JP2018203868A - Conductive polymer dispersion, method of manufacturing the same, and method of manufacturing conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a conductive polymer dispersion of the present invention, in which an organic solvent is used as a dispersion medium, the dispersibility of a conductive composite is high, and adhesion and conductivity to a film substrate are sufficiently high. A high conductive layer can be easily formed. A conductive polymer dispersion of the present invention contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, and an organic solvent, and the polyanion is a part of an anion group together with a part of the anion group. It further has a substituent (B) formed by reacting the isocyanate group-containing compound with the substituent (A) formed by the reaction of the anion group and the epoxy group-containing compound. [Selection diagram] 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 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, even in the method described in Patent Document 2, the dispersibility of the conductive composite with respect to the organic solvent may be insufficient. In some cases, the dispersibility of the conductive composite may be low. Moreover, in the conductive layer formed from the conductive polymer organic solvent dispersion described in Patent Document 2, the adhesion to the film substrate and the conductivity may be lowered.
Therefore, the present invention can easily form a conductive layer having high dispersibility of the conductive composite and sufficiently high adhesion and conductivity to the film substrate, despite using an organic solvent as a dispersion medium. It is an object to provide a conductive polymer dispersion and a method for producing the same. Moreover, it aims at providing the manufacturing method of the electroconductive film which can form easily the electroconductive layer with high adhesiveness with respect to a film base material, and electroconductivity.

The present invention includes the following aspects.
[1] A conductive complex containing a π-conjugated conductive polymer and a polyanion and an organic solvent, and the polyanion is formed by a reaction of a part of an anion group and an epoxy group-containing compound together with an anion group. A conductive polymer dispersion further comprising a substituent (B) formed by reacting an isocyanate group-containing compound with the substituted group (A).
[2] The conductive polymer dispersion according to [1], wherein the organic solvent contains a hydrocarbon solvent.
[3] The conductive polymer dispersion according to [2], wherein the hydrocarbon solvent content in the organic solvent is 50% by mass or more.
[4] The conductive polymer dispersion according to [2] or [3], wherein the hydrocarbon solvent is at least one of heptane and toluene.
[5] The conductive polymer dispersion according to any one of [1] to [4], wherein the organic solvent contains methyl ethyl ketone.
[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 an addition-curable silicone compound.

[11] An epoxy group-containing 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 form a precipitate. After obtaining, a precipitation collection step for collecting the precipitate, and an isocyanate group-containing compound addition step for obtaining a first preparation liquid by adding the first organic solvent and the isocyanate group-containing compound to the collected precipitate, A method for producing a conductive polymer dispersion.
[12] The method further includes a washing step of washing the precipitate with an organic solvent for washing containing an organic solvent having no hydroxy group between the precipitation collection step and the isocyanate group-containing compound addition step. [11] A method for producing a conductive polymer dispersion described in 1.
[13] The method for producing a conductive polymer dispersion according to [11] or [12], wherein the first organic solvent is methyl ethyl ketone.
[14] A drying step in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is dried in an aqueous dispersion containing an aqueous dispersion medium to obtain a dried product of the conductive composite;
A first preparation liquid preparation step of adding an epoxy group-containing compound and a first organic solvent to the dried product, and further adding an isocyanate group-containing compound to obtain a first preparation liquid. Production method.
[15] The method for producing a conductive polymer dispersion according to any one of [11] to [14], further comprising a binder component addition step of adding a binder component to the first preparation liquid.
[16] The high conductivity according to any one of [11] to [15], further comprising a second organic solvent addition step of adding a second organic solvent to the first preparation solution to obtain a second preparation solution. A method for producing a molecular dispersion.
[17] The method for producing a conductive polymer dispersion according to [16], wherein the second organic solvent is a hydrocarbon solvent.
[18] The method for producing a conductive polymer dispersion according to [16] or [17], further comprising a binder component addition step of adding a binder component to the second preparation liquid.
[19] A coating step of coating the conductive polymer dispersion according to any one of [1] to [10] 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.

The conductive polymer dispersion of the present invention has a conductive layer having high dispersibility of the conductive composite and sufficiently high adhesion and conductivity to the film substrate, despite using an organic solvent as a dispersion medium. Can be easily formed.
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 adhesion and high conductivity to a film substrate can be easily formed.

<Conductive polymer dispersion>
The conductive polymer dispersion of one embodiment of the present invention contains a conductive complex including 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.

  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 doping. Since the surplus anion group is a hydrophilic group, the conductive composite has high water dispersibility and low organic solvent dispersibility before being reacted with the epoxy group-containing compound as will be described later.

The polyanion used in this embodiment includes an anionic group and a substituent (B) formed by further reacting an isocyanate group-containing compound with the substituent (A) formed by the reaction of a part of the anionic group and the epoxy group-containing compound. ).
Although detailed analysis of the conductive complex is not always easy, it is assumed that the substituent (A) is a group represented by the following chemical formula (A) and the substituent (B) is a group represented by the following chemical formula (B). Is done. That is, in this embodiment, it is presumed that protons in some anion groups of the polyanion are replaced with the substituent (B).

R ¹ and R ² in chemical formula (A) and chemical formula (B) are each an arbitrary substituent. The hydroxy group in the chemical formula (A) is a group formed by the ring opening of the epoxy group of the epoxy group-containing compound, and R ¹ is a substituent derived from the epoxy group-containing compound described later. R ² in the chemical formula (B) is a substituent derived from an isocyanate group-containing compound described later.
The substituent (A) and the substituent (B) are each bonded to the oxygen atom of the anionic group.

The epoxy group-containing compound is a compound having one or more epoxy groups in one molecule. In terms of preventing aggregation or gelation, the epoxy group-containing compound is preferably a compound having one epoxy group in one molecule.
An epoxy group containing compound may be used individually by 1 type, and may use 2 or more types together.

  Examples of the monofunctional epoxy group-containing compound having one epoxy group in one molecule include propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, 1, 2-epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monooxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2-epoxy Octadecane, 1,2-epoxyhexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosane, 2- (chloromethyl) -1,2-epoxypropane, glycidol, epichlorohydrin, epib Mohydrin, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2- (chloromethyl) -1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2-epoxy-1H , 1H, 2H, 2H, 3H, 3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclododecane, 1-methyl -1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H, 1H, 2H, 2H, 3H, 3H-hepta Decafluorobutane, 3,4-epoxyte Lahydrofuran, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxy succinic acid, glycidyl phenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, benzyl glycidyl ether, diethoxy (3-glycidyloxypropyl) Methylsilane, 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane, 1,1,1,3,5,5,5-heptamethyl-3- (3-glycidyloxypropyl) trisiloxane, 9,10-epoxy-1,5-cyclododecadiene, glycidyl 4-tert-butylbenzoate, 2,2-bis (4-glycidyloxyphenyl) propane, 2-tert-butyl-2- [2- (4 -Chlorophenyl)] ethyloxy Lan, styrene oxide, glycidyl trityl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α, 6α-epoxide, stilbene oxide, glycidyl p-toluenesulfonate, 3 -Ethyl methyl-3-phenylglycidate, N-propyl-N- (2,3-epoxypropyl) perfluoro-n-octylsulfonamide, (2S, 3S) -1,2-epoxy-3- (tert- Butoxycarbonylamino) -4-phenylbutane, 3-nitrobenzenesulfonic acid (R) -glycidyl, 3-nitrobenzenesulfonic acid-glycidyl, parthenolide, N-glycidylphthalimide, endrin, dialdrin, 4-glycidyloxycarbazole 7,7-dimethyl-octanoic acid [oxiranylmethyl], 1,2-epoxy-4-vinyl cyclohexane, C12, C13 mixed higher alcohol glycidyl ether.

  Examples of the polyfunctional epoxy group-containing compound having two or more epoxy groups in one molecule include 1,6-hexanediol diglycidyl ether, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, 4- Butanediol diglycidyl ether, 1,2: 3,4-diepoxybutane, 1,2-cyclohexanedicarboxylic acid diglycidyl, isocyanuric acid triglycidyl neopentyl glycol diglycidyl ether, 1,2: 3,4-diepoxybutane, Polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Rudiglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin Examples include polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol-based polyglycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, and triglycidyl tris (2-hydroxyethyl) isocyanate.

  The epoxy group-containing compound preferably has a molecular weight of 50 or more and 2,000 or less because of its high solubility in organic solvents, and has a high carbon number because of its high solubility in low polarity organic solvents. 10 or more are preferable.

The isocyanate group-containing compound may be any of a monofunctional isocyanate group-containing compound having one isocyanate group in one molecule and a polyfunctional isocyanate group-containing compound having two or more isocyanates in one molecule.
Examples of the monofunctional isocyanate group-containing compound having one isocyanate group in one molecule include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate and the like. It is done.
Examples of the polyfunctional isocyanate group-containing compound having two or more isocyanate groups in one molecule include dicyclohexylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.
An isocyanate group containing compound may be used individually by 1 type, and may use 2 or more types together.

  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. On the other hand, if the polyanion content is less than or equal to the above upper limit, the amount of anion groups not involved in the dope is moderately suppressed, and can easily be converted to hydrophobicity when an anion group is reacted with an epoxy group-containing compound.

  The content of the conductive composite 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 0.5% by mass to 10% by mass, 1.0 mass% or more and 5.0 mass% or less are more preferable.

(Organic solvent)
Examples of the organic solvent used in this embodiment include hydrocarbon solvents, ketone solvents, alcohol solvents, ester solvents, nitrogen atom-containing compound 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 hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, decane, cyclohexane, and methylcyclohexane. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, and the like.
Examples of the ketone solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, and allyl alcohol.
Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate and the like.
Examples of the nitrogen atom-containing compound solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.

Among the organic solvents, hydrocarbon solvents are preferable in that the wettability of the conductive polymer dispersion with respect to the plastic film substrate is high and the low-polar binder component can be easily solubilized. Of the hydrocarbon solvents, at least one of heptane and toluene is preferred, and heptane is more preferred because of its versatility. Further, when a silicone compound is used as the binder component, at least one of heptane and toluene is preferable because of excellent silicone solubility.
When the organic solvent used in this embodiment contains a hydrocarbon solvent, the content is preferably 50% by mass or more when the total amount of the organic solvent is 100% by mass, and 60% by mass. More preferably. All of the organic solvent may be a hydrocarbon solvent. When a solvent other than the hydrocarbon solvent is contained, the content of the hydrocarbon solvent is preferably 90% by mass or less, and more preferably 80% by mass or less.
In the organic solvent used in this embodiment, it is preferable to contain methyl ethyl ketone since the dispersibility of the conductive composite becomes higher.
When heptane is used as the organic solvent, a solvent other than heptane may be used in combination. As the organic solvent used in combination with heptane, methyl ethyl ketone, toluene, ethyl acetate, butyl acetate, xylene, methyl isobutyl ketone and cyclohexane are preferable.
When the organic solvent contains heptane and a solvent other than heptane, the heptane content is preferably 10% by mass or more and 90% by mass or less when the total amount of the organic solvent is 100% by mass, and 30% by mass or more and 60% or less. It is more preferable that the amount is not more than mass%.

(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 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.

(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, and binder component are not classified as high conductivity agents. However, the epoxy group-containing compound, the isocyanate group-containing compound, and the organic solvent may correspond to the highly conductive agent described here.
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 is composed of a compound other than the aforementioned π-conjugated conductive polymer, polyanion, epoxy group-containing compound, isocyanate group-containing compound, 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 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)
[First production method]
The 1st manufacturing method of the conductive polymer dispersion of this aspect for obtaining the said conductive polymer dispersion has a precipitation collection | recovery process and an isocyanate group containing compound addition process.
Moreover, the 1st manufacturing method of the conductive polymer dispersion liquid of this aspect may further have a washing | cleaning process between a precipitation collection | recovery process and an isocyanate group containing compound addition process. Moreover, you may further have at least one of a 2nd organic solvent addition process and a binder component addition process after an isocyanate group containing compound addition process.

[Deposition recovery step]
The precipitation recovery step is a step of adding an epoxy group-containing 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 group-containing compound is added to the conductive polymer aqueous dispersion, at least a part of the epoxy group of the epoxy group-containing compound reacts with a part of the anion group of the polyanion. As a result, the substituent (A) is formed and the conductive composite becomes hydrophobic, so that it becomes difficult to stably disperse in the aqueous dispersion, resulting in precipitation.
The addition amount of the epoxy group-containing compound is preferably 0.1 or more and 1000 or less, and more preferably 1.0 or more and 100 or less, by mass ratio with respect to the polyanion. If the addition amount of the epoxy group-containing compound is not less than the above lower limit value, the hydrophobicity of the conductive composite will be sufficiently high. it can.
An organic solvent may be added before, at the same time as or after the addition of the epoxy group-containing compound to the conductive polymer aqueous dispersion. 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.

The conductive polymer aqueous dispersion to which the epoxy group-containing 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. The water content in the aqueous dispersion medium is preferably 20% by mass or more, more preferably 50% 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 a polyanion. In addition, 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 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.

[Washing process]
The washing step between the precipitation collection step and the isocyanate group-containing compound addition step is a step of washing the precipitate with a washing organic solvent. By this washing step, residual water, unreacted epoxy group-containing compound, and hydrolyzate of the epoxy group-containing compound are removed.
The organic solvent for cleaning contains an organic solvent having no hydroxy group. An organic solvent having a hydroxy group may react with an epoxy group-containing compound to produce a useless ester. Moreover, when the organic solvent which has a hydroxyl group remains in a deposit, there exists a possibility of reacting with the isocyanate group containing compound used at the next process. Therefore, the organic solvent for washing | cleaning used for this washing | cleaning process contains the organic solvent which does not have a hydroxyl group and has low reactivity with an epoxy group containing compound and an isocyanate group containing compound. The cleaning organic solvent may contain an organic solvent having a hydroxy group. An organic solvent having a hydroxy group is suitable for removing water. When an organic solvent having a hydroxy group is used as the cleaning organic solvent, the residue may react with the isocyanate group-containing compound, so after washing the precipitate with an organic solvent having a hydroxy group, It is preferable to wash with an organic solvent having no hydroxy group.
Moreover, the organic solvent for washing | cleaning uses the thing which can be wash | cleaned, without melt | dissolving a deposit. Therefore, as the cleaning organic solvent, ketone solvents, ester solvents, and nitrogen atom-containing compound solvents are preferable. One organic solvent for cleaning may be used alone, or two or more organic solvents may be used in combination.
The washing method is not particularly limited. For example, the washing may be performed by pouring a washing organic solvent over the deposit, or the deposit is washed by stirring the washing in the washing organic solvent. May be.

[Isocyanate group-containing compound addition step]
The isocyanate group-containing compound addition step is a step of obtaining the first preparation liquid by adding the first organic solvent and the isocyanate group-containing compound to the precipitate.
The first organic solvent and the isocyanate group-containing compound may be added simultaneously to the precipitate, or the isocyanate group-containing compound may be added after the first organic solvent is added.
By adding the isocyanate group-containing compound to the precipitate, the isocyanate group-containing compound can be reacted with the substituent (A) formed by the reaction between the anion group and the epoxy group-containing compound. When the isocyanate group-containing compound is reacted with the substituent (A), the substituent (B) is formed, and the hydrophobicity of the conductive composite becomes higher.
The addition amount of the isocyanate group-containing compound is preferably 0.1 or more and 100 or less, and more preferably 1 or more and 20 or less in terms of mass ratio to the polyanion. If the addition amount of the isocyanate group-containing compound is set to the above lower limit value or more, the hydrophobicity of the conductive composite becomes sufficiently high, and if it is set to the upper limit value or less, the decrease in conductivity due to the unreacted isocyanate group-containing compound is prevented. it can.
In the isocyanate group-containing compound addition step, heating is preferably performed in order to promote the reactivity of the isocyanate group-containing compound. The heating temperature is preferably 40 ° C. or higher and 100 ° C. or lower.

  Although the organic solvent mentioned above can be used as a 1st organic solvent, when it has the 2nd organic solvent addition process mentioned later, it is preferable to use methyl ethyl ketone as a 1st organic solvent. When methyl ethyl ketone is used as the first organic solvent, the dispersibility of the precipitate can be increased in the first preparation liquid, and the dispersibility of the conductive composite in the conductive polymer dispersion obtained by adding the second organic solvent. Can be further improved.

  After adding a 1st organic solvent and an isocyanate group containing compound to a deposit, you may stir the 1st preparation liquid and perform a dispersion process. In particular, when the production method does not include the second organic solvent addition step, it is preferable to perform a dispersion treatment on the first preparation solution. 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 1st manufacturing method of the conductive polymer dispersion liquid of this aspect does not have a 2nd organic solvent addition process, the 1st preparation liquid obtained in the isocyanate group containing compound addition process is conductive polymer dispersion | distribution. Become a liquid.

[Second organic solvent addition step]
The second organic solvent addition step is a step of obtaining a second preparation liquid by adding a second organic solvent different from the first organic solvent to the first preparation liquid. After adding the second organic solvent to the first preparation liquid, it is preferable to stir the second preparation liquid and perform a dispersion treatment. 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 methyl ethyl ketone is used as the first organic solvent, it is preferable to use a hydrocarbon solvent that is a low polarity solvent as the second organic solvent, and since it is highly versatile, at least one of heptane and toluene is used. More preferably it is used.
When the 1st manufacturing method of the conductive polymer dispersion liquid of this aspect has a 2nd organic solvent addition process, the 2nd preparation liquid obtained in the 2nd organic solvent addition process is a conductive polymer dispersion liquid. Become.

[Binder component addition process]
The binder component addition step is a step of adding a binder component to the first preparation liquid or the second preparation liquid. When the second organic solvent addition step is not included, it is preferable to add a binder component to the first preparation liquid. When the second organic solvent addition step is included, the binder component is added to the second preparation liquid. It is preferable.
After adding the binder component to the first preparation solution or the second preparation solution, it is preferable to increase the dispersibility of the binder component by stirring.
When the binder component is addition-curable silicone, it is preferable to add a platinum-based curing catalyst simultaneously with or after the addition of the binder component.

[Addition of highly conductive agents and additives]
In the case where a highly conductive agent, an additive and the like are contained in the conductive polymer dispersion, in any one or more of the isocyanate group-containing compound addition step, the second organic solvent addition step and the binder component addition step, What is necessary is just to add a highly conductive agent, an additive, etc.

[Second production method]
The 2nd manufacturing method of the conductive polymer dispersion of this aspect for obtaining the said conductive polymer dispersion has a drying process and a 1st preparation liquid preparation process.
Moreover, the 2nd manufacturing method of the conductive polymer dispersion liquid of this aspect may further have a washing | cleaning process between a drying process and a 1st preparation liquid preparation process. Moreover, you may further have at least one of a 2nd organic solvent addition process and a binder component addition process after a 1st preparation liquid preparation process. The cleaning step, the second organic solvent addition step, and the binder component addition step in the second manufacturing method are the same as the cleaning step, the second organic solvent addition step, and the binder component addition step in the first manufacturing method.
In this production method, when a highly conductive agent, an additive, or the like is contained in the conductive polymer dispersion, any one of the first preparation liquid preparation step, the second organic solvent addition step, and the binder component addition step In the above steps, a highly conductive agent, additive, etc. may be added.

[Drying process]
The drying step is a step of obtaining a dried conductive composite by drying an aqueous dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion in an aqueous dispersion medium.
As a drying method in the drying step, known methods such as freeze drying, vacuum drying, spray drying, air drying, warm air drying, and heat drying can be applied.
In lyophilization, the water in the conductive polymer aqueous dispersion is frozen and vacuum dried.
The temperature during lyophilization is preferably -60 to 60 ° C, more preferably -40 to 40 ° C. If the lyophilization temperature is equal to or higher than the lower limit, the temperature can be easily adjusted, and if the lyophilization temperature is equal to or lower than the upper limit, the conductive polymer aqueous dispersion can be easily lyophilized.
In vacuum drying, in order to sufficiently volatilize the aqueous dispersion medium, the temperature may be heated to, for example, 40 ° C. or higher after the lyophilization temperature.
In spray drying, the conductive polymer aqueous dispersion is sprayed into a vacuum container to evaporate moisture and dry.
The temperature during spray drying is preferably -20 to 40 ° C, more preferably 0 to 30 ° C. When the spray drying temperature is at least the lower limit, the conductive polymer aqueous dispersion can be easily dried. When the spray drying temperature is at most the upper limit, thermal deterioration of the conductive composite can be prevented.
The moisture content of the dried product obtained by the drying 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.
In order to reduce the amount of water, for example, the drying time may be increased, the drying temperature may be increased, and the degree of vacuum may be increased.

[First Preparation Solution Preparation Step]
A 1st preparation liquid preparation process is a process of adding an epoxy group containing compound and a 1st organic solvent to the said dried material, and also adding an isocyanate group containing compound, and obtaining a 1st preparation liquid.
As a 1st organic solvent, the organic solvent mentioned above can be especially used without a restriction | limiting. In particular, in the present production method, since the dried product contains almost no water, a low polarity solvent such as a hydrocarbon solvent can be used as the first organic solvent, and at least one of heptane and toluene can be preferably used.
The addition of the isocyanate group-containing compound is preferably after the addition of the epoxy group-containing compound and the first organic solvent because it becomes easy to react with the epoxy group-containing compound.
In this step, by adding an epoxy group-containing compound to the dried product, the anion group of the polyanion and the epoxy group-containing compound can be reacted to form the substituent (A). Moreover, a substituent (A) and an isocyanate group containing compound can be made to react after that by adding an isocyanate group containing compound, and a substituent (B) can be formed. During the addition of the epoxy group-containing compound and the isocyanate group-containing compound, heating may be performed to accelerate the reaction. The heating temperature is preferably 40 ° C. or higher and 100 ° C. or lower.
Also in the second production method, the first preparation liquid may be a conductive polymer dispersion, or the second preparation liquid obtained in the second organic solvent addition step may be a conductive polymer dispersion.

(Function and effect)
Since the substituent (A) formed by reacting an anion group of a polyanion with an epoxy group-containing compound, as described in Patent Document 2, is presumed to have a hydroxy group, it is hydrophilic compared to an anion group. Although it is low, it is not low enough. Therefore, the dispersibility of the conductive composite was insufficient for a low polarity organic solvent such as heptane. In this aspect, since the substituent (A) is reacted with the isocyanate group-containing compound to form the substituent (B), the hydrophilicity becomes lower and the lipophilicity (hydrophobicity) can be further improved. The reason is not clear, but when the isocyanate group-containing compound is reacted with the substituent (A), the isocyanate group of the isocyanate group-containing compound reacts with the hydroxy group of the substituent (A), resulting in a urethane bond. To form the substituent (B). The formed substituent (B) is presumed to have improved lipophilicity because the hydroxy group, which is a hydrophilic group contained in the substituent (A), is lost and the chain length is long.
Therefore, according to the conductive polymer dispersion of this embodiment, the dispersibility of the conductive composite in an organic solvent, particularly the dispersibility of the conductive composite in a low polar organic solvent such as heptane can be improved. In a conductive layer formed from such a conductive polymer dispersion, the dispersibility of the conductive composite is increased, so that the conductivity is sufficiently improved despite the use of an organic solvent as a dispersion medium. be able to. In particular, even when a low polarity organic solvent such as heptane is used, the conductivity can be sufficiently improved.
In addition, since the conductive polymer dispersion of this embodiment has high lipophilicity and high wettability with respect to the film substrate, the adhesion of the conductive layer formed from the conductive polymer dispersion can be improved.
In addition, the conductive polymer dispersion of this embodiment can easily dissolve or disperse a binder component, particularly a low-polar organic solvent such as a silicone compound, and can improve the dispersibility of the binder component. When a silicone compound is used as a binder component to make the conductive layer exhibit releasability, the dispersibility is improved because the silicone dispersibility in the conductive layer formed from the conductive polymer dispersion increases. Can be made.

<Method for producing conductive film>
The method for producing a conductive film according to this aspect includes a coating step of coating the conductive polymer dispersion on at least one surface of a film substrate, and a coating film comprising the coated conductive polymer dispersion. And a drying step of drying the (conductive layer).

(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 substituent (B).
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.

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 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.
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.
The thickness of the member in this specification is a value obtained by measuring the thickness at any 10 locations and averaging the measured values.

(Coating process)
Examples of the method for coating the conductive polymer dispersion in the coating step include a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a kiss coater, a fountain coater, a rod coater, and an air doctor. Apply coating methods using coaters such as coaters, knife coaters, blade coaters, cast coaters, screen coaters, spray methods using sprayers such as air spray, airless spray, rotor dampening, dipping methods such as dip, etc. be able to.
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.

(Drying process)
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, 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 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.

(Function and effect)
In the method for producing a conductive film of this aspect, the conductive polymer dispersion of the above aspect having high lipophilicity is applied to a film substrate. Therefore, the conductive layer formed from the conductive polymer dispersion is a film substrate. High adhesion to
In the conductive polymer dispersion of the above aspect, since the conductive composite is highly dispersed in the organic solvent, the conductive composite is also formed in the conductive layer formed from the conductive polymer dispersion. Can be contained in a highly dispersed state. 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 Compound dispersibility can be increased. Therefore, the release property of the conductive layer expressed by the silicone compound can be sufficiently increased.

(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 polystyrene sulfonic acid solution, and about 2000 ml of the 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 obtained 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.
Furthermore, 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% polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS aqueous dispersion) solution. In addition, content of PSS with respect to PEDOT-PSS solid content is 75 mass%.

(Production Example 3)
To 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 300 g of methanol and 25 g of an epoxy group-containing compound (Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd.) are added at 60 ° C. And stirred for 4 hours. As a result, a precipitate of a conductive composite formed from a π-conjugated conductive polymer, a polyanion, and an epoxy group-containing compound was obtained. The precipitate was collected by filtration and washed with 100 g of methanol and then 100 g of ethyl acetate to obtain 1.6 g of a conductive composite.

(Production Example 4)
300 g of methanol and 25 g of 1,2-epoxydecane were added to 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, and the mixture was heated and stirred at 60 ° C. for 4 hours. As a result, a precipitate of a conductive composite formed from a π-conjugated conductive polymer, a polyanion, and an epoxy group-containing compound was obtained. The precipitate was collected by filtration and washed with 100 g of methanol and then 100 g of ethyl acetate to obtain 1.5 g of a conductive composite.

(Production Example 5)
Addition-curable silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KS-3703T, solid content concentration 30% by mass, toluene solution) 1.5 g, toluene 25.5 g, methyl ethyl ketone 58.5 g, and platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.03 g of (CAT-PL-50T) was mixed to obtain a silicone solution (solid content concentration 0.53 mass%).

Example 1
1.6 g of the conductive composite obtained in Production Example 3 was mixed with 100 g of methyl ethyl ketone and 2.0 g of octadecyl isocyanate, and reacted at 80 ° C. for 4 hours with reflux using a condenser. Thereafter, 200 g of heptane was added and stirred for 1 hour, then returned to room temperature and stirred for 16 hours. The prepared solution thus obtained was dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion.
The obtained conductive polymer dispersion was designated as No.1. Using a 12 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-release-type conductive layer to obtain a conductive film.
Further, 14.3 g of the silicone solution obtained in Production Example 5 was mixed with 2.95 g of the obtained conductive polymer dispersion 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 were obtained in the same manner as in Example 1 except that octadecyl isocyanate was changed to butyl isocyanate.

Example 3
A conductive film and a conductive release film were obtained in the same manner except that octadecyl isocyanate was changed to dicyclohexylmethane-4,4′-diisocyanate.

(Example 4)
A conductive film and a conductive release film in the same manner as in Example 1 except that 1.6 g of the conductive composite obtained in Production Example 3 was changed to 1.5 g of the conductive composite obtained in Production Example 4. Got.

(Example 5)
1.6 g of the conductive composite obtained in Production Example 3 was mixed with 100 g of methyl ethyl ketone and 10.0 g of octadecyl isocyanate, and reacted at 80 ° C. for 4 hours while refluxing using a condenser. Thereafter, 200 g of heptane was added and stirred for 1 hour, then returned to room temperature and stirred for 16 hours. The prepared liquid thus obtained was filtered to separate the conductive composite, washed with 100 g of methanol and then 100 g of ethyl acetate to obtain 2.0 g of the conductive composite. 100 g of methyl ethyl ketone and 200 g of heptane were added to the 2.0 g of the conductive composite and dispersed using a high pressure homogenizer to obtain a conductive polymer solution. A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that the conductive polymer dispersion was used.

(Comparative Example 1)
100 g of methyl ethyl ketone and 200 g of heptane were added to 1.6 g of the conductive composite obtained in Production Example 3, and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion. A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that the conductive polymer dispersion was used.

(Comparative Example 2)
100 g of methyl ethyl ketone and 200 g of heptane were added to 1.5 g of the conductive composite obtained in Production Example 4, and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion. A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that the conductive polymer dispersion was used.

<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. In the table, “OVER” means that the measurable upper limit (1.0 × 10 ¹² Ω / □) of the surface resistance value was exceeded.
[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.
The conductive film and conductive release film of each comparative example had a large surface resistance value and low conductivity. Moreover, the electroconductive release film of each comparative example had large peeling force, and the mold release property was low.
In the examples, by reacting the polyanion of the conductive composite with an epoxy group-containing compound and further reacting with an isocyanate group-containing compound, the hydrophobicity of the conductive composite is improved and the conductive composite in an organic solvent is improved. It is estimated that the dispersibility of the body has increased. It is presumed that the dispersibility of the conductive composite in the organic solvent is increased, so that the dispersibility of the conductive composite in the conductive layer is increased and the conductivity is increased. In addition, in the conductive polymer dispersions of the examples, the dispersibility of the low-polarity addition-curable silicone can be increased, so that it is presumed that the release property of the conductive layer has increased.
On the other hand, in the comparative example, since the isocyanate group-containing compound was not reacted after reacting the epoxy group-containing compound with the polyanion of the conductive complex, the hydrophobicity of the conductive complex became insufficient, and the It is presumed that the dispersibility of the conductive composite was not sufficiently high. In the conductive layer of the comparative example formed from the conductive polymer dispersion having low dispersibility of the conductive composite in the organic solvent, the dispersibility of the conductive composite in the layer was low, and the conductivity was low. Guessed. In addition, in the conductive polymer dispersion of the comparative example, the dispersibility of the addition-curable silicone was also low, so it is presumed that the release property of the conductive layer was low.

Claims (19)

a conductive complex containing a π-conjugated conductive polymer and a polyanion, and an organic solvent,
The polyanion further has a substituent (B) formed by reacting an isocyanate group-containing compound with a substituent (A) formed by reaction of a part of an anion group and an epoxy group-containing compound together with an anion group. Polymer dispersion.   The conductive polymer dispersion according to claim 1, wherein the organic solvent contains a hydrocarbon solvent.   The conductive polymer dispersion according to claim 2, wherein a hydrocarbon solvent content in the organic solvent is 50% by mass or more.   The conductive polymer dispersion according to claim 2 or 3, wherein the hydrocarbon solvent is at least one of heptane and toluene.   The conductive polymer dispersion according to any one of claims 1 to 4, wherein the organic solvent contains methyl ethyl ketone.   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 an addition-curable silicone compound. After adding an epoxy group-containing compound 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 depositing the conductive complex to obtain a precipitate A precipitation collection step for collecting the precipitate;
An isocyanate group-containing compound addition step of adding a first organic solvent and an isocyanate group-containing compound to the collected precipitate to obtain a first preparation liquid.   12. The method according to claim 11, further comprising a washing step of washing the precipitate with an organic solvent for washing containing an organic solvent having no hydroxy group between the precipitation collection step and the isocyanate group-containing compound addition step. A method for producing a conductive polymer dispersion.   The method for producing a conductive polymer dispersion according to claim 11 or 12, wherein the first organic solvent is methyl ethyl ketone. a drying step in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is dried in an aqueous dispersion containing an aqueous dispersion medium to obtain a dried conductive composite;
A first preparation liquid preparation step of adding an epoxy group-containing compound and a first organic solvent to the dried product, and further adding an isocyanate group-containing compound to obtain a first preparation liquid. Production method.   The manufacturing method of the conductive polymer dispersion liquid as described in any one of Claims 11-14 which further has a binder component addition process which adds a binder component to a said 1st preparation liquid.   The conductive polymer dispersion liquid according to any one of claims 11 to 15, further comprising a second organic solvent addition step of adding a second organic solvent to the first preparation liquid to obtain a second preparation liquid. Production method.   The method for producing a conductive polymer dispersion according to claim 16, wherein the second organic solvent is a hydrocarbon solvent.   The method for producing a conductive polymer dispersion according to claim 16 or 17, further comprising a binder component addition step of adding a binder component to the second preparation liquid.   The coating process which coats the conductive polymer dispersion according to any one of claims 1 to 10 on at least one surface of the film substrate, and the coated conductive polymer dispersion is dried. The manufacturing method of an electroconductive film which has a drying process.