content in the dispersion medium is small, the drying speed of the conductive polymer dispersion is increased. Also, if the water content in the dispersion medium is small, the wettability with the film substrate to which the conductive polymer dispersion is applied becomes higher, and the conductive layer and film formed from the conductive polymer dispersion. Adhesiveness with a base material can be made higher.

The conductive polymer dispersion of this embodiment may contain a binder component in order to improve the film forming property of the conductive layer obtained.
Examples of the binder component include a resin, a thermosetting compound, and an active energy ray curable compound. When using a thermosetting compound, it is preferable to also contain a thermal polymerization initiator, and when using an active energy ray-curable compound, it is preferable to also contain a photoinitiator.
As the binder component, addition-curable silicone can be used as will be described later. When addition curable silicone is used as the binder component, it is also preferable to contain a platinum catalyst.

Examples of resins that can be used as the binder component include acrylic resins, polyester resins, epoxy resins, oxetane resins, polyurethane resins, polyimide resins, melamine resins, silicone resins, and vinyl acetate resins. Among these, acrylic resin and polyester resin are preferable in terms of low cost. In particular, when a polyethylene terephthalate film is used as the base material of the conductive film, it is preferable that the binder component is a polyester resin because the adhesion of the conductive layer to the base material becomes higher.
When a silicone resin is used as the binder component, the conductive layer exhibits releasability.

Examples of the thermosetting compound and the active energy ray-curable compound include a compound having a vinyl group, a compound having two or more epoxy groups, and a compound having two or more oxetane groups. These may be monomers or oligomers.
Among these binder components, an active energy ray-curable acrylic compound is preferable because it can be easily dispersed or dissolved in an organic solvent and can be easily cured. The active energy ray-curable acrylic compound is an acrylic compound that is cured by radical polymerization upon irradiation with active energy rays (ultraviolet rays, electron beams, visible rays).
Examples of the active energy ray-curable acrylic compound include acrylate, methacrylate, (meth) acrylamide, vinyl ether, carboxylic acid vinyl ester and the like. The active energy ray-curable acrylic compound may be a monofunctional monomer having only one vinyl group, a polyfunctional monomer having two or more vinyl groups, or a combination of a monofunctional monomer and a polyfunctional monomer. .

Examples of the acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polyethylene glycol diacrylate. 1,6-hexanediol diacrylate, bisphenol A / ethylene oxide modified diacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol monohydroxypentaacrylate, trimethylolpropane triacrylate, Such as glycerin propoxytriacrylate It is below.
Examples of the methacrylate include n-butyl methacrylate, t-butyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, and glycidyl methacrylate. , Tetrahydrofurfuryl methacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate and the like.
Examples of (meth) acrylamide include methacrylamide, 2-hydroxyethylacrylamide, N-methylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N-phenylacrylamide, N-methylolacrylamide, dimethylaminopropylacrylamide, Examples thereof include dimethylaminopropyl methacrylamide, diacetone acrylamide, N, N-dimethylacrylamide, N-vinylformamide, acryloylmorpholine, acryloylpiperidine and the like.
The active energy ray-curable acrylic compound may be a polyfunctional acrylate obtained by reacting an acrylic monomer with another compound, such as epoxy acrylate, urethane acrylate, polyester acrylate, or polyacryl acrylate.
The active energy ray-curable acrylic compound may be used alone or in combination of two or more.

The binder component may be a curable silicone. When the binder component is a curable silicone, the conductive layer can exhibit releasability by curing the curable silicone.
The curable silicone may be either addition curable silicone or condensation curable silicone.
When the binder component is an addition-curable silicone, curing inhibition occurs depending on the coexisting compound (for example, an amine compound), but even when an epoxy isocyanurate compound coexists, the curing inhibition of the addition-curable silicone compound hardly occurs. Therefore, the conductive polymer dispersion of this embodiment is suitable when an addition-curable silicone compound is blended as a binder component.
Examples of the addition-curable silicone include linear polymers having a siloxane bond, which have polydimethylsiloxane having vinyl groups at both ends of the linear chain and hydrogen silane. Such an addition-curable silicone is cured by forming a three-dimensional crosslinked structure by an addition reaction. In order to accelerate the curing, a platinum-based curing catalyst may be used.
Specific examples of the addition-curable silicone include KS-3703T, KS-847T, KM-3951, X-52-151, X-52-6068, X-52-6069 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. .
As the addition-curable silicone, those dissolved or dispersed in an organic solvent are preferably used.

  The content ratio of the binder component is preferably 1000 parts by mass or more and 100000 parts by mass or less, and more preferably 3000 parts by mass or more and 50000 parts by mass or less with respect to 100 parts by mass of the conductive composite. When the content ratio of the binder component is equal to or higher than the lower limit value, the strength and hardness of the obtained conductive layer can be sufficiently improved, and when it is equal to or lower than the upper limit value, sufficient conductivity can be ensured.

The conductive polymer dispersion may contain triallyl isocyanurate (triallyl isocyanurate). If the conductive polymer dispersion contains triallyl isocyanurate, the conductivity improving effect and the conductivity suppressing effect in air are further enhanced.
The content of triallyl isocyanurate is preferably 0.1 times or more and 10,000 times or less, more preferably 0.5 times or more and 5000 times or less, more preferably 1 time with respect to the conductive composite. It is more preferable that the amount is not less than 1000 times and not more than 1000 times. If the content of triallyl isocyanurate is equal to or higher than the lower limit, the conductivity enhancement effect and the conductivity suppression effect in air are sufficiently exhibited. If the content is equal to or lower than the upper limit, the π-conjugated conductive polymer concentration The decrease in conductivity due to the decrease can be prevented.

The conductive polymer dispersion may contain a highly conductive agent that improves the conductivity of the conductive layer containing the conductive composite in order to further improve the conductivity.
Specifically, the highly conductive agent includes a saccharide, a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxy groups, a compound having one or more hydroxy groups and one or more carboxy groups, an amide group At least one compound selected from the group consisting of a compound having an imide group, a compound having an imide group, a lactam compound, and a compound having a glycidyl group. The said highly conductive agent may be used individually by 1 type, and may use 2 or more types together.

  Examples of nitrogen-containing aromatic cyclic compounds include pyridines and derivatives thereof containing one nitrogen atom, imidazoles and derivatives thereof containing two nitrogen atoms, pyrimidines and derivatives thereof, pyrazines and derivatives thereof And triazines containing three nitrogen atoms and derivatives thereof. From the viewpoint of solvent solubility and the like, pyridines and derivatives thereof, imidazoles and derivatives thereof, and pyrimidines and derivatives thereof are preferable.

  Specific examples of pyridines and derivatives thereof include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, N-vinylpyridine, 2,4-dimethylpyridine, 2,4. , 6-trimethylpyridine, 3-cyano-5-methylpyridine, 2-pyridinecarboxylic acid, 6-methyl-2-pyridinecarboxylic acid, 4-pyridinecarboxaldehyde, 4-aminopyridine, 2,3-diaminopyridine, 2 , 6-diaminopyridine, 2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 4-pyridinemethanol, 2,6-dihydroxypyridine, 2,6-pyridinedimethanol, methyl 6-hydroxynicotinate, 2 -Hydroxy-5-pyridinemethanol, ethyl 6-hydroxynicotinate, 4-pi Lysine methanol, 4-pyridineethanol, 2-phenylpyridine, 3-methylquinoline, 3-ethylquinoline, quinolinol, 2,3-cyclopentenopyridine, 2,3-cyclohexanopyridine, 1,2-di (4- Pyridyl) ethane, 1,2-di (4-pyridyl) propane, 2-pyridinecarboxaldehyde, 2-pyridinecarboxylic acid, 2-pyridinecarbonitrile, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, Examples include 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, and 3-pyridinesulfonic acid.

  Specific examples of imidazoles and derivatives thereof include imidazole, 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, N-vinylimidazole, and N-allylimidazole. 1- (2-hydroxyethyl) imidazole (N-hydroxyethylimidazole), 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazoledicarbo Acid, dimethyl 4,5-imidazole dicarboxylate, benzimidazole, 2-aminobenzimidazole, 2-aminobenzimidazole-2-sulfonic acid, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole , 2- (2-pyridyl) benzimidazole and the like.

  Specific examples of pyrimidines and derivatives thereof include 2-amino-4-chloro-6-methylpyrimidine, 2-amino-6-chloro-4-methoxypyrimidine, 2-amino-4,6-dichloropyrimidine, 2-amino-4,6-dihydroxypyrimidine, 2-amino-4,6-dimethylpyrimidine, 2-amino-4,6-dimethoxypyrimidine, 2-aminopyrimidine, 2-amino-4-methylpyrimidine, 4,6 -Dihydroxypyrimidine, 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4,6-triaminopyrimidine, 2,4-dimethoxypyrimidine, 2,4,5-trihydroxypyrimidine, 2,4-pyrimidinediol, etc. Is mentioned.

  Specific examples of the pyrazines and derivatives thereof include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5-methylpyrazinecarboxylic acid, pyrazineamide, 5 -Methylpyrazine amide, 2-cyanopyrazine, aminopyrazine, 3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2,3-diethylpyrazine and the like.

  Specific examples of triazines and derivatives thereof include 1,3,5-triazine, 2-amino-1,3,5-triazine, 3-amino-1,2,4-triazine, and 2,4-diamino. -6-phenyl-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine, 2,4,6-tris (trifluoromethyl) -1,3,5-triazine, 2,4,6-tri-2-pyridine-1,3,5-triazine, 3- (2-pyridine) -5,6-bis (4-phenylsulfonic acid) -1,2,4-triazine disodium 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine, 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine-ρ, ρ′- Disodium disulphonate, 2-hydroxy-4,6-dichloro -1,3,5-triazine and the like.

Examples of the compound having two or more hydroxy groups include propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, D-glucose, D-glucitol, isoprene glycol, dimethylolpropionic acid, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, thiodiethanol, glucose, tartaric acid, D-glucar Polyhydric aliphatic alcohols such as acid and glutaconic acid;
Polymeric alcohols such as cellulose, polysaccharides, sugar alcohols;
1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 2,3-dihydroxy-1-pentadecylbenzene, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,4-dihydroxybenzophenone, 2,6 -Dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 2,4'-dihydroxydiphenylsulfone, 2,2 ', 5,5'-tetrahydroxydiphenylsulfone, 3,3', 5,5 '-Tetramethyl-4,4'-dihydroxydiphenylsulfone, hydroxyquinonecarboxylic acid and its salts, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6- Dihydroxybenzoic acid, 3,5-di Droxybenzoic acid, 1,4-hydroquinonesulfonic acid and its salts, 4,5-hydroxybenzene-1,3-disulfonic acid and its salts, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6- Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene-2,6-dicarboxylic acid, 1,6-dihydroxynaphthalene-2,5-dicarboxylic acid, 1,5-dihydroxy Naphthoic acid, 1,4-dihydroxy-2-naphthoic acid phenyl ester, 4,5-dihydroxynaphthalene-2,7-disulfonic acid and its salts, 1,8-dihydroxy-3,6-naphthalenedisulfonic acid and its salts, 6,7-Dihydroxy-2-naphthalenesulfonic acid and its 1,2,3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene, 5-methyl-1,2,3-trihydroxybenzene, 5-ethyl-1,2,3-tri Hydroxybenzene, 5-propyl-1,2,3-trihydroxybenzene, trihydroxybenzoic acid, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetra Aromatic compounds such as hydroxy-p-benzoquinone, tetrahydroxyanthraquinone, methyl garlic acid (methyl gallate), ethyl garlic acid (ethyl gallate), potassium hydroquinone sulfonate, and the like.

  Examples of the compound having one or more hydroxy groups and one or more carboxy groups include tartaric acid, glyceric acid, dimethylolbutanoic acid, dimethylolpropanoic acid, D-glucaric acid, and glutaconic acid.

The compound having an amide group is a monomolecular compound having an amide bond represented by -CO-NH- (CO portion is a double bond) in the molecule. That is, as the amide compound, for example, a compound having functional groups at both ends of the bond, a compound in which a cyclic compound is bonded to one end of the bond, urea and urea derivatives in which the functional groups at both ends are hydrogen Etc.
Specific examples of amide compounds include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluamide, formamide, N-methylformamide, propionamide , Propioluamide, butyramide, isobutylamide, palmitoamide, stearylamide, oleamide, oxamide, glutaramide, adipamide, cinnamamide, glycolamide, lactamide, glyceramide, tartaramide, citrulamide, glyoxylamide, pyruvamide, acetoacetamide, dimethylacetamide, benzyl Amide, anthranilamide, ethylenediaminetetraacetamide, Acetamide, triacetamide, dibenzamide, tribenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1,3-diethylurea and derivatives thereof Is mentioned.

Moreover, acrylamide can also be used as an amide compound. As acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, Examples thereof include N-diethyl methacrylamide, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.
The molecular weight of the amide compound is preferably 46 or more and 10,000 or less, more preferably 46 or more and 5,000 or less, and particularly preferably 46 or more and 1,000 or less.

  As the amide compound, a monomolecular compound having an imide bond (hereinafter referred to as an imide compound) is preferable because of higher conductivity. Examples of the imide compound include phthalimide and phthalimide derivatives, succinimide and succinimide derivatives, benzimide and benzimide derivatives, maleimide and maleimide derivatives, naphthalimide and naphthalimide derivatives from the skeleton.

Moreover, although an imide compound is classified into an aliphatic imide, an aromatic imide, etc. by the kind of functional group of both terminal, an aliphatic imide is preferable from a soluble viewpoint.
Furthermore, the aliphatic imide compound is classified into a saturated aliphatic imide compound having no unsaturated bond between carbons in the molecule and an unsaturated aliphatic imide compound having an unsaturated bond between carbons in the molecule. .
The saturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and is a compound in which both R ¹ and R ² are saturated hydrocarbons. Specifically, cyclohexane-1,2-dicarboximide, allantoin, hydantoin, barbituric acid, alloxan, glutarimide, succinimide, 5-butylhydantoic acid, 5,5-dimethylhydantoin, 1-methylhydantoin, 1,5 , 5-trimethylhydantoin, 5-hydantoin acetic acid, N-hydroxy-5-norbornene-2,3-dicarboximide, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimidooxycarbonyloxy) Ethyl] sulfone, α-methyl-α-propylsuccinimide, cyclohexylimide and the like.
The unsaturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and one or both of R ¹ and R ² are one or more unsaturated bonds. Specific examples are 1,3-dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 1,8-bis. Maleimide octane, N-carboxyheptylmaleimide and the like can be mentioned.
The molecular weight of the imide compound is preferably 60 or more and 5,000 or less, more preferably 70 or more and 1,000 or less, and particularly preferably 80 or more and 500 or less.

The lactam compound is an intramolecular cyclic amide of an aminocarboxylic acid, and a part of the ring is —CO—NR— (R is hydrogen or an arbitrary substituent). However, one or more carbon atoms in the ring may be replaced with an unsaturated or heteroatom.
Examples of the lactam compound include pentano-4-lactam, 4-pentanelactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexane lactam and the like.

  Examples of the compound having a glycidyl group include ethyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl phenyl ether, bisphenol A, diglycidyl ether, glycidyl acrylate, methacrylic acid Examples thereof include glycidyl compounds such as glycidyl ether.

  The content ratio of the highly conductive agent is preferably 1 to 1000 times, more preferably 2 to 100 times the total mass of the conductive composite. If the content ratio of the high conductive agent is equal to or higher than the lower limit value, the effect of improving the conductivity due to the addition of the high conductive agent is sufficiently exerted, and if it is equal to or lower than the upper limit value, the concentration of the π-conjugated conductive polymer is decreased. It is possible to prevent a decrease in conductivity due to the above.

The conductive polymer dispersion may contain a known additive.
The additive is not particularly limited as long as it has the effect of the present invention, and for example, a surfactant, an inorganic conductive agent, an antifoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like can be used. However, the additive comprises a compound other than the polyanion, the epoxy isocyanurate compound, the triallyl isocyanurate, the dispersion medium, the binder component, and the high conductivity agent.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferred from the viewpoint of storage stability. Moreover, you may add polymer type surfactants, such as polyvinyl alcohol and polyvinylpyrrolidone.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving a metal salt in water.
Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone oil.
Examples of the coupling agent include silane coupling agents having a vinyl group, an amino group, an epoxy group, and the like.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and saccharides.
Examples of UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. Is mentioned.

  When the conductive polymer dispersion contains the additive, the content ratio is appropriately determined according to the type of the additive, but is generally 0. 10 parts by mass relative to 100 parts by mass of the solid content of the conductive composite. It is in the range of not less than 001 parts by mass and not more than 5 parts by mass.

  The method for producing a conductive polymer dispersion for obtaining the conductive polymer dispersion includes a precipitation collection step and an organic solvent addition step.

The precipitation recovery step is a step of adding an epoxy isocyanurate compound to the conductive polymer aqueous dispersion to precipitate a conductive composite to obtain a precipitate, and then collecting the precipitate by filtration.
When an epoxy isocyanurate compound is added to the conductive polymer aqueous dispersion, at least a part of the epoxy group of the epoxy isocyanate compound reacts with the anion group of the polyanion. Thereby, since the conductive composite becomes hydrophobic, it becomes difficult to stably disperse in the aqueous dispersion, and precipitates into a precipitate.

The conductive polymer aqueous dispersion is a dispersion in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium.
The conductive polymer aqueous dispersion is obtained, for example, by chemical oxidative polymerization of a monomer that forms a π-conjugated conductive polymer in an aqueous solution of a polyanion. In addition, a commercially available conductive polymer aqueous dispersion may be used.

The amount of moisture in the precipitate obtained by the precipitation collection step is preferably as small as possible and most preferably contains no moisture, but from a practical point of view, it may contain moisture in the range of 10% by mass or less.
Examples of the method for reducing the amount of water include a method of washing the precipitate with an organic solvent, and a method of drying the precipitate.

The organic solvent addition step is a step of adding an organic solvent to the collected precipitate.
After adding the organic solvent to the precipitate, it is preferable to perform a dispersion treatment by stirring. The stirring method is not particularly limited, and may be stirring with a weak shearing force such as a stirrer, or may be performed using a high shearing force disperser (such as a homogenizer).
When the conductive polymer dispersion contains a binder component, a highly conductive agent, an additive, and the like, it is preferable to add a binder component, a highly conductive agent, an additive, and the like after adding the organic solvent.

In the conductive polymer dispersion, since the anion group of the polyanion is rendered non-hydrophilic by the epoxy isocyanurate compound, the conductive complex can be dispersed with high dispersibility in the organic solvent.
In addition, since the conductive composite can be dispersed in an organic solvent by the epoxy isocyanurate compound, it is not necessary to add an amine compound. Therefore, when an addition curable silicone that causes curing inhibition in the presence of an amine compound is used as a binder component, the conductive composite of this aspect in which the conductive composite is dispersible in an organic solvent without the addition of an amine compound. Molecular dispersions are preferred.
Further, although the reason is not clear, the conductive polymer dispersion containing the epoxy isocyanurate compound increases the conductivity of the conductive layer formed from the conductive polymer dispersion, and the conductive layer A decrease in conductivity over time in air can be suppressed. Specifically, a conductive layer formed from a conductive polymer dispersion containing an epoxy isocyanurate compound is more conductive than a conductive layer formed from a conductive polymer dispersion containing an epoxy compound having no isocyanurate ring. It is possible to suppress a decrease in conductivity of the layer over time in the air. This effect is the same even when the conductive polymer dispersion contains a binder component such as addition-curable silicone.

<Method for producing conductive film>
The method for producing a conductive film of one embodiment of the present invention includes a coating step of coating the conductive polymer dispersion on at least one surface of a film substrate to form a coated film, and a coated conductive film. A drying step of drying the functional polymer dispersion.
When the conductive polymer dispersion contains an active energy ray-curable binder component, there is an active energy ray irradiation step of irradiating the dried conductive polymer coating film with active energy rays after the drying step. May be. When it has an active energy ray irradiation process, the formation speed of a conductive layer can be made quick and the productivity of a conductive film improves.
The conductive film obtained by this manufacturing method includes a film substrate and a conductive layer formed on at least one surface of the film substrate, and the conductive layer includes a π-conjugated conductive polymer and a polyanion. Contains a conductive composite.
The average thickness of the conductive layer is preferably 10 nm or more and 20000 nm or less, more preferably 20 nm or more and 10,000 nm or less, and further preferably 30 nm or more and 5000 nm or less. If the average thickness of the conductive layer is equal to or higher than the lower limit, sufficiently high conductivity can be exhibited, and if the average thickness is equal to or lower than the upper limit, the conductive layer can be easily formed.

A plastic film is mentioned as a film base material used in the coating process of this aspect.
Examples of the resin for the film base material constituting the plastic film include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate. , Polyethylene naphthalate, Polyacrylate, Polycarbonate, Polyvinylidene fluoride, Polyarylate, Styrenic elastomer, Polyester elastomer, Polyethersulfone, Polyetherimide, Polyetheretherketone, Polyphenylene sulfide, Polyimide, Cellulose triacetate, Cellulose acetate propio And the like. Among these resins for film bases, polyethylene terephthalate and cellulose triacetate are preferable because they are inexpensive and have excellent mechanical strength.
The film base resin may be amorphous or crystalline.
Further, the film substrate may be unstretched or stretched.
In addition, the film substrate may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or flame treatment in order to improve the adhesion of the conductive layer formed from the conductive polymer dispersion.

The average thickness of the film substrate is preferably 10 μm or more and 500 μm or less, and more preferably 20 μm or more and 200 μm or less. If the average thickness of the film substrate is equal to or greater than the lower limit value, it is difficult to break, and if it is equal to or less than the upper limit value, sufficient flexibility as a film can be ensured.
The thickness in the present specification is a value obtained by measuring the thickness at any 10 locations and averaging the measured values.

Examples of the method for applying the conductive polymer dispersion 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, an air doctor coater, a knife coater, A coating method using a coater such as a blade coater, cast coater or screen coater, a spraying method using a sprayer such as air spray, airless spray or rotor dampening, a dipping method or the like can be applied.
Of these, a bar coater may be used because it can be applied easily. In the bar coater, the coating thickness varies depending on the type, and in the commercially available bar coater, a number is assigned to each type, and the larger the number, the thicker the coating can be made.
The amount of the conductive polymer dispersion applied to the film substrate is not particularly limited, but the solid content is preferably in the range of 0.1 g / m ² or more and 10.0 g / m ² or less.

Examples of the drying method in the drying step include heat drying and vacuum drying. As heat drying, for example, a normal method such as hot air heating or infrared heating can be employed.
When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium to be used, but is usually in the range of 50 ° C to 150 ° C. Here, the heating temperature is a set temperature of the drying apparatus.

When it has an active energy ray irradiation process, as an active energy ray used, an ultraviolet-ray, an electron beam, visible light, etc. are mentioned. Among active energy rays, ultraviolet rays are preferable because they are versatile. In the irradiation of ultraviolet rays, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used.
The illuminance upon UV irradiation is preferably 100 mW / cm ² or more. When the illuminance is less than 100 mW / cm ² , the active energy ray-curable binder component may not be sufficiently cured. Further, the integrated light quantity is preferably 50 mJ / cm ² or more. If the integrated light quantity is less than 50 mJ / cm ² , crosslinking may not be sufficient. In addition, the illumination intensity and integrated light quantity in this invention are measured using Topcon Co., Ltd. UVR-T1 (industrial UV checker, light receiver; UD-T36, measurement wavelength range: 300 nm to 390 nm, peak sensitivity wavelength: about 355 nm). It is the value.

The conductive layer formed by the method for producing the conductive film contains an epoxy isocyanurate compound, thereby suppressing a decrease in conductivity over time in the air.
In addition, since the film base is usually highly hydrophobic, the conductive layer formed using the above conductive polymer dispersion, in which the main component of the dispersion medium is an organic solvent, is adhesive to the film base. Is expensive. Furthermore, the adhesiveness of the conductive layer with respect to the substrate can be further increased by the epoxy isocyanurate compound contained in the conductive layer.
Therefore, according to the method for producing a conductive film of the present invention, a conductive film having high conductivity can be easily produced even if the conductive polymer dispersion contains an organic solvent.

(Production Example 1)
Dissolve 206 g of sodium styrenesulfonate in 1000 ml of ion-exchanged water and, while stirring at 80 ° C., add dropwise 1.14 g of ammonium persulfate oxidizer solution previously dissolved in 10 ml of water for 20 minutes. Stir.
To the obtained sodium styrenesulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, about 1000 ml of the polystyrenesulfonic acid-containing solution was removed by ultrafiltration, and 2000 ml of ion-exchanged water was added to the remaining liquid. About 2000 ml of solution was removed by ultrafiltration. The above ultrafiltration operation was repeated three times. Further, about 2000 ml of ion-exchanged water was added to the obtained filtrate, and about 2000 ml of solution was removed by ultrafiltration.
This ultrafiltration operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

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

Example 1
To 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 300 g of methanol and 1,3-diallyl-5- (2,3-epoxypropan-1-yl) -1,3,5-triazine-2, 25 g of 4,6-trione was added and stirred at 50 ° C. for 4 hours. After stirring, the deposited precipitate was collected by filtration, washed twice with 100 g of methanol, added with 315 g of methyl ethyl ketone, and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion.

(Example 2)
To 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 300 g of methanol and 1,3-diallyl-5- (2,3-epoxypropan-1-yl) -1,3,5-triazine-2, 5.0 g of 4,6-trione and 20.0 g of Epolite M-1230 (Kyoeisha Chemical Co., Ltd., C12, C13 mixed higher alcohol glycidyl ether) were added and stirred at 50 ° C. for 4 hours. After stirring, the deposited precipitate was collected by filtration, washed twice with 100 g of methanol, added with 315 g of methyl ethyl ketone, and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion.

(Comparative Example 1)
To 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 300 g of methanol and 25 g of Epolite M-1230 (Kyoeisha Chemical Co., Ltd., Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether) were added, and 50 Stir at 4 ° C. for 4 hours. After stirring, the deposited precipitate was collected by filtration, washed twice with 100 g of methanol, added with 315 g of methyl ethyl ketone, and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion.

[Evaluation]
The conductive polymer dispersion of each example was designated as No. 1 4 was applied to a polyethylene terephthalate film (Lumirror T60, manufactured by Toray Industries, Inc.) and dried at 120 ° C. for 1 minute to form a conductive layer to obtain a conductive film.
The surface resistance value _R0 of the conductive layer immediately after obtained was measured under the condition of an applied voltage of 10 V using a resistivity meter (Hiresta manufactured by Mitsubishi Chemical Analytic Co., Ltd.).
The conductive film was allowed to stand for 3 days in an environment of a temperature of 25 ° C. and a relative humidity of 50%, with the surface of the conductive layer being exposed to air, and then the surface resistance value R ₁ was measured in the same manner as described above.
The measurement results are shown in Table 1. The smaller the surface resistance value, the higher the conductivity. Moreover, the smaller the change with time of the surface resistance value represented by R ₁ / R ₀ , the more the decrease in conductivity over time can be suppressed.

The conductive polymer dispersions of Examples 1 and 2 containing an epoxy isocyanurate compound had high conductivity of the conductive layer, and the conductivity did not change even when left in the air.
The conductive polymer dispersion of Comparative Example 1 containing an epoxy compound having no isocyanurate ring instead of the epoxy isocyanurate compound had a decreased conductivity when left in the air.

(Example 3)
2 g of a polyester solution (Toyobo Co., Ltd., Byron 240, solid content concentration 15% by mass, methyl ethyl ketone: toluene = 9: 1) was mixed with 8 g of the conductive polymer dispersion obtained in Example 1, and Example 3 A conductive polymer dispersion was obtained.

(Comparative Example 2)
8 g of the conductive polymer dispersion obtained in Comparative Example 1 was mixed with 2 g of a polyester solution (Toyobo Co., Ltd., Byron 240, solid concentration 15% by mass, methyl ethyl ketone: toluene = 9: 1). A conductive polymer dispersion was obtained.

[Evaluation]
The conductive polymer dispersion of each example was designated as No. 1 4 was applied to a polyethylene terephthalate film (Lumirror T60, manufactured by Toray Industries, Inc.) and dried at 120 ° C. for 1 minute to form a conductive layer to obtain a conductive film.
The surface resistance value _R0 of the conductive layer immediately after obtained was measured under the condition of an applied voltage of 10 V using a resistivity meter (Hiresta manufactured by Mitsubishi Chemical Analytic Co., Ltd.).
The conductive film was allowed to stand for 7 days in an environment where the temperature was 25 ° C. and the relative humidity was 50% and the surface of the conductive layer was in contact with air, and then the surface resistance value R ₁ was measured in the same manner as described above.
The measurement results are shown in Table 2.

The conductive polymer dispersion of Example 3 containing an epoxy isocyanurate compound had high conductivity of the conductive layer, and the conductivity did not change even when left in the air.
The conductive polymer dispersion of Comparative Example 2 that did not contain an epoxy isocyanurate compound had decreased conductivity when left in the air.

Example 4
8 g of the conductive polymer dispersion obtained in Example 1 and 2 g of pentaerythritol triacrylate and 0.08 g of a photopolymerization initiator (BASF, Irgacure 184) are mixed, and the conductive polymer of Example 4 is mixed. A dispersion was obtained.

(Comparative Example 3)
8 g of the conductive polymer dispersion obtained in Comparative Example 1 was mixed with 2 g of pentaerythritol triacrylate and 0.08 g of a photopolymerization initiator (BASF, Irgacure 184) to obtain the conductive polymer of Comparative Example 3. A dispersion was obtained.

[Evaluation]
The conductive polymer dispersion of each example was designated as No. 1 Using a 4 bar coater, it was applied to a polyethylene terephthalate film (Lumirror T60, manufactured by Toray Industries, Inc.) and dried at 100 ° C. for 1 minute to obtain a dried coating film. Next, the dried coating film was cured by irradiation with ultraviolet rays of 400 mJ to form a conductive layer, and a conductive film was obtained.
The surface resistance value _R0 of the conductive layer immediately after obtained was measured under the condition of an applied voltage of 10 V using a resistivity meter (Hiresta manufactured by Mitsubishi Chemical Analytic Co., Ltd.).
The conductive film was allowed to stand for 7 days in an environment where the temperature was 25 ° C. and the relative humidity was 50% and the surface of the conductive layer was in contact with air, and then the surface resistance value R ₁ was measured in the same manner as described above.
Table 3 shows the measurement results.

The conductive polymer dispersion of Example 4 containing an epoxy isocyanurate compound had high conductivity of the conductive layer, and the conductivity did not change even when left in the air.
The conductive polymer dispersion of Comparative Example 3 that did not contain an epoxy isocyanurate compound had reduced conductivity when left in the air.

(Example 5)
To 0.45 g of the conductive polymer dispersion obtained in Example 1, 1.5 g of addition-curable silicone solution (manufactured by Shin-Etsu Chemical Co., Ltd., KS-3703T, solid content concentration 30 mass%, toluene solution) and toluene 25 0.5 g, 58.5 g of methyl ethyl ketone, and 0.03 g of platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) were mixed to obtain a conductive polymer dispersion of Example 5.

(Example 6)
A conductive polymer dispersion of Example 6 was obtained in the same manner as in Example 5 except that triallyl isocyanurate was mixed together with the addition-curable silicone solution and the platinum catalyst.

(Comparative Example 4)
To 0.45 g of the conductive polymer dispersion obtained in Comparative Example 1, 1.5 g of addition-curable silicone solution (manufactured by Shin-Etsu Chemical Co., Ltd., KS-3703T, solid content concentration 30% by mass, toluene solution) and toluene 25 0.5 g, methyl ethyl ketone 58.5 g, and platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) 0.03 g were mixed to obtain a conductive polymer dispersion of Comparative Example 4.

[Evaluation]
The conductive polymer dispersion of each example was designated as No. 1 Using an 8 bar coater, it was applied to a polyethylene terephthalate film (Lumirror T60, manufactured by Toray Industries, Inc.) and dried at 150 ° C. for 1 minute to form a conductive layer to obtain a conductive film.
The surface resistance value _R0 of the conductive layer immediately after obtained was measured under the condition of an applied voltage of 10 V using a resistivity meter (Hiresta manufactured by Mitsubishi Chemical Analytic Co., Ltd.).
The conductive film was allowed to stand for 1 day in a state where the surface of the conductive layer was exposed to air in an environment of a temperature of 25 ° C. and a relative humidity of 50%, and then the surface resistance value R ₁ was measured in the same manner as described above.
Table 4 shows the measurement results.

The conductive polymer dispersions of Examples 5 and 6 containing the epoxy isocyanurate compound had high conductivity of the conductive layer, and the conductivity did not change even when left in the air.
The conductive polymer dispersion of Comparative Example 4 that did not contain an epoxy isocyanurate compound had decreased conductivity when left in the air.

Claims (17)

  A conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an epoxy isocyanurate compound having an epoxy group and an isocyanurate ring, and an organic solvent. The conductive polymer dispersion according to claim 1, wherein the epoxy isocyanurate compound is a compound represented by the following formula (1).

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom or an arbitrary substituent.) The conductive polymer dispersion according to claim 1 or 2, wherein the epoxy isocyanurate compound is a compound represented by the following formula (2).

  The conductive polymer dispersion according to any one of claims 1 to 3, comprising a reaction product of the epoxy isocyanurate compound and the polyanion.   5. The conductive polymer dispersion according to claim 1, wherein the organic solvent is at least one of methyl ethyl ketone and toluene.   The conductive polymer dispersion according to claim 1, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).   The conductive polymer dispersion according to claim 1, wherein the polyanion is polystyrene sulfonic acid.   The conductive polymer dispersion according to any one of claims 1 to 7, further comprising a binder component.   The conductive polymer dispersion according to claim 8, wherein the binder component is a polyester resin.   The conductive polymer dispersion according to claim 8, wherein the binder component is an acrylic compound.   The conductive polymer dispersion according to claim 8, wherein the binder component is a silicone compound.   The conductive polymer dispersion according to claim 11, wherein the silicone compound is an addition-curable silicone compound.   The conductive polymer dispersion according to any one of claims 1 to 12, further comprising triallyl isocyanurate.   An epoxy isocyanurate compound having an epoxy group and an isocyanurate ring is added to an aqueous dispersion in which an electrically conductive composite containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium, and the conductive composite is obtained. A method for producing a conductive polymer dispersion, comprising: a precipitation collection step for collecting the precipitate after the precipitation to obtain; and an organic solvent addition step for adding an organic solvent to the collected precipitate. The method for producing a conductive polymer dispersion according to claim 14, wherein the epoxy isocyanurate compound is a compound represented by the following formula (1).

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom or an arbitrary substituent.) The method for producing a conductive polymer dispersion according to claim 14 or 15, wherein the epoxy isocyanurate compound is a compound represented by the following formula (2).

  A coating process for coating the conductive polymer dispersion according to any one of claims 1 to 13 on at least one surface of the film substrate, and drying the coated conductive polymer dispersion. The manufacturing method of an electroconductive film which has a drying process.