JP2020097680A - Electroconductive polymer-containing liquid, manufacturing method thereof and manufacturing method of conductive film - Google Patents

Abstract

To provide an electroconductive polymer-containing liquid excellent in dispersion properties of a conductive composite even though using an organic solvent as a dispersant and capable of easily forming a conductive layer excellent in conductivity.SOLUTION: An electroconductive polymer-containing liquid includes: a conductive composite containing a π-conjugated electroconductive polymer and polyanion; and an organic solvent. An anionic group in part of the polyanion includes a substituent group (A) formed through a reaction with an epoxy group-containing compound and a substituent group (B) formed through a reaction with an amine compound. Preferably, the π-conjugated electroconductive polymer is a poly(3,4-ethylenedioxythiophene), and preferably the polyanion is a polystyrene sulfonate.SELECTED DRAWING: None

Description

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

As a coating material for forming the conductive layer, a conductive polymer aqueous dispersion liquid obtained by doping poly(3,4-ethylenedioxythiophene) with polystyrenesulfonic acid may be used.
Usually, the film base material to which the conductive layer is applied is made of a hydrophobic plastic film. Therefore, the conductive polymer aqueous dispersion, which is an aqueous paint, tends to have low adhesion to the film substrate. Further, 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 liquid in which water, which is a dispersion medium of the conductive polymer water dispersion liquid, is replaced with an organic solvent may be used.
The conductive polymer organic solvent dispersion, freeze-dried conductive polymer aqueous dispersion containing a conductive complex consisting of π-conjugated conductive polymer and polyanion to obtain a dried body, the dried body What was 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 liquid containing an amine compound has lower conductivity than a conductive layer formed from a conductive polymer water dispersion liquid, and problems such as a change in color tone. Could occur. In addition, when an addition-curable silicone was blended with the conductive polymer organic solvent dispersion liquid in order to develop releasability in the conductive layer, the addition-curable silicone sometimes caused curing inhibition due to the presence of the amine compound. Therefore, in the conductive polymer organic solvent dispersion liquid using the amine compound, there is a problem that the conductive release film is hard to cure when the addition-curable silicone is blended.

As a measure against the above problem, to a conductive polymer aqueous dispersion containing a conductive complex composed of a π-conjugated conductive polymer and a polyanion, a cyclic ether compound having at least one of an oxirane group and an oxetane group is added, It is known to obtain a conductive polymer organic solvent dispersion liquid (Patent Document 2). In the method described in Patent Document 2, an oxirane group or an oxetane group of a cyclic ether compound is reacted with an anion group that is not doped in a π-conjugated conductive polymer to make it hydrophobic, thereby forming an organic conductive complex. Make it 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 silicone solution may be insufficient. Further, in the conductive layer formed from the conductive polymer organic solvent dispersion liquid described in Patent Document 2, the conductivity may be lowered.
Therefore, an object of the present invention is to provide a conductive polymer-containing liquid which has excellent dispersibility in a silicone solution and can easily form a conductive layer having excellent conductivity, 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 excellent in 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 are contained, and the polyanion comprises an anion group as a part of the polyanion, an epoxy group-containing compound and an amine compound. A conductive polymer-containing liquid that is a reaction product.
[2] The electroconductive polymer-containing liquid according to [1], wherein the organic solvent contains a hydrocarbon solvent.
[3] The conductive polymer-containing liquid according to [2], wherein the content of the hydrocarbon solvent is 50% by mass or more based on the total mass of the organic solvent.
[4] The electroconductive polymer-containing liquid according to [2] or [3], wherein the hydrocarbon solvent is at least one selected from the group consisting of heptane and toluene.
[5] The electroconductive polymer-containing liquid according to any one of [1] to [4], wherein the organic solvent contains methyl ethyl ketone.
[6] The conductive polymer-containing liquid according to any one of [1] to [5], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene).
[7] The electroconductive polymer-containing liquid according to any one of [1] to [6], wherein the polyanion is polystyrene sulfonic acid.
[8] The conductive polymer-containing liquid according to any one of [1] to [7], wherein the epoxy group-containing compound has 7 or more carbon atoms.
[9] The electroconductive polymer-containing liquid according to any one of [1] to [8], wherein the amine compound has a substituent having 6 or more carbon atoms on a nitrogen atom.
[10] The electroconductive polymer-containing liquid according to any one of [1] to [9], which further contains a binder component.
[11] The conductive polymer-containing liquid according to [10], wherein the binder component is a silicone compound.
[12] The conductive polymer-containing liquid according to [11], wherein the silicone compound is an addition-curable silicone.
[13] An epoxy group-containing compound and an amine compound are added to an aqueous dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion in an aqueous dispersion medium, and then the precipitate is recovered. A collection process,
An organic solvent adding step of adding an organic solvent to the precipitate to obtain a preparation liquid, the method for producing a conductive polymer-containing liquid.
[14] The conductive polymer-containing liquid according to [13], further including a cleaning step of cleaning the precipitate with a cleaning organic solvent between the precipitation recovery step and the organic solvent addition step. Production method.
[15] The method for producing a conductive polymer-containing liquid according to [13] or [14], wherein the organic solvent is at least one selected from the group consisting of methyl ethyl ketone, heptane, and toluene.
[16] The method for producing a conductive polymer-containing liquid according to any one of [13] to [15], further including a binder component addition step of adding a binder component to the preparation liquid.
[17] A coating step of applying the conductive polymer-containing liquid according to any one of [1] to [12] to at least one surface of the film substrate, and the coated conductive polymer. And a drying step of drying the contained liquid.

The conductive polymer-containing liquid of the present invention has excellent dispersibility in a silicone solution and can easily form a conductive layer having excellent conductivity.
According to the method for producing a conductive polymer-containing liquid of the present invention, a conductive polymer-containing liquid 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 excellent conductivity can be easily formed.

<Conductive polymer-containing liquid>
The conductive polymer-containing liquid of the present invention contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, and an organic solvent.
In the electroconductive polymer-containing liquid of the present invention, the electroconductive complex may be in a dispersed state or a dissolved state.

(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 it is an organic polymer whose main chain is composed of a π-conjugated system, and examples thereof include polypyrrole-based conductive polymers and polythiophene-based polymers. Conductive polymer, polyacetylene-based conductive polymer, polyphenylene-based conductive polymer, polyphenylene vinylene-based conductive polymer, polyaniline-based conductive polymer, polyacene-based conductive polymer, polythiophene vinylene-based conductive polymer, and These copolymers etc. are mentioned. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable, and polythiophene-based conductive polymers are more preferable from the viewpoint of transparency.

Examples of the polythiophene-based conductive polymer include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), poly(3-hexylthiophene). , Poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly (3-chlorothiophene), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene) , Poly(3-hydroxythiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene) , Poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3 , 4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene) , Poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-didodecyloxythiophene), poly( 3,4-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-carboxy) Butylthiophene).
Examples of the polypyrrole-based conductive polymer include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butyl). Pyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3 -Carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole) , Poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), poly(3-hexyloxypyrrole), and poly(3-methyl-4-hexyloxypyrrole).
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 above π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferable in terms 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 this polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity of the π-conjugated conductive polymer.
The anion group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such a polyanion include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ester having a sulfo group, and polymethacrylic acid ester having a sulfo group (for example, poly(4-sulfobutyl methacrylate). , Polysulfoethylmethacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprenesulfonic acid, and other polymers having a sulfo group, polyvinylcarboxylic acid, polystyrenecarboxylic acid, Examples thereof include polymers having a carboxy group such as polyallylcarboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), and polyisoprenecarboxylic acid, which are homopolymers thereof. It may be a copolymer of two or more kinds.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the polymer can have higher conductivity.
The polyanions may be used alone or in combination of two or more.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, and more preferably 100,000 or more and 500,000 or less.

The polyanion forms a conductive composite by doping the π-conjugated conductive polymer. However, in the polyanion, all anion groups do not dope the π-conjugated conductive polymer and have an excess anion group that does not participate in the doping. Since this surplus anionic group is a hydrophilic group, the conductive composite has high water dispersibility and low organic solvent dispersibility in a state before being reacted with an epoxy group-containing compound or an amine compound as described later.
The surplus anion group in all the anion groups in the polyanion is preferably 30 to 90 mol% and more preferably 45 to 75 mol% with respect to all the anion groups in the polyanion.

The polyanion of the present invention is a reaction product of an excess anion group of the polyanion (hereinafter, also referred to as “a part of anion group”), an epoxy group-containing compound and an amine compound. That is, the polyanion of the present invention includes a substituent (A) formed by the reaction of an epoxy group-containing compound and a part of anion groups, and a substituent (B) formed by a reaction of an amine compound and a part of anion groups. ) And.

(Substituent A)
Although detailed analysis of the conductive composite is not always easy, it is presumed that the substituent (A) is a group represented by the following formula (A1) or a group represented by the following formula (A2).

[In Formula (A1), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom or an arbitrary substituent. ]

[In the formula (A2), m is an integer of 2 or more, and a plurality of R ⁵ , a plurality of R ⁶ , a plurality of R ⁷ , and a plurality of R ⁸ are each independently a hydrogen atom or an arbitrary substituent. A plurality of R ⁵ may be the same or different, a plurality of R ⁶ may be the same or different, a plurality of R ⁷ may be the same or different, and a plurality of R ⁸ may be the same or different. May be. ]

In Formulas (A1) and (A2), the bond at the left end represents that the substituent (A) is substituted with the proton of the anion group. Examples of the anion group having a proton to be substituted include an anion group having an active proton bonded to an oxygen atom such as “—SO ₃ H”.

In formula (A1), as the optional substituents of R ¹ , R ² , R ³ , and R ⁴ , there may be mentioned an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent. Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be possessed. R ¹ and R ³ may be bonded to each other to form a ring which may have a substituent. For example, R ¹ and R ³ are the hydrocarbon group, the divalent hydrocarbon group obtained by removing any one hydrogen atom of a monovalent hydrocarbon group R ^1, a monovalent hydrocarbon of R ³ Examples include a case where a hydrogen atom and a divalent hydrocarbon group excluding any one hydrogen atom are bonded to each other by the carbon atoms excluding the hydrogen atom to form a ring.
In formula (A2), as the optional substituents of R ⁵ , R ⁶ , R ⁷ , and R ⁸ , an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, and a substituent are exemplified. Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be possessed. R ⁵ and R ⁷ may be bonded to each other to form a ring which may have a substituent. Examples of forming a ring are the same as above.
In the present specification, “which may have a substituent” means that a hydrogen atom (—H) is replaced with a monovalent group and that a methylene group (—CH ₂ —) is a divalent group. Including both cases of replacement.
The monovalent group as a substituent includes an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), trialkoxysilyl group. (Trimethoxysilyl group and the like), and the like.
Examples of the divalent group as a substituent include an oxygen atom (-O-), -C(=O)-, and -C(=O)-O-.
m is an integer of 2 or more, preferably 2 to 100, more preferably 2 to 50, and further preferably 2 to 25. When m is at least the above lower limit value, the hydrophobicity of the conductive composite will be sufficiently high. When m is equal to or less than the above upper limit, it is possible to prevent the hydrophobicity from becoming too high and the conductivity from decreasing.

The epoxy group-containing compound is a compound having one or more epoxy groups in one molecule. From the viewpoint of preventing aggregation or gelation, the epoxy group-containing compound is preferably a compound having one epoxy group in one molecule.
The epoxy group-containing compound may be used alone or in combination of two or more.

Examples of the monofunctional epoxy group-containing compound having one epoxy group in one molecule include ethylene oxide, propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide and 1,2-epoxyhexane. , 1,2-epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadienemonooxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1, 2-epoxy octadecane, 1,2-epoxy hexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxy eicosane, 2-(chloromethyl)-1,2-epoxy propane, glycidol, Epichlorohydrin, epibromohydrin, butylglycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2-(chloromethyl)-1,2-epoxybutane, 2-ethylhexylglycidyl 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-epoxycyclo Dodecane, 1-methyl-1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H,1H,2H,2H, 3H,3H-heptadecafluorobutane, 3,4-epoxytetrahydrofuran, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxysuccinic acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxy Norbornene, 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) Ethyl) oxirane, styrene oxide, glycidyl trityl ether, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α,6α-epoxide, stilbene oxide, p-toluenesulfonic acid Glycidyl, ethyl 3-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, dayldrin, 4-glycidyloxycarbazole, 7 , 7-dimethyloctanoic acid [oxiranylmethyl], 1,2-epoxy-4-vinylcyclohexane, higher alcohol glycidyl ether having 10 to 16 carbon atoms, and the like.

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

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 diglycidyl 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 polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol-based Examples thereof include polyglycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, and triglycidyl tris(2-hydroxyethyl)isocyanate.

Since the epoxy group-containing compound has high dispersibility in an organic solvent, it preferably has a molecular weight of 50 or more and 2,000 or less. Further, the epoxy group-containing compound preferably has 7 or more and 100 or less carbon atoms, more preferably 10 or more and 80 or less carbon atoms, and more preferably 15 or more and 50 or less carbon atoms because the dispersibility in a low polar organic solvent is high. More preferred are:

(Substituent B)
Although detailed analysis of the conductive composite is not always easy, it is presumed that the substituent (B) is a group represented by the following formula (B).

^{-HN + R 11 R 12 R 13} ··· (B)
[In the formula (B), R ^{11 to} R ¹³ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, provided that at least one of R ^{11 to} R ¹³ is a substituent. It is a hydrocarbon group which may have. ]

In the substituent (B), the bond at the left end represents that the negative charge of the anion group and the positive charge of the amine compound are bonded. Examples of the anion group that can be negatively charged include anion groups in which an active proton is bound to an oxygen atom, such as “—SO ₃ ⁻ ”.

R ^{11 to} R ¹³ in the chemical formula (B) are a hydrogen atom or a hydrocarbon group which may have a substituent. R ^{11 to} R ¹³ in the chemical formula (B) are substituents derived from the amine compound described later.
The hydrocarbon group in the chemical formula (B) is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Groups.
Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group.
Examples of the substituent of the aliphatic hydrocarbon group include a phenyl group and a hydroxyl group.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
Examples of the substituent of the aromatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group and the like.

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

It is preferable that the amine compound has a substituent having 6 or more carbon atoms on the nitrogen atom, and a substituent having 8 or more carbon atoms on the nitrogen atom, because the dispersibility in a low-polarity organic solvent is high. It is more preferable to have.

In the polyanion, the mass ratio (hereinafter, also referred to as A/B ratio) represented by [substituent (A)]:[substituent (B)] is preferably 10:90 to 90:10, and 20:80 to. 80:20 is more preferable, and 25:75 to 75:25 is further preferable. When the A/B ratio is within the above range, it becomes easy to balance the dispersibility and the conductivity. In addition, the mass of the [substituent (A)] is [(the mass of the reaction product A obtained by reacting the epoxy group-containing compound and the conductive complex)-(the conductivity before the reaction with the epoxy group-containing compound) The mass of the complex)]]. In addition, the mass of the [anion group to which the substituent (B) is bonded] is [(mass of the reaction product B obtained by reacting the reaction product A with an amine compound)-(epoxy group-containing compound and conductive composite). Mass of the reaction product A obtained by reacting with the body)].

The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer, and 10 parts by mass or more and 700 parts by mass or less. Is more preferable, and the range of 100 parts by mass or more and 500 parts by mass or less is further preferable. When the content ratio of the polyanion is not less than the lower limit value, the doping effect on the π-conjugated conductive polymer tends to be strong, and the conductivity becomes higher. On the other hand, when the content of the polyanion is not more than the upper limit value, the amount of the anion group that does not participate in the dope is appropriately suppressed, and when the anion group is reacted with the epoxy group-containing compound, it can be easily converted into hydrophobic.

The content of the conductive composite with respect to the total mass of the conductive polymer-containing liquid is, for example, preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, It is more preferably 1.0% by mass or more and 5.0% by mass or less.

(Organic solvent)
Examples of the organic solvent used in this embodiment include a hydrocarbon solvent, a ketone solvent, an alcohol solvent, an ester solvent, a nitrogen atom-containing compound solvent, and the like. The organic solvents may be used alone or in combination of two or more.
Examples of the hydrocarbon solvent include an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent. Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane and the like. 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 and diacetone alcohol.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, allyl alcohol and the like.
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 above organic solvents, hydrocarbon solvents are preferable because the wettability of the conductive polymer-containing liquid with respect to the plastic film substrate becomes high and the low-polarity binder component can be easily solubilized. Further, among hydrocarbon solvents, toluene is preferable because it is versatile. Further, when a silicone compound is used as the binder component, at least one of heptane and toluene is preferable because the solubility of the silicone compound is excellent.
In the organic solvent used in this embodiment, it is preferable to contain methyl ethyl ketone because the dispersibility of the conductive composite will be higher.

The content of the hydrocarbon solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even 100% by mass with respect to the total mass of the organic solvent. When the content of the hydrocarbon solvent is within the above range, the dispersibility of the conductive polymer can be improved.

(Binder component)
The conductive polymer-containing liquid of this embodiment may contain a binder component in order to improve the film-forming property of the obtained conductive layer.
Since the conductive polymer-containing liquid of this embodiment uses an organic solvent as a dispersion medium, a low-polarity silicone compound can be preferably used as a binder component.

A curable silicone is mentioned as a silicone compound. When the binder component is a curable silicone, the releasability of the conductive layer can be exhibited by curing the curable silicone.
The curable silicone may be either addition curable silicone or condensation curable silicone. In this embodiment, even if an addition-curable silicone is used, curing inhibition hardly occurs, which is preferable.
Examples of the addition-curable silicone include a linear polymer having a siloxane bond and having polydimethylsiloxane having vinyl groups at both ends of the linear chain and hydrogen silane. Such an addition-curable silicone forms a three-dimensional crosslinked structure by an addition reaction and cures. A platinum-based curing catalyst may be used to accelerate the curing.
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 which are dissolved or dispersed in an organic solvent are preferably used.

As the binder component, a thermoplastic resin (for example, polyester), a thermosetting compound (for example, a polyfunctional epoxy compound), or an active energy ray-curable compound (for example, an acrylic compound) other than the silicone compound is used. 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 50,000 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 at least the lower limit value, the strength and hardness of the obtained conductive layer can be sufficiently improved, and when it is at most the upper limit value, sufficient conductivity can be secured.

(High conductivity agent)
The conductive polymer-containing liquid may contain a high conductivity agent in order to further improve the conductivity.
Here, the π-conjugated conductive polymer, organic solvent, polyanion, and binder component described above are not classified as a high-conductivity agent. However, the epoxy group-containing compound and the amine compound 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 hydroxyl groups, a compound having one or more hydroxyl groups and one or more carboxy groups, a compound having an amide group, an imide group It is preferable that it is at least one compound selected from the group consisting of a compound having a lactam compound, a lactam compound and a compound having a glycidyl group.
The highly conductive agent contained in the conductive polymer-containing liquid may be one kind or two or more kinds.
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, and 100 parts by mass with respect to 100 parts by mass of the conductive composite. It is more preferable that the amount is 2,500 parts by mass or more.
If the content ratio of the highly conductive agent is at least the lower limit value, the effect of improving conductivity by the addition of the highly conductive agent is sufficiently exerted, and if it is at most the upper limit value, the π-conjugated conductive polymer concentration decreases. It is possible to prevent a decrease in conductivity due to

(Other additives)
The conductive polymer-containing liquid may contain other known additives.
The additive is not particularly limited as long as the effects of the present invention can be obtained, and for example, a surfactant, an inorganic conductive agent, a defoaming 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 π-conjugated conductive polymer, the polyanion, the epoxy group-containing compound, the ester-forming compound, the binder component, and the highly conductive agent.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and the nonionic surfactant is preferable from the viewpoint of storage stability. Further, a polymer-based surfactant such as polyvinylpyrrolidone 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 defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and the like.
Examples of the coupling agent include a silane coupling agent having a vinyl group or an amino group.
As the ultraviolet absorber, benzotriazole ultraviolet absorber, benzophenone ultraviolet absorber, salicylate ultraviolet absorber, cyanoacrylate ultraviolet absorber, oxanilide ultraviolet absorber, hindered amine ultraviolet absorber, benzoate ultraviolet absorber, etc. Are listed.
When the conductive polymer-containing liquid contains the above-mentioned additive, the content ratio thereof is appropriately determined according to the kind of the additive, and for example, 0. The range can be 001 parts by mass or more and 5 parts by mass or less.

(Method for producing liquid containing conductive polymer)
[First Manufacturing Method]
A first method for producing a conductive polymer-containing liquid of this aspect for obtaining the conductive polymer-containing liquid has a precipitation recovery step and an organic solvent addition step.
Further, the first method for producing a conductive polymer-containing liquid according to this aspect may further include a washing step between the precipitation collecting step and the organic solvent adding step. Moreover, you may further have a binder component addition process after an organic solvent addition process.

[Deposition recovery process]
The precipitation recovery step is a step of adding an epoxy group-containing compound and an amine compound to a conductive polymer aqueous dispersion, depositing a conductive complex to obtain a precipitate, and then collecting the precipitate by filtration. ..
When the epoxy group-containing compound is added to the conductive polymer aqueous dispersion, the epoxy group of the epoxy group-containing compound reacts with a part of the anions 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 it in the aqueous dispersion liquid, and it becomes a precipitate.
When adding the epoxy 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.
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 in terms of mass ratio to the polyanion. If the addition amount of the epoxy group-containing compound is not less than the lower limit value, the hydrophobicity of the conductive composite becomes sufficiently high, and if it is not more than the upper limit value, the decrease in conductivity due to the unreacted epoxy group-containing compound is prevented. it can.
An organic solvent may be added before, simultaneously with, 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. Here, the water-soluble organic solvent is an organic solvent having a solubility of 1 g or more in 100 g of water at a temperature of 20°C. 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 amine compound is added to the conductive polymer aqueous dispersion, the amine compound reacts with a part of the anions of the polyanion. As a result, the substituent (B) is formed and the conductive composite becomes hydrophobic, so that it becomes difficult to stably disperse it in the aqueous dispersion liquid, and it becomes a precipitate.
The addition amount of the amine compound 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, and more preferably 50 parts by mass with respect to 100 parts by mass of the conductive composite. The amount is more preferably 10000 parts by mass or less. When the addition amount of the amine compound is not less than the lower limit value described above, the hydrophobicity of the conductive composite can be sufficiently improved. When the addition amount of the amine compound is not more than the above upper limit value, it is possible to prevent the conductivity of the conductive layer formed from the conductive polymer-containing liquid from decreasing.

In the precipitation recovery step, the order of adding the epoxy group-containing compound and the amine compound is not particularly limited. Since the synthetic intermediate is easy to handle, the epoxy group-containing compound is added to the conductive polymer aqueous dispersion to react with a part of the anion groups of the polyanion, and then the amine compound is added to the polyanion. It is preferable to react with some anionic groups.

The conductive polymer aqueous dispersion liquid is a dispersion liquid 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 is water or a mixed liquid of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents and ester solvents. The water-soluble organic solvent may be used alone or in combination of two or more.
The content of water with respect to the total mass of the aqueous dispersion medium is more than 50% by mass, preferably 60% 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 chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in an aqueous solution of polyanion. Further, as the conductive polymer aqueous dispersion liquid, a commercially available product 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 oxidant can return the reduced catalyst to its original oxidized state.

The water content of the precipitate obtained by the precipitation recovery step is preferably as small as possible, and most preferably contains no water, but from the viewpoint of practical use, the water content may be 10% by mass or less.
Examples of the method of reducing the water content include a method of washing the precipitate with an organic solvent and a method of drying the precipitate.

[Washing process]
The cleaning step between the precipitation recovery step and the organic solvent addition step is a step of cleaning the precipitate with a cleaning organic solvent. By this washing step, residual water, unreacted epoxy group-containing compound, unreacted amine compound, reaction product of epoxy group-containing compound and amine compound, and hydrolysis product of epoxy group-containing compound are removed.
As the organic solvent for washing, those which can be washed without dissolving the precipitate are preferably used. Therefore, the organic solvent for cleaning is preferably a ketone solvent, an alcohol solvent, an ester solvent, or a nitrogen atom-containing compound solvent. The cleaning organic solvent may be used alone or in combination of two or more.
The washing method is not particularly limited, and for example, the precipitate may be washed by pouring a washing organic solvent over the precipitate, or the precipitate may be stirred in the washing organic solvent to wash the precipitate. You may.

[Organic solvent addition process]
The organic solvent adding step is a step of adding an organic solvent to the precipitate to obtain a preparation liquid.
As the organic solvent, the above-mentioned organic solvents can be used, but among them, methyl ethyl ketone, heptane, and toluene are preferably used. When methyl ethyl ketone, heptane, or toluene is used as the organic solvent, the dispersibility of the precipitate in the preparation liquid can be increased.

After adding the organic solvent to the precipitate, the preparation liquid may be stirred and subjected to dispersion treatment. The stirring method is not particularly limited, and stirring with weak shearing force such as a stirrer may be used, or stirring may be performed using a disperser with high shearing force (homogenizer, etc.).

When the first method for producing a conductive polymer-containing liquid of this embodiment does not have the [binder component addition step] described below, the prepared liquid obtained in the organic solvent addition step is a conductive polymer-containing liquid. Become.

[Binder component addition process]
The binder component addition step is a step of adding a binder component to the preparation liquid. In this step, an organic solvent may be added together with the binder component.
After adding the binder component to the preparation liquid, it is preferable to stir it to enhance the dispersibility of the binder component.
When the binder component is an addition-curable silicone, it is preferable to add the platinum-based curing catalyst at the same time as or after the addition of the binder component.

[Addition of high conductivity agent and additives]
When the conductive polymer-containing liquid contains a high-conductivity agent, an additive, etc., the high-conductivity agent, the additive, etc. are added in any one or more of the organic solvent addition step and the binder component addition step. May be added.

[Second manufacturing method]
The second method for producing a conductive polymer-containing liquid of the present embodiment for obtaining the conductive polymer-containing liquid has a drying step and a preparation liquid preparation step.
Further, the second method for producing a conductive polymer-containing liquid of this aspect may further include a washing step between the drying step and the preparation liquid preparation step. In addition, at least one of the binder component addition steps may be further included after the preparation liquid preparation step. The cleaning step and the binder component adding step in the second manufacturing method are the same as the cleaning step and the binder component adding step in the first manufacturing method.
In the present production method, when a conductive polymer-containing liquid is made to contain a highly conductive agent, an additive, etc., it is made highly conductive in any one or more of the preparation liquid preparation step and the binder component addition step. Agents, additives, etc. may be added.

[Drying process]
The drying step is a step of obtaining a dried product of the conductive complex by drying the aqueous dispersion containing the conductive complex containing the π-conjugated conductive polymer and the polyanion in the aqueous dispersion medium.
As the 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 freeze-drying, the water content in the conductive polymer aqueous dispersion is frozen and vacuum-dried.
The temperature during freeze-drying is preferably −60 to 60° C., and more preferably −40 to 40° C. When the freeze-drying temperature is at least the lower limit value, the temperature can be easily adjusted.
In vacuum drying, in order to sufficiently volatilize the aqueous dispersion medium, it may be heated to, for example, 40° C. or higher after the freeze-drying temperature.
In the spray drying, the conductive polymer aqueous dispersion is sprayed into a vacuum container to evaporate water and dry.
The temperature during spray drying is preferably −20 to 40° C., more preferably 0 to 30° C. If the spray-drying temperature is at least the lower limit, the conductive polymer aqueous dispersion can be easily dried, and if it is at most the upper limit, thermal deterioration of the conductive composite can be prevented.
The water content of the dried product obtained by the drying step is preferably as small as possible, and most preferably contains no water at all, but from the viewpoint of practical use, the water content may be 10% by mass or less.
In order to reduce the water content, for example, the drying time may be extended, the drying temperature may be increased, and the degree of vacuum may be increased.

[Preparation liquid preparation process]
The preparation liquid preparation step is a step in which an epoxy group-containing compound, an amine compound, and an organic solvent are added to the dried product and reacted to obtain a preparation liquid.
As the organic solvent, the above-mentioned organic solvents can be used without particular limitation. In particular, in the present production method, since the dried product contains almost no water, a low polar solvent such as a hydrocarbon solvent can be used as the organic solvent, and at least one of heptane and toluene can be preferably used.
In the step, by adding the epoxy group-containing compound to the dried product, a part of the anion group of the polyanion can be reacted with the epoxy group-containing compound to form the substituent (A). When adding the epoxy 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.
In the step, by adding an amine compound to the dried product, a part of the anion groups of the polyanion and the amine compound can be reacted to form the substituent (B).
In the preparation liquid preparation step, the order of adding the epoxy group-containing compound and the amine compound is not particularly limited. Since the synthetic intermediate is easy to handle, an epoxy group-containing compound is added to the dried product to react with a part of the anion groups of the polyanion, and then an amine compound is added to add a part of the polyanion. It is preferred to react with a group.

(Action effect)
According to the electroconductive polymer-containing liquid of this aspect, the polyanion has the substituent (A) and the substituent (B), whereby the dispersibility of the electroconductive complex in the silicone solution is enhanced and the electroconductivity is excellent. A conductive layer can be formed.
Further, since the proportion of the substituent (B) derived from the amine compound can be reduced, it is possible to suppress the inhibition of the effect of the addition-curable silicone when the conductive polymer-containing liquid contains the addition-curable silicone. Thereby, the conductivity at the time of forming the conductive layer can be improved.

<Method for producing conductive film>
The method for producing a conductive film of the present embodiment, a coating step of applying the conductive polymer-containing liquid on at least one surface of the film substrate, and a coating film comprising the coated conductive polymer-containing liquid And a drying step of drying the (conductive layer).

(Conductive film)
The conductive film obtained by the production method of the present embodiment includes a film base material and a conductive layer formed on at least one surface of the film base material. The conductive layer contains a conductive complex containing a π-conjugated conductive polymer and a polyanion. Hydrogen atoms of a part of the anion groups of the polyanion contained in the conductive layer are substituted with the substituent (A) and the substituent (B).
When the conductive polymer-containing liquid contains a binder component, the conductive layer contains 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 10000 nm or less, and further preferably 30 nm or more and 5000 nm or less. When the average thickness of the conductive layer is at least the lower limit value, sufficiently high conductivity can be exhibited, and when the average thickness is at most the upper limit value, the conductive layer can be easily formed.

Examples of the film base material used in the production method of the present embodiment include plastic films and paper.
Examples of the resin for the film substrate that constitutes the plastic film include, for example, 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 Nate and the like. Among these resins for film base materials, polyethylene terephthalate and cellulose triacetate are preferable because they are inexpensive and have excellent mechanical strength.
The resin for a film substrate may be amorphous or crystalline.
The film substrate may be unstretched or stretched.
Further, the film substrate may be subjected to surface treatment such as corona discharge treatment, plasma treatment, and flame treatment in order to further improve the adhesion of the conductive layer formed from the conductive polymer-containing liquid.

The average thickness of the film substrate is preferably 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 at least the above lower limit, it will be difficult to break, and if it is at most the above upper limit, sufficient flexibility can be secured as a film.
The thickness of the member in the present specification is a value obtained by measuring the thickness at arbitrary 10 points and averaging the measured values.

(Coating process)
Examples of the method of applying the conductive polymer-containing liquid in the coating step include, for example, 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 a coating method using a coater such as coater, knife coater, blade coater, cast coater, screen coater, spraying method using a sprayer such as air spray, airless spray, rotor dampening, dipping method etc. be able to.
Of the above, a bar coater may be used because it can be applied easily. In bar coaters, the coating thickness differs depending on the type, and in commercially available bar coaters, numbers are given for each type, and the larger the number, the thicker the coating.
The coating amount of the conductive polymer-containing liquid on 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 the heating and drying, for example, a usual method such as hot air heating or infrared heating can be adopted. When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium used, and can be set to, for example, 50° C. or higher and 150° C. or lower. Here, the heating temperature is the set temperature of the drying device.
When the conductive polymer-containing liquid 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 is performed. You may also have. By including the active energy ray irradiation step, the formation speed of the conductive layer can be increased, and the productivity of the conductive film is improved.
When the method has an active energy ray irradiation step, examples of the active energy ray used include ultraviolet rays, electron beams, and visible rays. As the light source of ultraviolet rays, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used.
The illuminance in ultraviolet 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 amount is preferably 50 mJ/cm ² or more. If the integrated light amount is less than 50 mJ/cm ² , it may not be sufficiently crosslinked. In addition, the illuminance and the integrated light amount in the present specification use UVR-T1 (industrial UV checker, light receiver; UD-T36, measurement wavelength range: 300 nm or more and 390 nm or less, peak sensitivity wavelength: about 355 nm) manufactured by Topcon Corporation. It is the measured value.

(Action effect)
In the conductive polymer-containing liquid of this embodiment, 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-containing liquid. It can be included in the dispersion. Therefore, the conductivity of the conductive layer can be sufficiently increased. Furthermore, since the dispersibility is good, the storage stability of the conductive polymer-containing liquid can be improved.
Further, by having both the substituent (A) derived from the epoxy group-containing compound and the substituent (B) derived from the amine compound, inhibition of curing of the silicone compound by the amine compound can be suppressed. Therefore, the curability is excellent, and the releasability of the conductive layer, which is exhibited by the silicone compound, can be sufficiently increased.

(Production Example 1)
Dissolve 206 g of sodium styrenesulfonate in 1000 ml of ion-exchanged water, add 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water while stirring at 80° C. for 20 minutes, and allow this solution for 12 hours. It was stirred.
1000 ml of sulfuric acid diluted to 10 mass% was added to the obtained sodium styrenesulfonate-containing solution, and about 1000 ml of the solvent of the polystyrenesulfonic acid-containing solution was removed by an ultrafiltration method. Next, 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by an ultrafiltration method, and polystyrene sulfonic acid was washed with water. This water washing operation was repeated 3 times.
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrenesulfonic acid.

(Production Example 2)
A solution of 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrenesulfonic acid dissolved in 2000 ml of ion-exchanged water was mixed at 20°C.
The mixed solution thus obtained was kept at 20° C., 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of an oxidation catalyst solution of ferric sulfate were slowly added while stirring, The reaction was allowed to stir 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 by the ultrafiltration method. This operation was repeated 3 times.
Then, 200 ml of 10% by mass diluted sulfuric acid and 2000 ml of ion-exchanged water were added to the obtained solution, and about 2000 ml of the solvent was removed by the ultrafiltration method. 2000 ml of ion-exchanged water was added to the residual liquid, and about 2000 ml of solution was removed by ultrafiltration. This operation was repeated 3 times.
Further, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solvent was removed by the ultrafiltration method. This operation was repeated 5 times to obtain a 1.2% polystyrenesulfonic acid-doped poly(3,4-ethylenedioxythiophene) (PEDOT-PSS aqueous dispersion) solution. The PSS content based on the PEDOT-PSS solid content was 75% by mass.

(Production Example 3)
To a mixture of 91.7 g of methanol and 183.3 g of isopropyl alcohol, 100 g of the PEDOT-PSS aqueous dispersion liquid obtained in Production Example 2 was added and stirred at 80°C for 5 minutes. Subsequently, 22.5 g of an epoxy group-containing compound (manufactured by Kyoeisha Chemical Co., Ltd., Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether) was added, and a mixed solution of 8.3 g of methanol and 16.7 g of isopropyl alcohol was added. And stirred at 80° C. for 8 hours. Then, the temperature was returned to room temperature, 10 g of tri-n-octylamine was added, and the mixture was stirred for 10 minutes. Thereby, a deposit of a conductive composite having a substituent (A) derived from the epoxy group-containing compound and a substituent (B) derived from the amine compound was obtained. The precipitate was collected by filtration, added with 100 g of isopropyl alcohol, stirred for 30 minutes, and then collected by filtration again for washing. This operation was repeated once. Subsequently, 100 g of heptane was poured and washed to obtain 1.6 g of a conductive composite.

(Production Example 4)
To a mixture of 91.7 g of methanol and 183.3 g of isopropyl alcohol, 100 g of the PEDOT-PSS aqueous dispersion liquid obtained in Production Example 2 was added and stirred at 80°C for 5 minutes. Subsequently, 2.5 g of 1,2-epoxy-4-vinylcyclohexane and 22.5 g of an epoxy group-containing compound (Kyoeisha Chemical Co., Ltd., Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether) were added, and methanol was added. A mixed solution of 8.3 g and isopropyl alcohol 16.7 g was added, and the mixture was stirred at 80° C. for 8 hours. Then, the temperature was returned to room temperature, 10 g of tri-n-octylamine was added, and the mixture was stirred for 10 minutes. Thereby, a deposit of a conductive composite having a substituent (A) derived from the epoxy group-containing compound and a substituent (B) derived from the amine compound was obtained. The precipitate was collected by filtration, added with 100 g of isopropyl alcohol, stirred for 30 minutes, and then collected by filtration again for washing. This operation was repeated once. Then, 100 g of heptane was poured and washed to obtain 1.8 g of a conductive composite.

(Production Example 5)
Addition-curable silicone (KS-3703T, manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration 30% by mass, toluene solution) 1.5 g and toluene 34.5 g, methyl ethyl ketone 7.75 g, heptane 42.75 g, platinum catalyst (Shin-Etsu Chemical Industry Co., Ltd. (CAT-PL-50T) 0.03 g was mixed to obtain a silicone solution (solid content concentration 0.53%).

(Production Example 6)
Addition curable silicone (KS-3703T, manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration 30% by mass, toluene solution) 1.5 g and toluene 34.5 g, methyl ethyl ketone 7.65 g, heptane 41.85 g, platinum catalyst (Shin-Etsu Chemical Industry Co., Ltd. (CAT-PL-50T) 0.03 g was mixed to obtain a silicone solution (solid content concentration 0.53%).

(Production Example 7)
Addition-curing silicone (KS-3703T, manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration 30% by mass, toluene solution) 1.5 g and toluene 33.21 g, methyl ethyl ketone 7.71 g, heptane 43.28 g, platinum catalyst (Shin-Etsu Chemical Industry Co., Ltd. (CAT-PL-50T) 0.03 g was mixed to obtain a silicone solution (solid content concentration 0.53%).

(Production Example 8)
1.5 g of addition-curable silicone (KS-3703T, manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration 30 mass%, toluene solution) and toluene 34.5 g, methyl ethyl ketone 4.5 g, heptane 45 g, platinum catalyst (Shin-Etsu Chemical Co., Ltd. 0.03 g of CAT-PL-50T manufactured by Co., Ltd. was mixed to obtain a silicone solution (solid content concentration 0.53%).

(Example 1)
30 g of methyl ethyl ketone and 70 g of heptane were added to 0.6 g of the conductive composite obtained in Production Example 3, and a dispersion treatment was performed using a high pressure homogenizer to obtain a conductive polymer-containing liquid.
The resulting conductive polymer-containing liquid was Using a bar coater No. 8, a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.) was applied and dried at 150° C. for 2 minutes to form a non-releasing conductive layer to obtain a conductive film.
Further, 17.1 g of the silicone solution obtained in Production Example 6 was mixed with 0.9 g of the obtained conductive polymer-containing liquid to obtain a silicone-containing conductive polymer-containing liquid.
The resulting conductive polymer-containing liquid was 8 bar coater was used to apply to a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.) and dried at 150° C. for 2 minutes to form a release conductive layer, thereby obtaining a conductive release film. ..

(Example 2)
30 g of methyl ethyl ketone and 70 g of heptane were added to 0.6 g of the electroconductive complex obtained in Production Example 4, and dispersion treatment was carried out using a high pressure homogenizer to obtain an electroconductive polymer-containing liquid.
The resulting conductive polymer-containing liquid was Using a bar coater No. 8, a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.) was applied and dried at 150° C. for 2 minutes to form a non-releasing conductive layer to obtain a conductive film.
Further, 17.1 g of the silicone solution obtained in Production Example 6 was mixed with 0.9 g of the obtained conductive polymer-containing liquid to obtain a silicone-containing conductive polymer-containing liquid.
The resulting conductive polymer-containing liquid was 8 bar coater was used to apply to a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.) and dried at 150° C. for 2 minutes to form a release conductive layer, thereby obtaining a conductive release film. ..

(Example 3)
90 g of methyl ethyl ketone, 90 g of toluene and 120 g of heptane were added to 1.8 g of the conductive composite obtained in Production Example 4, and dispersion treatment was performed using a high pressure homogenizer to obtain a conductive polymer-containing liquid.
The resulting conductive polymer-containing liquid was Using a bar coater No. 8, a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.) was applied and dried at 150° C. for 2 minutes to form a non-releasing conductive layer to obtain a conductive film.
Further, 17.14 g of the silicone solution obtained in Production Example 7 was mixed with 0.86 g of the obtained conductive polymer-containing liquid to obtain a silicone-containing conductive polymer-containing liquid.
The resulting conductive polymer-containing liquid was 8 bar coater was used to apply to a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.) and dried at 150° C. for 2 minutes to form a release conductive layer, thereby obtaining a conductive release film. ..

(Comparative Example 1)
165 g of methyl ethyl ketone and 185 g of heptane were added to 1.6 g of a conductive complex obtained in the same manner as in Production Example 3 except that tri-n-octylamine was not added, and a high-pressure homogenizer was used for dispersion treatment to improve the conductivity. A molecule-containing liquid was obtained.
Using the obtained conductive polymer-containing liquid, a conductive film having a non-releasing conductive layer formed thereon was obtained in the same manner as in Example 1.
The obtained conductive polymer-containing liquid was added to the silicone solution obtained in Production Example 5, but the conductive polymer was aggregated without being dispersed. A conductive release film having a release conductive layer was obtained in the same manner as in Example 1 using the conductive polymer-containing liquid containing the aggregate.

(Comparative example 2)
123.8 ml of water was added from 1.25 g of 3,4-ethylenedioxythiophene and 62.5 g of polystyrene sulfonic acid aqueous solution (solid content concentration 10%), and the mixture was stirred at 30° C. for 10 minutes. Subsequently, 0.075 g of ferric sulfate previously dissolved in 12.4 ml of water and 2.75 g of ammonium persulfate dissolved in 22.4 ml of water were added, and the mixture was stirred at 30° C. for 6 hours to obtain PEDOT. A -PSS-containing reaction liquid was obtained.
After adding 75 ml of water to the obtained PEDOT-PSS-containing reaction solution and stirring at 30° C. for 1 hour, 10 g of tri-n-octylamine dissolved in 150 g of isopropyl alcohol was added and stirred at room temperature for 16 hours. By doing so, a deposit of a conductive composite having a substituent (B) derived from an amine compound was obtained.
The precipitate was collected by filtration, added with 250 g of acetone, stirred for 3 hours, and then collected by filtration again for washing. By repeating this operation twice, 4.4 g of a conductive composite was obtained. 140 g of methyl ethyl ketone was added to 0.74 g of the obtained conductive complex, and the dispersion treatment was performed with a high pressure homogenizer to obtain 130 g of a conductive polymer-containing liquid.
Using the obtained conductive polymer-containing liquid, a conductive film was obtained in the same manner as in Example 1.
The obtained conductive polymer-containing liquid was added to the silicone solution obtained in Production Example 8, but the conductive polymer was aggregated without being dispersed. A conductive release film having a release conductive layer was obtained in the same manner as in Example 1 using the conductive polymer-containing liquid containing the aggregate.

(Comparative example 3)
165 g of methyl ethyl ketone and 185 g of heptane were added to 1.6 g of the conductive complex obtained in the same manner as in Production Example 4 except that tri-n-octylamine was not added, and the dispersion was treated with a high pressure homogenizer to obtain a high conductivity. A molecule-containing liquid was obtained. The obtained conductive polymer-containing liquid was added to the silicone solution obtained in Production Example 6, but the conductive polymer was aggregated without being dispersed.

(Comparative Example 4)
123.8 ml of water was added from 1.25 g of 3,4-ethylenedioxythiophene and 62.5 g of polystyrene sulfonic acid aqueous solution (solid content concentration 10%), and the mixture was stirred at 30° C. for 10 minutes. Subsequently, 0.075 g of ferric sulfate previously dissolved in 12.4 ml of water and 2.75 g of ammonium persulfate dissolved in 22.4 ml of water were added, and the mixture was stirred at 30° C. for 6 hours to obtain PEDOT. A -PSS-containing reaction liquid was obtained.
After adding 75 ml of water to the obtained PEDOT-PSS-containing reaction solution and stirring at 30° C. for 1 hour, 10 g of tri-n-octylamine dissolved in 150 g of isopropyl alcohol was added and stirred at room temperature for 16 hours. By doing so, a deposit of a conductive composite having a substituent (B) derived from an amine compound was obtained.
The precipitate was collected by filtration, added with 250 g of acetone, stirred for 3 hours, and then collected by filtration again for washing. By repeating this operation twice, 4.4 g of a conductive composite was obtained. 70 g of methyl ethyl ketone and 70 g of heptane were added to 0.74 g of the obtained conductive composite, and dispersion treatment was carried out with a high pressure homogenizer to obtain 130 g of a conductive polymer-containing liquid.
The obtained conductive polymer-containing liquid was added to the silicone solution obtained in Production Example 5, but the conductive polymer was aggregated without being dispersed.

<Evaluation>
[Measurement of surface resistance]
With respect to the conductive film and the conductive release film of each example, the surface resistance value of the conductive layer was measured under the condition of an applied voltage of 10 V using a resistivity meter (HIRESTA manufactured by Mitsubishi Chemical Analytical Co., Ltd.). The measurement results are shown in Table 1. In Table 1, "NT" means untested.

[Dispersibility]
The state of the silicone-containing conductive polymer-containing liquid after the silicone solution was added to the conductive polymer-containing liquid of each example was visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.
◯: No precipitation was confirmed.
X: Precipitation was confirmed.

[Measurement of peeling force]
The releasability was evaluated by measuring the peeling force in the conductive layer of the conductive release film of each example by the following method.
A 25 mm wide polyester adhesive tape (Nitto Denko Corporation, 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, the adhesive tape attached to the conductive layer was peeled off at an angle of 180° (peeling speed 0.3 m/min) using a tensile tester to give a peeling force (unit: N). It was measured. The measurement results are shown in Table 1. The smaller the peeling force, the higher the releasability of the conductive layer.

The conductive polymer-containing liquid of each example was able to form a conductive film having high conductivity. Further, the conductive polymer-containing liquids of the respective examples exhibited excellent dispersibility in silicone solutions. Furthermore, the silicone-containing conductive polymer-containing liquid of each example was able to form a conductive release film having excellent conductivity.
The conductive polymer-containing liquid of Comparative Example 1 was inferior in dispersibility in a silicone solution. Further, the conductive release film of Comparative Example 1 was inferior in conductivity.
The conductive polymer-containing liquid of Comparative Example 2 was inferior in dispersibility in a silicone solution. Further, the conductive release film of Comparative Example 2 was inferior in conductivity.
The conductive polymer-containing liquids of Comparative Examples 3 and 4 were inferior in dispersibility in a silicone solution.

Claims (17)

Containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, and an organic solvent,
A conductive polymer-containing liquid, wherein the polyanion is a reaction product of a part of anion groups of the polyanion, an epoxy group-containing compound and an amine compound. The electroconductive polymer-containing liquid according to claim 1, wherein the organic solvent contains a hydrocarbon solvent. The conductive polymer-containing liquid according to claim 2, wherein the content of the hydrocarbon solvent is 50% by mass or more based on the total mass of the organic solvent. The conductive polymer-containing liquid according to claim 2, wherein the hydrocarbon solvent is at least one selected from the group consisting of heptane and toluene. The conductive polymer-containing liquid according to any one of claims 1 to 4, wherein the organic solvent contains methyl ethyl ketone. The conductive polymer-containing liquid according to claim 1, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene). The electroconductive polymer-containing liquid according to claim 1, wherein the polyanion is polystyrene sulfonic acid. The electroconductive polymer-containing liquid according to any one of claims 1 to 7, wherein the epoxy group-containing compound has 7 or more carbon atoms. The electroconductive polymer-containing liquid according to claim 1, wherein the amine compound has a substituent having 6 or more carbon atoms on a nitrogen atom. The electroconductive polymer-containing liquid according to claim 1, further containing a binder component. The electroconductive polymer-containing liquid according to claim 10, wherein the binder component is a silicone compound. The electroconductive polymer-containing liquid according to claim 11, wherein the silicone compound is addition-curable silicone. In a water dispersion liquid in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium, after adding an epoxy group-containing compound and an amine compound, a precipitation collecting step of collecting precipitates and ,
An organic solvent addition step of adding an organic solvent to the precipitate to obtain a preparation liquid, the method for producing a conductive polymer-containing liquid. The method for producing a conductive polymer-containing liquid according to claim 13, further comprising a cleaning step of cleaning the precipitate with a cleaning organic solvent between the precipitation recovery step and the organic solvent addition step. The method for producing a conductive polymer-containing liquid according to claim 13 or 14, wherein the organic solvent is at least one selected from the group consisting of methyl ethyl ketone, heptane, and toluene. The method for producing a conductive polymer-containing liquid according to any one of claims 13 to 15, further comprising a binder component addition step of adding a binder component to the prepared liquid. A coating step of coating the conductive polymer-containing liquid according to any one of claims 1 to 12 on at least one surface of the film substrate, and drying the coated conductive polymer-containing liquid. The manufacturing method of a conductive film which has a drying process.