JP2019196464A - Conductive polymer dispersion liquid and method for producing the same, and method for producing conductive film - Google Patents

Abstract

To provide a conductive polymer dispersion liquid containing a π-conjugated conductive polymer, which easily forms a conductive layer of high conductivity with high dispersibility of a conductive complex regardless of using an organic solvent as a dispersion medium, and a method for producing the same, and a method for producing a conductive film.SOLUTION: A conductive polymer dispersion liquid contains: a conductive complex containing a π-conjugated conductive polymer obtained by chemical oxidation polymerization of a monomer forming the π-conjugated conductive polymer in an aqueous solution of a polyanion, and a polyanion; and an organic solvent. The polyanion has anion groups, and an oxygen atom of some anion groups is bonded to a substituent represented by the following chemical formula (A): -CHOH-R [where R is any organic group].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, sufficient release properties cannot be expressed in the conductive layer.

  As a countermeasure for the above problem, 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 that is not doped in a π-conjugated conductive polymer is reacted with an oxirane group or 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, even in the method described in Patent Document 2, the dispersibility of the conductive composite in the organic solvent may be insufficient, and the conductive layer formed from the conductive polymer organic solvent dispersion described in Patent Document 2 In this case, the conductivity may be lowered.
Therefore, the present invention provides a conductive polymer dispersion that can easily form a conductive layer having a high dispersibility of the conductive composite and a high conductivity despite using an organic solvent as a dispersion medium, and the production thereof. It aims to provide a method. Moreover, it aims at providing the manufacturing method of the electroconductive film which can form a conductive layer with high electroconductivity easily.

The present invention includes the following aspects.
[1] A conductive complex containing a π-conjugated conductive polymer and a polyanion, and an organic solvent. The polyanion has an anion group, and an oxygen atom of a part of the anion group has the following chemical formula (A A conductive polymer dispersion in which a substituent represented by
[In the chemical formula (A), R is an arbitrary organic group. ]
[2] The conductive polymer dispersion according to [1], wherein the content of the organic solvent is 50% by mass or more and 99.9% by mass or less based on the total mass of the conductive polymer dispersion.
[3] The conductive polymer dispersion according to [1] or [2], wherein the organic solvent contains methyl ethyl ketone.
[4] The conductive polymer dispersion according to any one of [1] to [3], wherein the organic solvent contains a water-insoluble organic solvent.
[5] The conductive polymer dispersion according to any one of [1] to [4], wherein the organic solvent contains 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 silicone compound.
[10] The conductive polymer dispersion according to [9], wherein the silicone compound is addition-curable silicone.

[12] An aldehyde compound 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, and the conductive complex is precipitated to obtain a precipitate. Then, the manufacturing method of the electroconductive polymer dispersion liquid which collect | recovering this deposit and adding an organic solvent to the collect | recovered deposit.
[13] A conductive composite containing a π-conjugated conductive polymer and a polyanion is dried in an aqueous dispersion containing the aqueous dispersion medium to obtain a dried conductive composite; Adding an aldehyde compound and an organic solvent, and producing a conductive polymer dispersion.
[14] The method for producing a conductive polymer dispersion according to [12] or [13], further comprising adding a binder component.
[15] Applying the conductive polymer dispersion according to any one of [1] to [11] to at least one surface of the film substrate; and applying the applied conductive polymer dispersion. The manufacturing method of an electroconductive film including drying.

Although the conductive polymer dispersion of the present invention uses an organic solvent as a dispersion medium, the conductive composite has a high dispersibility and can easily form a conductive layer with high conductivity.
According to the method for producing a conductive polymer dispersion of the present invention, a conductive polymer dispersion having the above effects can be easily produced.
According to the method for producing a conductive film of the present invention, a conductive layer having high conductivity can be easily formed.

<Conductive polymer dispersion>
Hereinafter, an embodiment of the conductive polymer dispersion of the present invention will be described.
The conductive polymer dispersion of this embodiment contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, and an organic solvent.

(Π-conjugated conductive polymer)
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 polymer 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 contained in the conductive composite may be 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 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 is a mass-based average molecular weight determined by gel permeation chromatography and calculated in terms of polystyrene.

  A polyanion forms a conductive composite by doping a π-conjugated conductive polymer. However, in the polyanion, all the anion groups are not doped into the π-conjugated conductive polymer, and have an excess anion group that does not participate in the doping. Since the surplus anion group is a hydrophilic group, the conductive complex has a high water dispersibility and a low organic solvent dispersibility before being reacted with the aldehyde compound as described later.

  The polyanion used in this embodiment has an anion group, and a substituent represented by the above chemical formula (A) is bonded to an oxygen atom of a part of the anion group. That is, the proton of the anion group is substituted with the substituent represented by the chemical formula (A).

R in the chemical formula (A) is an arbitrary organic group. However, from the viewpoint of hydrophobizing the conductive composite, R is preferably a hydrophobic organic group. The hydrophobic organic group is an organic group having no acid group such as a carboxy group.
Specific examples of R include an alkyl group, a cycloalkyl group, a phenyl group, and the like, and an alkyl group is preferable.
As the alkyl group, an alkyl group having 1 to 12 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, i-butyl group, pentyl group, hexyl group, heptyl group, Examples include octyl group, decyl group, dodecyl group, 2-ethylhexyl group and the like.
Examples of the cycloalkyl group include a cycloalkyl group having 5 to 8 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
The alkyl group, cycloalkyl group or phenyl group may have a substituent other than the acid group.

  The substituent represented by the chemical formula (A) is a hydrophobic substituent formed by a reaction between an anion group of a polyanion and an aldehyde compound. By this reaction, protons in some anion groups of the polyanion can be replaced with the hydrophobic substituent.

An aldehyde compound is a compound having an aldehyde group.
Specific examples of the aldehyde compound include alkyl aldehydes having an alkyl group and an aldehyde group, cycloalkyl aldehydes having a cycloalkyl group and an aldehyde group, phenyl aldehydes having a phenyl group and an aldehyde group, and the like.
Examples of the alkyl group of the alkyl aldehyde include alkyl groups having 1 to 12 carbon atoms. Examples of the alkyl aldehyde having an alkyl group having 1 to 12 carbon atoms include, for example, methanal (formaldehyde), etanal (acetaldehyde), propanal (propionaldehyde), butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, dodecanal. Examples of the cycloalkyl group of the cycloalkyl aldehyde include cycloalkyl groups having 5 to 8 carbon atoms. Examples of the cycloalkyl aldehyde having a cycloalkyl group having 5 to 8 carbon atoms include cyclopentane aldehyde, cyclohexane aldehyde, cyclopentene aldehyde, cyclooctene aldehyde, and the like.
An aldehyde compound may be used individually by 1 type, and may use 2 or more types together. That is, the hydrophobic substituent may be one type or two or more types.

The amount of the anion group that reacts with the aldehyde compound is preferably 0.1 mol% or more and 90 mol% or less, and preferably 1 mol% or more and 80 mol% or less, based on the number of moles of all anion groups of the polyanion. Is more preferable. If the amount of the anion group that reacts with the aldehyde compound is not less than the lower limit, the polyanion can be sufficiently hydrophobized by the reaction with the aldehyde compound. If the amount of the anionic group that reacts with the aldehyde compound is equal to or less than the upper limit, conductivity can be secured.
From the viewpoint of reaction controllability and prevention of dedoping, the polyanion preferably has substantially no hydrophobic substituent formed by reaction of at least one of an epoxy compound and an amine compound with some anion groups. For example, it is preferable that the ratio of the hydrophobic substituent formed by reacting at least one of an epoxy compound and an amine compound with an anion group is less than 0.01 mol% with respect to the number of moles of the total hydrophobic substituent.

  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 in the range of 100 parts by mass or more and 500 parts by mass or less. If the content ratio of the polyanion is not less than the lower limit, the doping effect on the π-conjugated conductive polymer tends to become strong, and the conductivity becomes higher. When the polyanion content is not more than the above upper limit, the conductive complex can be easily hydrophobized.

  The content of the conductive complex with respect to the total mass of the conductive polymer dispersion is, for example, preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, 0.4 mass% or more and 5.0 mass% or less are more preferable.

(Organic solvent)
The organic solvent used in this embodiment may be a water-soluble organic solvent, a water-insoluble organic solvent, or both a water-soluble organic solvent and a water-insoluble organic solvent. Here, the water-soluble organic solvent is an organic solvent having a solubility of 1 g or more with respect to 100 g of water at a temperature of 20 ° C., and the water-insoluble organic solvent has a solubility of less than 1 g with respect to 100 g of water at a temperature of 20 ° C. It is an organic solvent.

Examples of the water-soluble organic solvent include alcohol solvents, ether solvents, ketone 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, Examples 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 nitrogen atom-containing solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide 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.
A water-soluble organic solvent may be used individually by 1 type, and may use 2 or more types together.
When the conductive polymer dispersion of this embodiment is used as a coating liquid for forming a conductive layer, methyl ethyl ketone is preferred as the water-soluble organic solvent because the suitability as a coating liquid is improved.

Examples of the water-insoluble organic solvent include hydrocarbon solvents. Examples of the hydrocarbon solvent include an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent.
Examples of the aliphatic hydrocarbon solvent include hexane, cyclohexane, pentane, heptane, octane, nonane, decane, dodecane, and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, and the like.
A water-insoluble organic solvent may be used individually by 1 type, and may use 2 or more types together.
Among the water-insoluble organic solvents, an aromatic hydrocarbon solvent is preferable and toluene is more preferable in that the conductive polymer dispersion in this embodiment can be easily produced.

  The content ratio of the organic solvent in the conductive polymer dispersion of this embodiment is preferably 50% by mass or more and 99.9% by mass or less of the organic solvent with respect to the total mass of the conductive polymer dispersion. % To 99.9% by mass, more preferably 90% to 99.9% by mass. If the content ratio of the organic solvent is equal to or higher than the lower limit value, the hydrophobic conductive composite can be easily dispersed. If the organic solvent content is equal to or lower than the upper limit value, the conductive layer can be easily removed from the conductive polymer dispersion. Can be formed.

(Binder component)
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.
Since the conductive polymer dispersion of this embodiment uses an organic solvent as a dispersion medium, a low polarity silicone compound can be suitably used as a binder component.

A curable silicone is mentioned as a silicone compound. 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. In this embodiment, even if addition-curable silicone is used, curing inhibition is unlikely to occur, which is preferable.
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.

  Further, as the binder component, a thermoplastic resin (such as polyester), a thermosetting compound (such as a polyfunctional epoxy compound), or an active energy ray curable compound (such as an acrylic compound) other than the silicone compound is used. Also good. When using a thermosetting compound, it is preferable to further contain a thermal polymerization initiator, and when using an active energy ray-curable compound, it is preferable to further contain a photopolymerization initiator.

  The content ratio of the binder component is preferably 50 parts by mass or more and 100000 parts by mass or less, more preferably 100 parts by mass or more and 50000 parts by mass or less, with respect to 100 parts by mass of the conductive composite. More preferably, it is 10000 parts by mass or less. 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.

(High conductivity agent)
The conductive polymer dispersion may contain a highly conductive agent in order to further improve the conductivity.
Here, the above-described π-conjugated conductive polymer, polyanion, aldehyde compound, organic solvent and binder component are not classified as a highly conductive agent.
The highly conductive agent is 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, a compound having an amide group, It is preferably at least one compound selected from the group consisting of a compound having an imide group, a lactam compound, and a compound having a glycidyl group.
The highly conductive agent contained in the conductive polymer dispersion may be one type or two or more types.
The content ratio of the highly conductive agent is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, with respect to 100 parts by mass of the conductive composite. More preferably, it is not less than 2500 parts by mass.
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.

(Other additives)
The conductive polymer dispersion may contain other known additives.
The additive is not particularly limited as long as the effect of the present invention is obtained, 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 above-described π-conjugated conductive polymer, polyanion, aldehyde compound, organic solvent, binder component, and high conductivity agent.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferred from the viewpoint of storage stability. Further, a polymer surfactant such as polyvinyl pyrrolidone may be added.
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 a silane coupling agent having a vinyl group or an amino group.
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. For example, the content is 0. 10 parts by mass with respect to 100 parts by mass of the solid content of the conductive composite. The range can be 001 parts by mass or more and 5 parts by mass or less.

(Method for producing conductive polymer dispersion)
Examples of the method for producing the conductive polymer dispersion of this embodiment include a first production method including precipitation, recovery, and dispersion, and a second production method including drying and dispersion.

[First manufacturing method]
Precipitation Precipitation in the first production method is to add an aldehyde compound to a conductive polymer aqueous dispersion containing a conductive composite, to precipitate the conductive composite to form a precipitate.
When an aldehyde compound is added to the aqueous dispersion, an anion group that is part of the polyanion constituting the conductive complex, specifically, an anionic group that does not participate in doping to the π-conjugated conductive polymer, Reaction with aldehyde compound occurs. Thereby, an aldehyde compound is added to the anion group of the polyanion, the anion group disappears, a hydrophobic substituent represented by the chemical formula (A) is formed, and the conductive complex is hydrophobized.
However, the aldehyde compound may not react with all of the anion groups that do not participate in doping to the π-conjugated conductive polymer, and some anion groups that do not participate in doping may remain.
The hydrophobized conductive composite (hereinafter sometimes referred to as “hydrophobized conductive composite”) cannot be dispersed in an aqueous dispersion medium, and thus precipitates to form a precipitate.

  The amount of the aldehyde compound added is preferably 1 part by mass or more and 100000 parts by mass or less, more preferably 10 parts by mass or more and 50000 parts by mass or less, with respect to 100 parts by mass of the conductive composite. More preferably, it is 10000 parts by mass or less. If the addition amount of the aldehyde compound is not less than the lower limit, the hydrophobicity of the conductive composite can be sufficiently improved. If the addition amount of the aldehyde compound is not more than the above upper limit value, it is possible to prevent a decrease in conductivity of the conductive layer formed from the conductive polymer dispersion.

  In the first production method, when the aldehyde compound is reacted with the anion group of the polyanion, it is preferable not to add at least one of an epoxy compound and an amine compound. Even when at least one of an epoxy compound and an amine compound is added, the addition amount is preferably less than 1 part by mass with respect to 100 parts by mass of the conductive composite.

In the precipitation, the conductive polymer aqueous dispersion to which an aldehyde compound is added is a dispersion in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium. Here, the aqueous dispersion medium contains water and may contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents, and ester solvents. A water-soluble organic solvent may be used individually by 1 type, and may use 2 or more types together.
The water content in the aqueous dispersion medium is preferably 50% by mass or more, more preferably 80% by mass or more, and may be 100% by mass.
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 polyanion. A commercially available conductive polymer aqueous dispersion may be used.
A known catalyst may be applied to the chemical oxidative polymerization. For example, a catalyst and an oxidizing agent can be used. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. The oxidizing agent can return the reduced catalyst to its original oxidation state.
The content of the conductive complex contained in the conductive polymer aqueous dispersion is preferably 0.1% by mass or more and 10% by mass or less, and 0.3% by mass with respect to the total mass of the conductive polymer dispersion. % To 5% by mass is preferable, and 0.5% to 4% by mass is more preferable.

An organic solvent may be added before the aldehyde compound is added to the conductive polymer aqueous dispersion, simultaneously with the addition, or after the addition. Since the aldehyde compound is hydrophobic, it is preferable to add it to the conductive polymer aqueous dispersion after being dispersed in an organic solvent. The concentration of the aldehyde compound in the solution in which the aldehyde compound is dispersed in the organic solvent is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 20% by mass or less.
As the organic solvent, a water-soluble organic solvent is preferable. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents, and ester solvents. When a water-soluble organic solvent is included, one type may be used alone, or two or more types may be used in combination.

In the preparation liquid prepared by adding an aldehyde compound and an organic solvent to the conductive polymer aqueous dispersion, preferred concentrations of the conductive complex, water, the aldehyde compound and the organic solvent are as follows.
The concentration of the conductive composite is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 5% by mass or less with respect to the total mass of the preparation solution.
The concentration of water is preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 70% by mass or less with respect to the total mass of the preparation solution.
The concentration of the aldehyde compound is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 1% by mass or more and 40% by mass or less with respect to the total mass of the preparation solution.
The concentration of the organic solvent is preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 70% by mass or less with respect to the total mass of the preparation solution.
When the concentration of each component in the preparation solution is within the above range, the aldehyde compound can be easily reacted with the anion group of the polyanion of the conductive complex, and the precipitate can be easily recovered.

You may heat in the range of 50 degreeC or more and 100 degrees C or less before adding the aldehyde compound to the electroconductive polymer aqueous dispersion, during the addition, or after adding, for example. The reaction between the anion group and the aldehyde compound can be promoted by heating.
Moreover, it is preferable to stir and mix during or after adding the aldehyde compound to the conductive polymer aqueous dispersion.

-Recovery The recovery in the first manufacturing method is to recover the precipitate formed of the hydrophobic conductive composite.
As a method for separating and recovering the precipitate from the aqueous dispersion medium, for example, a known sorting method such as filtration, precipitation, or extraction can be applied. Among these fractionation methods, filtration is preferable, and it is preferable to perform filtration using a coarse filter so that the polyanion used for forming the conductive complex passes along with the filtrate. According to this filtration method, the precipitate can be separated and the excess polyanion not forming the conductive complex can be left on the filtrate side to separate the precipitate from the excess polyanion. By removing the excess polyanion, the conductivity of the precipitate can be increased.

  As the filter used for filtration, filter paper used in the chemical analysis field is preferable. Examples of the filter paper include a filter paper manufactured by Advantech, and a reserved particle diameter of 7 μm. Here, the retained particle diameter of the filter paper is a measure of the roughness of the eyes, and is obtained from the leaked particle diameter when barium sulfate or the like specified by JIS P 3801 [filter paper (for chemical analysis)] is naturally filtered. The retained particle diameter of the filter paper can be, for example, 2 μm or more and 20 μm or less. The retained particle diameter is preferably 5 μm or more and 10 μm or less because it can be easily separated by permeating excess polyanions.

-Dispersion Dispersion in the first production method is to disperse the collected precipitate in an organic solvent. By this dispersion, a conductive polymer dispersion in which the hydrophobic conductive composite is dispersed in an organic solvent is obtained.
When the precipitate is dispersed in the organic solvent, it is preferable to perform a dispersion treatment on the organic solvent containing the precipitate. As the dispersion treatment, it is preferable to use a pressurizable high-pressure homogenizer from the viewpoint that the dispersibility of the precipitate in the organic solvent can be enhanced.

-Addition of binder component When the conductive polymer dispersion liquid of this embodiment contains a binder component, the conductive polymer aqueous dispersion liquid, the precipitate, or the conductive polymer dispersion liquid obtained by the dispersion described above. A binder component may be added.
Among these addition methods, in order to stably disperse the binder component in the conductive polymer dispersion, it is preferable to add the binder component to the conductive polymer dispersion obtained by the dispersion.
When the binder component is an addition-curable silicone, it is preferable to add a curing catalyst together with the addition-curable silicone.

-Addition of highly conductive agent and additive In the first production method, when adding a highly conductive agent, additive, etc. to the conductive polymer dispersion, examples of the addition method include the following (i) to The method of (iii) is mentioned.
(I) A method of adding one kind selected from the group consisting of a highly conductive agent and an additive to the conductive polymer aqueous dispersion before precipitation.
(Ii) A method of adding one kind selected from the group consisting of a highly conductive agent and an additive to the precipitate.
(Iii) A method of adding one type selected from the group consisting of a high conductivity agent and an additive to the conductive polymer dispersion obtained by the dispersion.
Among these methods, the method (iii) is capable of stably dispersing one selected from the group consisting of a high conductivity agent and an additive in the conductive polymer dispersion obtained by the dispersion. Is preferred.

[Second manufacturing method]
-Drying Drying in the second production method is to remove water from the conductive polymer aqueous dispersion and dry it to obtain a dried product. The conductive polymer aqueous dispersion used in the second production method is the same as the conductive polymer aqueous dispersion used in the first production method.
Examples of the method for drying the conductive polymer aqueous dispersion include a method of freeze-drying the conductive polymer aqueous dispersion, a method of heating and drying the conductive polymer aqueous dispersion, and a vacuum of the conductive polymer aqueous dispersion. Examples thereof include a drying method, a method of heating and vacuum drying the conductive polymer aqueous dispersion, and a method of removing water by membrane separation. Among the water removal methods described above, the method of freeze-drying the conductive polymer aqueous dispersion is preferred because the water of the conductive polymer aqueous dispersion can be sufficiently removed without degrading the conductive composite.
In lyophilization, the water in the conductive polymer aqueous dispersion is frozen and vacuum dried. The temperature during lyophilization is preferably 0 ° C. or lower. If the lyophilization temperature is not more than the above upper limit value, it is easy to freeze water. The freeze-drying temperature is preferably −60 ° C. or higher, more preferably −40 ° C. or lower. If lyophilization temperature is more than the said lower limit, temperature can be adjusted easily.

  In this drying, water is removed until the content of water with respect to the total mass of the obtained dried body is preferably 0% by mass or more and 50% by mass or less, more preferably 0% by mass or more and 10% by mass or less. If the content of water in the dried product is set to the upper limit or less, the content of water with respect to the total mass of the conductive polymer dispersion of this embodiment can be easily reduced to 1.0% by mass or less.

-Dispersion The dispersion | distribution in a 2nd manufacturing method is adding an aldehyde compound to the dried body obtained by the said drying, mixing an organic solvent, and dispersing the dried body containing a conductive composite in an organic solvent. By this dispersion, a conductive polymer dispersion in which the hydrophobic conductive composite is dispersed in an organic solvent is obtained.
In this dispersion, an aldehyde compound is added to the dried product to cause a reaction between some anion groups of the polyanion contained in the dried product and the aldehyde compound. Thereby, the substituent represented by the chemical formula (A) is formed to obtain the hydrophobic conductive composite. The obtained hydrophobic conductive composite is dispersed in an organic solvent.
In order to promote the reaction between the anion group and the aldehyde compound, after adding the aldehyde to the dried product, for example, heating may be performed in a range of 50 ° C to 100 ° C.

An organic solvent may be added before or after the aldehyde compound is added to the dried product. Since the aldehyde compound is hydrophobic, it is preferably added to the dried product after being dispersed in an organic solvent. The concentration of the aldehyde compound in the solution in which the aldehyde compound is dispersed in the organic solvent is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 20% by mass or less.
As the organic solvent, a water-soluble organic solvent is preferable. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents, and ester solvents. When a water-soluble organic solvent is included, one type may be used alone, or two or more types may be used in combination.

  When the hydrophobic conductive composite is dispersed in the organic solvent, it is preferable to perform a dispersion treatment on the organic solvent containing the hydrophobic conductive composite. Similar to the first production method, it is preferable to use a high-pressure homogenizer in the dispersion treatment.

  The addition amount of the aldehyde compound is preferably 1 part by mass or more and 100000 parts by mass or less, and preferably 10 parts by mass or more and 50000 parts by mass or less with respect to 100 parts by mass of the conductive composite, as in the first production method. More preferably, it is 50 parts by mass or more and 10,000 parts by mass or less.

  In the second production method, when the aldehyde compound is reacted with the anion group of the polyanion, it is preferable not to add at least one of an epoxy compound and an amine compound. Even when at least one of an epoxy compound and an amine compound is added, the addition amount is preferably less than 1 part by mass with respect to 100 parts by mass of the conductive composite.

-Addition of binder component When the conductive polymer dispersion liquid of this embodiment contains a binder component, the conductive polymer aqueous dispersion liquid, the dried body, or the conductive polymer dispersion liquid obtained by the dispersion described above. A binder component may be added.
In order to stably disperse the binder component in the conductive polymer dispersion, it is preferable to further add a binder component to the conductive polymer dispersion obtained by the dispersion.
When the binder component is an addition-curable silicone, it is preferable to add a curing catalyst together with the addition-curable silicone.

-Addition of highly conductive agent and additive In the second production method, when adding a highly conductive agent, additive, etc. to the conductive polymer dispersion, examples of the addition method include the following (iv) to The method of (vi) is mentioned.
(Iv) A method of adding one kind selected from the group consisting of a highly conductive agent and an additive to the conductive polymer aqueous dispersion before drying.
(V) A method of adding one kind selected from the group consisting of a highly conductive agent and an additive to the dried body.
(Vi) A method of adding one type selected from the group consisting of a high conductivity agent and an additive to the conductive polymer dispersion obtained by the dispersion.
Among these methods, the method (vi) is capable of stably dispersing one selected from the group consisting of a high conductivity agent and an additive in the conductive polymer dispersion obtained by the dispersion. Is preferred.

(Function and effect)
In this embodiment, the conductive complex has a hydrophobic substituent formed by the reaction of a part of the anion group of the polyanion and the aldehyde compound, specifically, a substituent represented by the chemical formula (A). Therefore, it is hydrophobized. Therefore, although the organic solvent is used as the dispersion medium, the dispersibility of the conductive composite can be increased. In addition, by applying a conductive polymer dispersion liquid with high dispersibility of the conductive composite, the conductive composite in the conductive layer can also be highly dispersible, so a highly conductive layer can be easily formed. it can.
When the anion group of the polyanion is hydrophobized with an amine compound or the like, the anion group of the polyanion may be dedope from the π-conjugated conductive polymer and the conductivity may be lowered. However, when the polyanion is hydrophobized by reacting an aldehyde compound with an anion group as in this embodiment, de-doping of the anion group of the polyanion from the π-conjugated conductive polymer is unlikely to occur. Therefore, it is possible to suppress a decrease in the conductive layer when the polyanion is hydrophobized. Also from this point, the conductivity of the conductive layer formed from the conductive polymer dispersion can be increased.
In addition, the conductive polymer dispersion of this embodiment in which the main component of the dispersion medium is an organic solvent can disperse a binder component, particularly a hydrophobic binder component such as a silicone compound, with high dispersibility. A conductive layer formed from a conductive polymer dispersion containing a binder component has high strength. When the binder component is a silicone compound, a conductive layer having high peelability can be easily formed.

<Method for producing conductive film>
Hereinafter, one aspect of the method for producing a conductive film of the present invention will be described.
The method for producing a conductive film according to this aspect comprises: coating the conductive polymer dispersion liquid according to the above aspect on at least one surface of a film substrate; and a coating film comprising the coated conductive polymer dispersion liquid. Drying the (conductive layer).

Examples of the film substrate used in the manufacturing method of this embodiment include a plastic film and paper.
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, styrene elastomer, polyester elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio And the like. Among these resins for film base materials, polyethylene terephthalate is preferable because it is inexpensive and has excellent mechanical strength.
The film base resin may be amorphous or crystalline.
Further, the film substrate may be unstretched or stretched.
The film substrate may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or flame treatment in order to further 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.

(Coating)
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.

(Dry)
Examples of the method for drying the coated conductive polymer dispersion 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, and can be set to 50 ° C. or higher and 150 ° C. or lower, for example. Here, the heating temperature is a set temperature of the drying apparatus.

When the conductive polymer dispersion contains a thermosetting binder component, it is preferable that the coating film be thermally cured by applying heat drying during the drying.
When the conductive polymer dispersion contains an active energy ray-curable binder component, after the drying step, an active energy ray irradiation step of irradiating the dried conductive polymer coating film with active energy rays Furthermore, you may have. 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.
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. As the ultraviolet light source, 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 specification are using Topcon 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 a measured value.
When the conductive polymer dispersion contains a curable silicone as a binder component, the silicone is uncured and can be easily adhered to the substrate. When the coating film is cured, the silicone is cured and the cohesive force of the silicone is improved, so that the releasability can be expressed.

(Conductive film)
The conductive film obtained by the manufacturing method according to this aspect includes a film base and a conductive layer formed on at least one surface of the film base. The conductive layer contains a conductive complex including a π-conjugated conductive polymer and a polyanion. Hydrogen atoms of some anion groups of the polyanion contained in the conductive layer are substituted with the hydrophobic substituent represented by the chemical formula (A). When the conductive polymer dispersion includes a binder component, the conductive component includes a binder component or a cured product obtained by curing the binder component.
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.
The average thickness in the present specification is a value obtained by observing a cross section at any 10 locations, measuring the thickness, and averaging the measured values.

(Function and effect)
In the conductive polymer dispersion of the above aspect, since the conductive composite is highly dispersed in an organic solvent, the conductive composite is highly dispersed even in a conductive layer formed from the conductive polymer dispersion. It can be included in the dispersion. Therefore, the conductivity of the conductive layer can be sufficiently increased.
Further, when the conductive polymer dispersion contains a silicone compound, the silicone compound is highly dispersed in the conductive polymer dispersion, so that the silicone in the conductive layer formed from the conductive polymer dispersion The dispersibility of the compound can be increased. Therefore, the release property of the conductive layer expressed by the silicone compound can be sufficiently increased.
Moreover, in the manufacturing method of the electroconductive film of this aspect, since the electroconductive polymer dispersion liquid of the said aspect with high lipophilicity is applied to a film base material, the electroconductive layer formed from an electroconductive polymer dispersion liquid is a film. High adhesion to the substrate.

(Production Example 1)
Dissolve 206 g of sodium styrenesulfonate in 1000 ml of ion-exchanged water, add dropwise 1.14 g of ammonium persulfate oxidizer solution previously dissolved in 10 ml of water for 20 minutes while stirring at 80 ° C. Stir for hours.
To the obtained sodium styrenesulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, and 1000 ml of the solvent of the polystyrenesulfonic acid-containing solution was removed using an ultrafiltration method. 2000 ml of ion-exchanged water was added to the remaining liquid, about 2000 ml of the solvent was removed using an ultrafiltration method, and polystyrene sulfonic acid was washed with water. 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 obtained by dissolving 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 in 2000 ml of ion-exchanged water were mixed at 20 ° C. While stirring the mixed solution obtained at 20 ° C., 29.64 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added. The reaction was stirred for 3 hours.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solvent was removed using an ultrafiltration method. This operation was repeated three times. Next, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the resulting solution, and about 2000 ml of solvent was removed using an ultrafiltration method. 2000 ml of ion-exchanged water was added to the remaining liquid, about 2000 ml of the solvent was removed using an ultrafiltration method, and polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS) was washed with water. This operation was repeated 8 times to obtain a PEDOT-PSS aqueous dispersion having a solid concentration of 1.2% by mass. In addition, content of PSS with respect to PEDOT-PSS solid content is 75 mass%.

(Production Example 3)
300 g of methanol and 25 g of decanal were added to 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, and the mixture was heated and stirred at 80 ° C. for 4 hours. Thereby, the deposit of the electroconductive complex formed from PEDOT-PSS and decanal was obtained. The precipitate was collected by filtration, washed with 100 g of methanol, and 1.3 g of a conductive composite was obtained.

(Production Example 4)
300 g of methanol and 25 g of butanal were added to 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, and the mixture was heated and stirred at 80 ° C. for 4 hours. As a result, a precipitate of a conductive composite formed from a π-conjugated conductive polymer, a polyanion, and butanal was obtained. The precipitate was collected by filtration and washed with 100 g of methanol to obtain 1.2 g of a conductive composite.

(Example 1)
300 g of methyl ethyl ketone was added to 1.3 g of the conductive composite obtained in Production Example 3, and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion.
The obtained conductive polymer dispersion was designated as No.1. Using a 14 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 form a non-molding conductive layer, thereby obtaining a conductive film.
In addition, 8.55 g of the obtained conductive polymer dispersion was added to an addition-curing type silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KS-3703T, solid content concentration 30 mass%, toluene solution) 0.15 g and a platinum catalyst (Shin-Etsu). Chemical Industry Co., Ltd. (CAT-PL-50T) (0.03 g) was mixed to obtain a silicone-containing conductive polymer dispersion.
The obtained silicone-containing conductive polymer dispersion was designated No. Using a 14 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 releasable conductive layer to obtain a conductive release film. .

(Example 2)
A conductive film and a conductive release film in the same manner as in Example 1 except that 1.3 g of the conductive composite obtained in Production Example 3 was changed to 1.2 g of the conductive composite obtained in Production Example 4. Got.

(Comparative Example 1)
300 g of methanol was added to the PEDOT-PSS aqueous dispersion obtained in Production Example 2, and the mixture was heated and stirred at 80 ° C. for 4 hours. Although the obtained solution was filtered, no precipitate was left on the filter paper, so the production of the conductive polymer dispersion was stopped.

<Evaluation>
[Measurement of surface resistance]
About the electroconductive film and electroconductive release film of each example, the surface resistance value of the electroconductive layer was measured on the conditions of the applied voltage of 10V using the resistivity meter (Mitsubishi Chemical Analytic Co., Ltd. Hiresta). The measurement results are shown in Table 1.
[Measurement of peel force]
The release force was measured by the following method in the conductive layer of the conductive release film of each example to evaluate the release property.
A 25 mm wide polyester adhesive tape (Nitto Denko, No. 31B) was placed on the surface of the conductive layer of the conductive release film of each example, and a load of 1976 Pa was placed on the adhesive tape at 25 ° C. for 20 hours. Pressurized. Next, according to JIS Z0237, using a tensile tester, the adhesive tape affixed to the conductive layer was peeled off at an angle of 180 ° (peeling speed 0.3 m / min), and the peeling force (unit: N) was It was measured. The measurement results are shown in Table 1. The smaller the peeling force, the higher the release property of the conductive layer.

  The conductive film and conductive release film of each Example had a small surface resistance value and high conductivity. Moreover, the electroconductive release film of each Example had small peeling force, and had high release property.

Claims (14)

a conductive complex containing a π-conjugated conductive polymer and a polyanion, and an organic solvent,
The polyanion has an anionic group and is a conductive polymer dispersion in which a substituent represented by the following chemical formula (A) is bonded to an oxygen atom of a part of the anionic group.

[In the chemical formula (A), R is an arbitrary organic group. ]   2. The conductive polymer dispersion according to claim 1, wherein the content of the organic solvent is 50% by mass or more and 99.9% by mass or less based on the total mass of the conductive polymer dispersion.   The conductive polymer dispersion according to claim 1, wherein the organic solvent contains methyl ethyl ketone.   The conductive polymer dispersion according to any one of claims 1 to 3, wherein the organic solvent contains a water-insoluble organic solvent.   The conductive polymer dispersion according to claim 1, wherein the organic solvent contains 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 silicone compound.   The conductive polymer dispersion according to claim 9, wherein the silicone compound is addition-curable silicone. After adding the aldehyde compound to the aqueous dispersion in which the conductive complex containing the π-conjugated conductive polymer and the polyanion is contained in the aqueous dispersion medium, the conductive complex is precipitated to obtain a precipitate, Collecting the precipitate,
A method for producing a conductive polymer dispersion, comprising adding an organic solvent to the collected precipitate. a conductive composite containing a π-conjugated conductive polymer and a polyanion is dried in an aqueous dispersion contained in an aqueous dispersion medium to obtain a dried conductive composite;
Adding an aldehyde compound and an organic solvent to the dried product, and a method for producing a conductive polymer dispersion.   The method for producing a conductive polymer dispersion according to claim 11 or 12, further comprising adding a binder component.   Applying the conductive polymer dispersion according to any one of claims 1 to 10 to at least one surface of the film substrate, and drying the coated conductive polymer dispersion; The manufacturing method of the electroconductive film containing this.